Cobalt-Catalyzed Cross-Coupling Reactions

Chem. Rev.
2010, 110, 14351462
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Cobalt-Catalyzed Cross-Coupling Reactions

Gerard Cahiez* and Alban Moyeux
Department of Chemistry (FRE 3043), CNRS-Universite de Paris 13, 74 Rue Marcel Cachin, F-93017 Bobigny, France
Received February 28, 2009
Contents
1. Introduction
2. Homocoupling Reactions
3. Csp2-Csp2 Cross-coupling Reactions
3.1. Alkenylation
3.1.1. From Aromatic Organomagnesium
Reagents
3.1.2. From Vinylic Grignard Reagents
3.1.3. From Aryl Halides and Alkenyl Acetates
3.2. Aryl-Aryl Cross-coupling
3.2.1. From Aromatic Organometallic Reagents
3.2.2. From Two Aromatic Halides
4.1. Alkenylation
4.1.1. From Aliphatic Organometallic Reagents
4.1.2. From Aliphatic Halides
4.2. Arylation
4.2.2. From Aromatic Halides
4.3. Allylation of Aromatic Organometallics
5. Alkynylation
5.1. Pioneering Works
5.2. Benzylation of Acetylenic Grignard Reagents
5.3. Alkylation of Acetylenic Grignard Reagents
5.4. Alkenylation of Acetylenic Grignard Reagents
6. Csp3-Csp3 Cross-coupling
6.1. Allylation
6.1.1. Allylation of Aliphatic Organozinc
Compounds
6.1.2. Alkylation of Allylic Grignard Reagents
6.1.3. Allylation of Trimethylsilylmethylmagnesium
Chloride
6.1.4. Allylation of Allylic Grignard Reagents
6.2. Benzylation
6.3. Alkylation
7. Acylation
7.1. From Organometallic Compounds
7.2. Cobalt-Mediated Acylation of Aryl Bromides
8. Reductive Cyclization and Heck-Type Reactions
8.1. Radical Cyclization
8.1.1. Intramolecular Radical Cyclization
8.1.2. Cyclization via an Intermolecular Radical
Addition
8.2. Cobalt-Catalyzed Heck-Type Reactions
9. Miscellaneous Reactions
9.1. Cobalt-Mediated Michael Addition
* E-mail: gerard.cahiez@univ-paris13.fr.
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9.2. Allylation of 1,3-Dicarbonyl Compounds

9.3. Activation of C-H Bonds: C-N Coupling
Reactions
9.4. Three-Component Reactions
9.4.1. Synthesis of -Acetamido Ketones
9.4.2. Synthesis of Homoallylsilanes
9.5. Coupling of Alkenes and Alkynes
9.6. Various Reactions
10. Conclusion
11. Acknowledgments
12. References
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1. Introduction
Since the pioneering work of Kharasch1 on the metalcatalyzed homocoupling reaction of aromatic Grignard
reagents (see 2) in the middle of the 20th century, cobaltcatalyzed carbon-carbon bond-forming reactions have received particular attention.2 The scope of these reactions is
different from that of the palladium- and nickel-mediated
procedures. Thus, cobalt-catalyzed cross-coupling reactions
are very efficient for the elaboration of Csp2-Csp2 bonds (see
section 2), but they are especially interesting for couplings
involving alkyl halides, since the decomposition by -hydrogen elimination of alkyl-cobalt intermediates is not a
limitation as in the case of palladium or nickel catalyzed
reactions (see sections 3, 4, and 5). Cobalt-mediated acylations, radical cyclizations, and Heck-type reactions have also
been described (see sections 6 and 7). All these reactions
will be discussed hereafter.
It is worthy of note that cobalt salts have also been
extensively used as catalysts for Pauson-Khand3 and hydroformylation4 reactions but also for the cyclopropanation5 of
olefins and for [2 + 2 + 2]6 and [2 + 2]7 cycloaddition
reactions. These reactions will not be discussed herein.
2. Homocoupling Reactions
The first reports on cobalt-catalyzed cross-coupling reactions describe the homocoupling reaction of Grignard
reagents. In 1939, Gilman and Lichtenwalter8 obtained nearly
quantitative yields of homocoupling product by treating
aromatic Grignard reagents with a stoichiometric amount of
cobalt chloride. In 1941, Kharasch1 discovered that good
yields of homocoupling products are obtained by using only
catalytic amounts (i.e., 3 mol %) of cobalt chloride and a
stoichiometric amount of an oxidant such as aromatic or
aliphatic halides (Scheme 1). The role of this latter is to
oxidize the Cobalt(0) species into a cobalt(II) species after
the reductive elimination step.
Twenty years later, in 1962, Morizur applied the Kharasch
reaction to the synthesis of various biaryls.9a The yields are
10.1021/cr9000786 2010 American Chemical Society

Published on Web 02/11/2010
1436 Chemical Reviews, 2010, Vol. 110, No. 3
Cahiez and Moyeux

Scheme 1. The Kharasch Reaction
Gerard Cahiez received his Ph.D. in 1973, at the University Pierre &
Marie Curie (Paris VI), under the supervision of Professor Jean Francois
Normant, on the carbocupration of terminal alkynes (vinyl copper reagents).
Then, he joined the CNRS. After a postdoctoral year in the Roussel Uclaf
Laboratories (now Sanofi Aventis) on the chemistry of steroid, he came
back to the University Pierre and Marie Curie, and in 1980, he became
Director of Research at the CNRS. Then, he moved to the Ecole
Superieure de Chimie Organique et Minerale (ESCOM, Cergy-Pontoise)
in 1993. From 1993 to 2008 he was Director of Research at the CNRS
and Professor of Chemistry at ESCOM. From 2000 to 2009, he was also
Director of the UMR 8123, a joint research unit CNRS-University of Cergy
Pontoise-ESCOM. In 2009, he moved to the University of Paris 13, as
Director of Research at the CNRS, to create a new research group in
organometallic chemistry. The research developed since 1973 dealt with
the use of organometallic reagents in organic synthesis and especially
with the development of the chemistry of organomanganese reagents.
His current interest is always focused on organomanganese chemistry
but more generally on the search for new highly selective organometallic
reactions, i.e., Mn-, Co-, and Fe-catalyzed cross-coupling reactions,
involving no toxic and expensive metal or additive.
Scheme 2. Cobalt-Catalyzed Homocoupling Reaction of

Aromatic Grignard Reagents

3.1. Alkenylation
3.1.1. From Aromatic Organomagnesium Reagents
Alban Moyeux was born in La Bassee (France) in 1982. He obtained his

B.Sc. Degree from the University of Lens in 2004. He obtained his M.Sc.
Degree from the University of Cergy-Pontoise in 2005. He then worked
on iron- and cobalt-catalyzed cross-coupling reactions under the supervision of Professor Gerard Cahiez and was awarded his Ph.D. Degree in
November 2008. He finally joined the group of Professor Alois Furstner
as a postdoctoral fellow at the Max-Planck Institute of Mulheim (Germany),
where he is currently working on total synthesis.
significantly lower than those previously reported by Kharasch. Almost identical results were obtained by using butyl
bromide (Scheme 2) or bromobenzene (Table 1) as an
oxidant.
It should be underlined that aryllithium and arylmagnesium
compounds give similar yields9b (Table 1).
Interestingly, benzylic or homobenzylic Grignard reagents
can also be used (Table 1, entries 6-10).
In 1943, Kharasch described the first cobalt-catalyzed

alkenylation of aromatic Grignard reagents10 (Table 2).
The very reactive vinyl or 1-propenyl halides give moderate yields (Table 2, entries 1-3) whereas sterically hindered
or more substituted alkenyl halides only afford very poor
results. Large amounts of homocoupling products are then
obtained from both alkenyl halide and aryl Grignard reagent
(Table 2, entries 4-6). The synthetic interest of this reaction
is limited, since, even in the best cases, 2 equiv of alkenyl
halides are used.
In 1982, Uemura reported the cross-coupling reaction
between aryl Grignard reagents and alkenyl tellurides under
cobalt catalysis11 (Scheme 3).
Yields are quantitative, but a large excess of Grignard
reagent is used (2.5 equiv). It should be underlined that a
substantial amount of homocoupling product (biaryl) is
formed as a side product. This is a clear drawback, since
the purification of the final product is often tricky.
In 1998, Cahiez reinvestigated the cobalt-catalyzed alkenylation of aromatic Grignard reagents.12 A clear improvement was observed by using a THF/NMP mixture as a
solvent (Table 3). Thus, various alkenyl halides have been
coupled stereospecifically in good to excellent yields (Table
3, entries 1-5).
Very recently, Hayashi13 described the cobalt-catalyzed
coupling between alkenyl triflates and aryl Grignard reagents.

Table 1. Cobalt-Catalyzed Homocoupling Reaction of
Aryllithium and Arylmagnesium Halides
Chemical Reviews, 2010, Vol. 110, No. 3 1437

Scheme 3. Cross-coupling between Alkenyl Tellurides and
Table 3. Cobalt-Catalyzed Alkenylation of Aromatic Grignard

Reagents in the Presence of NMP
Table 2. Cobalt-Catalyzed Alkenylation of Aromatic Grignard

Reagents
Scheme 4. Cobalt-Catalyzed Cross-coupling between

Alkenyl Triflates and Aromatic Grignard Reagents
3.1.2. From Vinylic Grignard Reagents
The coupling takes place under mild conditions (Scheme 4).

The presence of NMP is not necessary, but PPh3 is used as
a ligand.
This method can be complementary to the precedent
method using alkenyl bromides, since vinyl triflates can be
easily prepared from the corresponding ketones.
Until now, there have only been very few cobalt-catalyzed

alkenyl-alkenyl cross-coupling reactions. In 1998, Cahiez12
described one example of cobalt-catalyzed cross-coupling
between an alkenyl halide and an alkenyl Grignard reagent
(Scheme 5) in moderate yield. The reaction is stereospecific
and gives only the pure trans-diene.
Recently, Hayashi13 described the cobalt-catalyzed crosscoupling between alkenyl triflates and alkenyl Grignard
reagents. Good yields are obtained from R-monosubstituted

Scheme 5. Cobalt-Catalyzed Coupling between
Styrylmagnesium Bromide and 2-Methyl-1-bromopropane
Cahiez and Moyeux

Scheme 7. Cross-coupling between Chloropyridines and
Isopropenyl Acetate

Alkenylmagnesium Halides and Alkenyl Triflates
Scheme 8. Mechanism Proposal for the Cobalt-Catalyzed

Alkenylation of Aryl Halides by Vinyl Acetates
Table 4. Cobalt-Catalyzed Coupling between Functionalized

Aryl Halides and Alkenyl Acetates
1-6). However, in some cases, aryl chlorides lead to better

yields (2- and 4-halobenzonitriles, entries 7-8 and 13-14).
Aryl iodides such as 4-iodoanisole and ethyl 4-iodobenzoate are not suitable substrates, since they lead essentially
to a mixture of reduced and homocoupling products.
The reaction was extended to halopyridines (Scheme 7).
A mechanistic pathway was proposed (Scheme 8). In the
first step, CoII is reduced by manganese powder in the
presence of pyridine either in CoI or in Co0. In a precedent
work, Perichon demonstrated that CoI is stabilized by vinylic
acetate in an acetonitrile/pyridine mixture.15 The low-valent
cobalt species formed is probably coordinated by the vinyl
acetate. It then undergoes an oxidative addition of the aryl
halide to give an arylcobalt species. This species could
then react with vinylic acetate according to a six-membered
transition state [A]. After reductive elimination, cobalt is
reduced by the excess of Mn0 to regenerate the active cobalt
species.
or R,- and ,-disubstituted alkenyl Grignard reagents
(Scheme 6).
3.2. Aryl-Aryl Cross-coupling
3.1.3. From Aryl Halides and Alkenyl Acetates
In 1983, Uemura described the cross-coupling between

diaryltellurides (Ar2Te) and aromatic organomagnesium
reagents in the presence of cobalt salts11 (Scheme 9).
The reaction affords poor yields, and a substantial amount of
homocoupling product accruing from the Grignard reagent is
produced. The purification of the final product is thus often delicate.
In 2003, Knochel and Cahiez reported the cross-coupling
between heteroaryl chlorides and aryl- or heteroarylmagnesium halides16 (Scheme 10).
In 2005, Perichon reported the cobalt-catalyzed coupling

between functionalized aryl halides and alkenyl acetates. It
is the only example of a cobalt-catalyzed arylation of enol
esters. The reaction is performed by using a catalytic amount
of cobalt bromide (5%) in the presence of 10 equiv of
manganese (Table 4).14
Moderate to good yields are obtained. As a rule, aryl
chlorides or bromides give similar results (Table 4, entries
3.2.1. From Aromatic Organometallic Reagents

Scheme 9. Cross-coupling between Diaryltellurides and

Nonactivated Aryl Halides or Heteroaryl Bromides and
Scheme 10. CoCl2-Catalyzed Cross-coupling between

Heteroaryl Chlorides and Aromatic or Heteroaromatic
Grignard Reagents

Functionalized Arylcyanocuprates and ortho-Bromo or
ortho-Chloro Aromatic Ketones, Esters, or Aldehydes
Scheme 11. Cobalt or Iron Powder-Mediated Aryl-Aryl

Coupling Reactions
Yields are excellent in most cases. Noteworthy, the

influence of steric hindrance is not very important. Thus,
the reaction between mesitylmagnesium chloride and 1-chloroisoquinoline leads to 85% of coupling product. Two
equivalents of Grignard reagent are required.
Interestingly, cobalt or iron powders are suitable catalysts
for the reaction16 (Scheme 11).
One year later, Oshima16b reported a very similar reaction.
The coupling is achieved in dioxane in the presence of
cobalt(II) acetylacetonate whereas diethyl ether and cobalt(II)
chloride were used in the previous method16a (Scheme 10).
Yields are comparable, but 3 equiv of phenyl magnesium
bromide are used instead of 2 and the amount of catalyst is
twice higher.
The above examples were performed by using heteroaromatic
or actived aromatic halides. Very recently, Nakamura17 described a cobalt-catalyzed cross-coupling reaction from
nonactivated aryl chlorides or heteroaryl bromides and
aromatic Grignard reagents (Scheme 12). The reaction is
performed in the presence of cobalt(II) fluoride and NHC
ligand.
Then, Knochel has shown that the chemoselective coupling

between polyfunctional aryl- or heteroarylcyanocuprates
ArCu(CN)MgCl and ortho-bromo or ortho-chloro aromatic
ketones, esters, or aldehydes can be performed under cobalt
catalysis.18 Numerous polyfunctional biaryls were successfully synthesized according to this methodology. Selected
examples are presented in Scheme 13.
To react the starting halide completely, it is essential to
perform the coupling in the presence of Bu4NI (1 equiv) and
4-fluorostyrene (20 mol %) by using a large excess of
cyanoarylcuprate (3 equiv).19 The use of a THF/DME/DMPU
mixture instead of THF as a solvent clearly accelerates the
reaction (15 min instead of 21 h).

Scheme 14. Cobalt-Catalyzed Reaction of
p-Anisylcyanocuprates with o-, m-, and
p-Bromobenzophenones
Cahiez and Moyeux

Scheme 17. Cobalt-Catalyzed Coupling Reaction between
Arylcyanocuprates and Pentafluorobenzophenone
Scheme 18. Synthesis of Unsymmetrical Biaryl Compounds

by Coupling Two Aryl Halides under Cobalt Catalysis
Heteroarylcyanocuprates and Activated Aryl Bromides
Table 5. Cobalt-Catalyzed Coupling of Two Aryl Halides:

Influence of the Nature of the Aryl Halides

Activated Aryl Fluorides or Tosylates and
Arylcyanocuprates
a
Isolated yield. b Yields in parentheses refer to GC yield.
Scheme 19. Cobalt-Catalyzed Coupling Reaction between

-Bromostyrene and Methylmagnesium Iodide
The yields are significantly lower when the activating

carbonyl group is in the meta or the para position (Scheme
14).
Heteroarylcyanocuprates can also be used successfully
(Scheme 15).
The reaction has been extended to ortho-fluoro aromatic
ketones, esters, or aldehydes20 (Scheme 16). The corresponding tosylates also react successfully. This is worthy of note,
since the use of aryl fluorides21 and tosylates22 in metalcatalyzed cross-coupling reactions is not usual. As a rule,
good to excellent yields are obtained.
With pentafluorobenzophenone, the two fluorine atoms in
the ortho-positions can be selectively substituted (Scheme
17). However, yields are moderate and 6 equiv of arylcyanocuprate are required.
successfully (Table 5, entry 7). It should be underlined that

a significant amount of homocoupling product is produced
during the reaction. This is a practical drawback, since the
expected product could then be very tricky to isolate.
3.2.2. From Two Aromatic Halides
Very recently, Gosmini reported the synthesis of unsymmetrical biaryl compounds by coupling two aromatic halides
ArX and ArX under cobalt catalysis23 (Scheme 18). The
use of 2 equiv of the more reactive aryl halide is generally
required to obtain satisfactory yields of cross-coupling
products.
Similar results were obtained from aryl iodides, bromides,
or chlorides (Table 5). Interestingly, aryl triflates also react
Scheme 20. Influence of NMP on the Cobalt-Catalyzed

Alkenylation of Grignard Reagents
4.1. Alkenylation
4.1.1. From Aliphatic Organometallic Reagents
In 1945, Kharasch24 showed that the coupling between
methyl magnesium iodide and -bromostyrene takes place
in good yield in the presence of cobalt chloride (Scheme
19).

Scheme 21. Cobalt-Catalyzed Alkenylation of Grignard
Reagents: Stereospecificity of the Reaction

Scheme 22. Chemoselective Cobalt-Catalyzed Alkenylation
of Grignard Reagents
Scheme 23. Synthesis of (E)-1-Alkenyl Chlorides from

(E)-Dichloroethylene
Table 6. Cobalt-Catalyzed Coupling between Alkenyl Halides

and Aliphatic Grignard Reagents
Scheme 24. Cobalt-Catalyzed Alkenylation of Functionalized

Organozinc Halides
Scheme 25. Cobalt-Catalyzed Alkenylation of Benzylzinc

Bromide
However, the method is limited to the very reactive

-bromostyrene, and 2 equiv of Grignard reagent are
necessary.
In 1998, Cahiez discovered that the use of N-methylpyrrolidone (NMP) as a cosolvent allows a dramatic improvement (Scheme 20; see also section 3.1). The yields are clearly
better, and only 1.1 equiv of Grignard reagent is required.12
Alkenyl iodides, bromides, and chlorides give good yields
of cross-coupling product (Scheme 21).
It is important to note that the reaction is stereospecific
(Scheme 21).
The procedure has been applied to the synthesis of various
olefins (Table 6).
Good yields are obtained by coupling primary (Table 6,
entries 1-3) or secondary (entries 4-5) aliphatic Grignard
reagents with various alkenyl bromides. It is noteworthy that
tertiary aliphatic Grignard reagents give poor results (entry
6).
The reaction is highly chemoselective. Thus, the presence
of an ester or even a keto group is tolerated (Scheme 22).
Finally, it should be underlined that (E)-1,2-dichloroethylene reacts to give only the corresponding (E)-alkenyl
chlorides. The formation of the product resulting from a
substitution of both chlorine atoms is not observed (Scheme
23). This result is in sharp contrast with that obtained under
iron catalysis, since, in this case, the double substitution

product is formed exclusively.25
Cahiez and Knochel then extended the reaction to alkylzinc
halides.26 These reagents are less reactive than the corresponding organomagnesium halides, and the coupling takes
place slowly at a higher temperature (55 C, 4-8 h). In
addition, 20-30 mol % of catalyst and a large excess of
organozinc halide (3 equiv) are necessary. As with Grignard
reagents,12 the reaction is chemoselective and stereospecific.
Good yields of cross-coupling product are obtained (Scheme
24).
It is worthy of note that benzylic organozinc halides can
be coupled with alkenyl iodides (Scheme 25).
The coupling of various silylated Grignard reagents with
1,2-dihalogenoethylenes was also reported (Table 7).27
Excellent yields are obtained from trimethylsilylmethylmagnesium chloride (Table 7, entries 1 and 3) or phenyldimethylsilylmethylmagnesium chloride (Table 7, entry 2). As
previously reported by Cahiez,12 the formation of the
disubstituted products was not observed. It is noteworthy that
stereodifferentiation between (E)- and (Z)-1,2-dihaloethylenes
is possible. Thus, by reacting a mixture of (E)- and (Z)-1,2dibromoethylenes (5 equiv) with trimethylsilylmethyl magnesium chloride, the only product is the (E)-1-bromoalkene
(Table 7, entry 3).

Table 7. Cobalt-Catalyzed Selective Coupling between
1,2-Dihalogenoethylenes and PhMe2SiCH2MgCl or
Me3SiCH2MgCl
Cahiez and Moyeux

Table 9. Cross-coupling between Primary or Secondary Alkyl
Halides and 1-(Trimethylsilyl)ethenylmagnesium Bromide
a
a
5 equiv of 1,2-dibromoethylene was used.
Table 8. Cobalt-Catalyzed Cross-coupling between Alkenyl

Halides and Silylated Grignard Reagents
The trans isomer was formed exclusively.
Table 10. Tandem Radical Cyclization and Cross-coupling

Reaction
The reaction was performed at 35 C.
Scheme 26. Cobalt-Catalyzed Alkylation of

Styrylmagnesium Bromide
Later, the cross-coupling between alkenyl halides and

dimethylalkylsilylmethylmagnesium chlorides was reported
by Oshima.28 Good to excellent yields are obtained (Table
8).
R- or -monosubstituted as well as ,-bisubstituted
alkenyl iodides, bromides, or chlorides afford good yields
(entries 1-6). On the other hand, R,-bisubstituted alkenyl
halides only lead to poor results (entry 7).

29
In 2006, Oshima described the reaction between octyl

bromide and styrylmagnesium bromide in the presence of 5
mol % cobalt chloride and N,N,N,N-tetramethyl-1,2-cyclohexanediamine as a ligand (Scheme 26).
The same year, he reported the cobalt-catalyzed crosscoupling between various alkyl halides and 1-(trimethylsilyl)ethenylmagnesium bromide by using TMEDA as a sol-
a
Diastereomeric ratio. b The product was isolated as a lactone after
oxidation of the cyclic acetal.
vent.30 Good to excellent yields are obtained from either

primary or secondary alkyl halides, but a large excess of
organometallic reagent (4 equiv) has to be used and the
reaction seems limited to this specific Grignard reagent
(Table 9).
From -unsaturated alkyl iodides 1, a cyclic product is
formed via a radical cyclization followed by a cross-coupling
reaction (Table 10). The mechanism proposed by Oshima is
depicted in Scheme 27. Thus, various heterocyclic compounds have been synthesized in good to excellent yields.
4.2. Arylation
The first example of cobalt-catalyzed arylation of a Csp3
center was described in 1969. In this report, Hey31 noted
that the yield of the reaction between 2-bromopyridine and
methylmagnesium iodide is clearly improved in the presence
of catalytic amounts of cobalt(II) chloride (Scheme 28).

Scheme 27. Mechanism for Tandem Radical Cyclization and
Cross-coupling Reaction
Scheme 28. First Cobalt-Catalyzed Arylation of Aliphatic

Grignard Reagents

Table 11. Tandem Radical Cyclization and Cross-coupling
Reaction from Unsaturated Haloacetal 2
Isolated yield. The diastereomeric ratio is given in parentheses.
Scheme 29. Heck-Type Reaction from Unsaturated

Haloacetals 3 and 4
However, the reaction is not general and very poor yields

are obtained in most other cases.
In 2001, Oshima32 described the cobalt-catalyzed tandem
radical cyclization and arylation reaction from ethylenic
haloacetal 2 (Table 11). This methodology has been applied
to the synthesis of heterocyclic (entries 1-7) and carbocyclic
(entry 8) compounds. It should be noted that the yield clearly
depends on both the position and the number of substituents
on the substrate (entries 4 and 6). The mechanism proposed
in this case is similar to the one described in Scheme 27.
It is noteworthy that when the double bond of the starting
product is not terminal (haloacetals 3 and 4, Scheme 29)
the arylation product is not obtained. In this case, the reaction
leads to a Heck-type product (see section 9).
In 2006, this reaction was successfully applied to the
synthesis of oxasilacyclopentanes (Scheme 30).33
These compounds can easily be converted into 4-aryl-1,3diols by Tamao-Fleming oxidation.34 This approach has
been used in a synthesis of an antagonist of human CCR5
receptor (Scheme 31).
The same year, Oshima described the cross-coupling
between primary alkyl halides and aromatic Grignard
reagents in the presence of CoCl2(dppp).35 Selected examples
are presented in Table 12. It must be underlined that a large
excess of Grignard reagent is required (3 equiv). As a rule,
moderate yields are obtained from primary alkyl bromides
whereas the corresponding iodides give low yields (entries
1 and 2). Moreover, secondary cyclic alkyl bromides such
as cyclohexyl bromide lead to poor results (entry 4) and alkyl
chlorides do not react.
Scheme 30. Synthesis of Oxasilacyclopentanes
Heteroaromatic organomagnesium compounds can be used

successfully (entry 5). The reaction is sensitive to steric
hindrance; thus, ortho-substituted aryl Grignard reagents do
not afford the expected cross-coupling product (entry 6).
Interestingly, some functional groups such as an ester or an
acetal are tolerated (entries 7 and 8).
Oshima has finally shown29 that better results are obtained
by using a diamine (N,N,N,N-tetramethyl-1,2-cyclohexanediamine) as a ligand instead of dppp (Table 13).
Moreover, only a slight excess (1.2 equiv) of Grignard

Scheme 31. Synthesis of an Antagonist of Human CCR5
Receptor
Cahiez and Moyeux

Table 13. Cobalt-Catalyzed Cross-coupling between Primary or
Secondary Alkyl Halides and Aromatic Grignard Reagents
Table 12. Cobalt-Catalyzed Cross-coupling between Primary

Alkyl Halides and Aromatic Grignard Reagents
Scheme 32. Synthesis of AH13205
Only 3-chloropropylbenzene is formed.
reagent is then used. With this catalytic system, the yields

are significantly higher from primary alkyl iodides than from
the corresponding bromides (entries 3 and 4). In addition,
secondary cyclic and acyclic alkyl halides (entries 1 and 2)
can also be used successfully. Finally, the reaction is less
sensitive to steric hindrance; as an example, ortho-tolylmagnesium bromide leads to an excellent yield (entry 7).
The reaction is highly chemoselective, and various halogenoesters were coupled successfully (entries 9-11).
This methodology has been applied to the synthesis of
AH13205, a synthetic prostaglandin used as an EP2-receptor
agonist that lowers intraocular pressure (Scheme 32).36
The reaction of five- and six-membered cyclic halo acetals
5 having a stereogenic center in the R position of the C-Br
bond has been examined (Scheme 33). The stereoselectivity
of this reaction is highly dependent on the size of the ring.
Thus, good enantioselectivity was only obtained with the
five-membered cyclic acetal.
Very recently, Cahiez37 described the cobalt-catalyzed
cross-coupling between primary or secondary alkyl bromides
and aromatic organomagnesium compounds. A cheap and

simple catalytic system, cobalt(III) acetylacetonate/TMEDA
(1:1), is used. This is very interesting, since commercial
TMEDA is a very simple and inexpensive starting material
compared to the N,N,N,N-tetramethyl-1,2-cyclohexanediamine previously employed by Oshima.29
It is possible to couple secondary alkyl bromides with
excellent yields, whereas, under the conditions described by
Oshima,29 alkyl bromides lead to clearly lower yields than
alkyl iodides. This point is very interesting, since alkyl

Scheme 33. Cobalt-Catalyzed Stereoselective Arylation of
Cyclic Haloacetals 5

Table 15. Cross-coupling of Aryl Grignard Reagents with
Functionalized Primary Alkyl Bromides
Table 14. Cobalt-Catalyzed Cross-coupling between Aliphatic

Bromides and Aromatic Grignard Reagents
Scheme 34. Cobalt-Catalyzed Chemoselective Arylation of

Functionalized Secondary Alkyl Bromides
Scheme 35. Cobalt-Catalyzed Cross-coupling between Aryl

Bromides and Alkyl Grignard Reagents
bromides are cheaper and more stable than the corresponding

iodides. Results are summarized in Table 14.
As a rule, excellent yields are obtained from primary and
secondary alkyl Grignard reagents (entries 1-8). On the other
hand, tertiary alkyl bromides cannot be used (entry 9). It
should be underlined that only a slight excess (1.1 equiv) of
Grignard reagent was used. Alkyl iodides and bromides lead
to similar results (entries 3-4) whereas alkyl chlorides or
tosylates only afford poor yields (entry 5).
The reaction is not very sensitive to steric hindrance, and
it is possible to couple an ortho-substituted aromatic Grignard
reagent with a secondary alkyl bromide in high yields (entry
8).
The reaction is highly chemoselective (Table 15). Thus,
1-bromo-5-chloropentane couples selectively to give the
corresponding alkyl chloride in good yield (entry 1). In
addition, the presence of various sensitive groups such as
an acetate (entry 2), an ester (entry 3), an amide (entry 4),
or even a ketone (entry 5) is tolerated.
The reaction is also highly chemoselective in the case of
secondary alkyl bromides (Scheme 34). It is the first report
of a metal-catalyzed cross-coupling between an aromatic
Grignard reagent and a functionalized secondary alkyl
bromide.
4.2.2. From Aromatic Halides

In 2008, Oshima38 described the cobalt-catalyzed coupling
between aryl bromides and aliphatic Grignard reagents
(Scheme 35). It is the only report in this field. This reaction
is an interesting alternative to the related palladium or nickel
procedures.
Yields are generally good to excellent; however, this
reaction can only be applied to primary alkyl Grignard
reagents.

Scheme 36. Cobalt-Catalyzed Coupling between Allyl
Acetate and Functionalized Aryl Bromides
Cahiez and Moyeux

Scheme 38. Cobalt-Catalyzed Cross-coupling between 1- and
3-Phenyl-2-propenyl Methyl Ethers and Phenylmagnesium
Bromide
Scheme 39. Cobalt-Catalyzed Arylation of Allylic Acetals
Scheme 37. Cobalt-Catalyzed Coupling between Allyl

Acetate and Functionalized Aryl Chlorides

2-Bromo-1-phenylacetylene and Methylmagnesium Bromide

Phenylethynylmagnesium Bromide and Phenylethynyl Iodide
4.3. Allylation of Aromatic Organometallics

In 2003, Perichon reported the coupling of aryl halides with allyl
acetates in the presence of a catalytic amount of cobalt bromide;
zinc is used as a reductant.39
Moderate yields were obtained from various aryl bromides
(Scheme 36). It should be noted that the presence of an ester
or a nitrile is tolerated. This method is complementary to
the cobalt-catalyzed electrochemical methods previously
reported.40
The reaction can also be achieved with aryl chlorides
(Scheme 37), but the reaction conditions are very different.
It is necessary to increase the amount of cobalt bromide (40%
instead of 20%), zinc dust has to be replaced by manganese
dust as a reductant, and the presence of pyridine as well as
a stoichiometric amount of iron bromide is required. Moreover, the coupling is performed at a higher temperature
(50 C), and the reaction time is longer (24 h). However,
yields are generally better than those previously obtained
from the corresponding aryl bromides.
In 2004, Oshima41 described the reaction between allylic
ethers and phenylmagnesium bromide in the presence of
cobalt salts. Good yields were obtained, but the reaction is
not regioselective, excepted with 1- and 3-phenyl-2-propenyl
methyl ethers (Scheme 38).
Under similar conditions, allylic acetals lead to the
monosubstitution product (Scheme 39).
Table 16. Cobalt-Catalyzed Alkynylation of Various Grignard

Reagents
the presence of cobalt chloride (Scheme 40). It is the first

example of cobalt-catalyzed alkynylation of Grignard reagents.
A few years later, the cobalt-catalyzed coupling between
phenylethynylmagnesium bromide and phenylethynyl iodide
was reported (Scheme 41).43 A satisfactory yield of diphenylbutadiyne was obtained.
In 1954, several examples of coupling between aliphatic,
aromatic, or acetylenic Grignard reagents and 1-haloalkynes
were reported by Weedon.44 As a rule, only poor yields were
obtained (Table 16).
5. Alkynylation
5.1. Pioneering Works
In 1945, Kharasch42 reported the coupling between methylmagnesium bromide and 2-bromo-1-phenylacetylene in
5.2. Benzylation of Acetylenic Grignard Reagents

In 2006, Oshima reported the benzylation of acetylenic
Grignard reagents under cobalt catalysis.45 Moderate to
excellent yields are obtained (Table 17).

Table 17. Cobalt-Catalyzed Benzylation of Alkynylmagnesium
Halides
Scheme 42. Preparation of Diynes from

1,2-Bis(bromomethyl)- or 1,3-Bis(chloromethyl)benzene

Table 18. Cobalt-Catalyzed Tandem Radical Cyclization and
Alkynylation Reaction
a
Diastereomeric ratio. b The product was isolated as a lactone after
oxidation of the cyclic acetal.
Scheme 44. Cobalt-Catalyzed Tandem Radical Cyclization

and Alkynylation Reaction

Primary or Secondary Alkyl Bromides and
1-Trimethylsilylethynylmagnesium Bromide
Trimethylsilylethynylmagnesium bromide reacts with benzylic chlorides or bromides to give good yields of crosscoupling products (entries 1-4, R ) Me3Si). On the other
hand, only benzylic bromides lead to good results from
1-hexynylmagnesium bromide (entry 1, R ) n-Bu).
With 1,2-bis(bromomethyl)- or 1,3-bis(chloromethyl)benzene, the double substitution is possible and the reaction
affords diynes (Scheme 42).
5.3. Alkylation of Acetylenic Grignard Reagents

Recently, Oshima reported the reaction between alkyl
halides and trimethylsilylethynylmagnesium bromide in the
presence of cobalt chloride.29 Satisfactory yields are obtained
from primary or secondary alkyl halides (Scheme 43), but a
large excess of Grignard reagent is used.
-Haloalkenes 6 react with trimethylsilylethynylmagnesium
bromide according to a tandem radical cyclization and cross-
coupling reaction. Various heterocyclic compounds have thus

been synthesized in moderate to good yields (Table 18).
Oshima46 showed that simple acetylenic Grignard reagents
can also be used (Scheme 44).
However, it is important to note that 5 equiv of Grignard
reagent have to be used in this case.
5.4. Alkenylation of Acetylenic Grignard Reagents

The cobalt-catalyzed coupling between alkynylmagnesium
halides and alkenyl triflates was described by Hayashi in
2007.47 Good to excellent yields are obtained from a wide
range of substrates (Scheme 45).
Some examples of chemoselective couplings in the presence of an alkenyl, an alkyl, or an aryl bromide are described
(Table 19). It is noteworthy that no additional ligand was
used in this case.

Scheme 45. Cobalt-Catalyzed Coupling between Alkenyl
Triflates and Alkynyl Grignard Reagents
Cahiez and Moyeux

Scheme 47. Cobalt-Catalyzed Coupling between Diethyl
Cinnamyl Phosphate and Dipentylzinc
Table 20. Cobalt-Catalyzed Coupling between Unactivated

Alkyl Halides and Allylmagnesium Chloride
Table 19. Chemoselective Cobalt-Catalyzed Alkenylation of

Acetylenic Grignard Reagents
trans/cis ) 86:14. b dppe was used as a ligand.
Scheme 48. Cobalt-Catalyzed Alkylation of Crotyl- and

Prenylmagnesium Chlorides
Scheme 46. Cobalt-Catalyzed Allylation of Diorganozinc
Compounds
6. Csp3-Csp3 Cross-coupling
6.1. Allylation
6.1.1. Allylation of Aliphatic Organozinc Compounds
In 1996, Knochel48 described the allylation of organozinc
compounds (R2Zn or RZnX) under cobalt catalysis (Scheme
46).
It should be pointed out that both R groups from R2Zn
are transferred. Moreover, only the SN2 substitution
products are obtained. Dialkylzincs and alkylzinc halides
give similar yields, but the latter require longer reaction
times (about 5 h at -10 C).
Allylic phosphates can also be used successfully (Scheme
47).
6.1.2. Alkylation of Allylic Grignard Reagents

The coupling between unactivated alkyl halides and
allylic Grignard reagents in the presence of cobalt chloride
and dppp was described by Oshima in 2002 (Table 20).49

Good yields are obtained under mild conditions from primary
(entry 1), secondary (entries 2 and 3), or tertiary (entries 4
and 5) alkyl halides. Benzylic halides can also be used (entry
6).
With substituted allylic Grignard reagents, the regioselectivity is very dependent on the structure of the allylic
moiety. A mixture of products resulting from an alkylation
on the less and the more substituted sides of the allylic
system is generally obtained (Scheme 48).
A tandem radical cyclization and cross-coupling reaction
was used to prepare various cyclic compounds in good to
excellent yields (Scheme 49). For the mechanism of the
reaction, see Scheme 27.
Unexpectedly, by using ether as a solvent, a cyclopropane
derivative is formed (Scheme 50).
The following mechanism is proposed. At first, cobalt
chloride is converted to an active reduced species [Con]
by action of the Grignard reagent. After a single electron
transfer to the halide (formation of a radical anion) and
then cleavage of the C-I bond, a radical is obtained.
Sequential 5-exo radical cyclization and trapping of the
resulting radical by the catalytic cobalt species then afford
the cobalt intermediate 10. In diethyl ether, 10 undergoes
Scheme 49. Cobalt-Catalyzed Tandem Radical Cyclization

and Alkylation of Allylic Grignard Reagents
Scheme 52. Cobalt-Catalyzed Cross-coupling between 1- and

3-Phenyl-2-propenyl Methyl Ethers and
Trimethylsilylmethylmagnesium Chloride
Scheme 50. Mechanism of the Cobalt-Catalyzed Reaction of

-Iodoallylic Acetal 9 with Allylmagnesium Chloride
Scheme 53. Cobalt-Catalyzed Coupling of Allylic Acetals

with Trimethylsilylmethylmagnesium Chloride
Scheme 51. Cobalt-Catalyzed Reaction of -Iodoallylic

Acetal 9 with Crotyl- and Prenylmagnesium Chlorides

Allylmagnesium Bromide and Cinnamyl Methyl Ether
Scheme 55. Cobalt-Catalyzed Benzylation of

4-Acetoxybutylzinc Iodide
a rapid elimination of BuO-Metal (Metal ) Co or Mg) to

give the cyclopropane derivative 11. Such an elimination
probably involves the complexation of the metallic center
of 10 (Co or Mg) with the oxygen atom of the butoxy
group (in THF, this complexation is much more difficult
and the elimination does not occur). The resulting aldehyde 11 then reacts with allylmagnesium chloride to afford
the alcohol 12.
The reaction was extended to prenyl- or crotylmagnesium
chlorides (Scheme 51).
6.1.3. Allylation of Trimethylsilylmethylmagnesium

Chloride
The coupling between allylic ethers and trimethylsilylmethylmagnesium chloride under cobalt catalysis was reported
in 2004.41 As with phenylmagnesium bromide (see section
4.3), good yields and selectivity are obtained from 1- and
3-phenyl-2-propenyl methyl ethers (Scheme 52). However,
the reaction is generally not regioselective with the other
allylic ethers.
It is noteworthy that, from allylic acetals 13 (Scheme 53),
it is possible to substitute one or two methoxy groups by
using respectively 1.5 or 3 equiv of Grignard reagent.
6.1.4. Allylation of Allylic Grignard Reagents

A cobalt-catalyzed coupling reaction between allylic
Grignard reagents and allylic ethers has been described by
Oshima (Scheme 54).41
Good yields are obtained. Interestingly, the regioselectivity
of the reaction can be easily controlled by changing the
nature of the catalyst. Thus, only the linear substitution
product 14 is formed in the presence of uncomplexed cobalt
chloride whereas the branched substitution product 15 is the
main isomer when the complex CoCl2dppp is used.
6.2. Benzylation
An example of cobalt-catalyzed benzylation of an organozinc compound (Scheme 55) was reported by Knochel
in1996.48
In 2004, Oshima achieved the coupling between secondary
alkyl halides and benzylic Grignard reagents in the presence
of CoCl2dppp. As a rule, yields are moderate (Table 21).49
Tertiary alkyl iodides also react but lead to poor yields (entry
7).

Table 21. Cobalt-Catalyzed Alkylation of Benzylic Grignard
Reagents
Cahiez and Moyeux

Table 23. Cobalt-Catalyzed Alkyl-Alkyl Coupling Reaction:
Effect of Iodide Anion on the Course of the Reaction
Entry
Catalytic system (5 mol %)
Yield (%)
1
2
3
4
5
CoCl2
CoCl2; 4TMEDA
CoCl22LiCl; 4TMEDA
CoCl22LiBr; 4TMEDA
CoCl22LiI; 4TMEDA
traces
35
27
30
79
Table 24. Cobalt-Catalyzed Coupling between Unactivated

Alkyl Halides and Aliphatic Grignard Reagents
3 equiv of Grignard reagent was used.
Table 22. Cobalt-Catalyzed Tandem Radical Cyclization and

Alkylation Reaction of Various -Iodo Ethylenic Compounds
with RMe2SiCH2MgCl
Diastereomeric ratio.
6.3. Alkylation
In 2007, Oshima reported the tandem radical cyclization
and cross-coupling reaction of various -halogeno ethylenic
compounds with RMe2SiCH2MgCl under cobalt catalysis.46
N-Heterocyclic carbenes are employed as ligands. As a rule,
good yields are obtained under mild conditions. Selected
examples are shown in Table 22.
Very recently, Cahiez described the cross-coupling between functionalized alkyl halides and aliphatic Grignard
A mixture of decane and 1-decene was mainly obtained.
reagents in the presence of the ate complex CoCl22LiI.50

TMEDA is used as a ligand.
By using cobalt chloride as a catalyst, only traces of crosscoupling product are obtained (Table 23, entry 1). In the
presence of TMEDA, the yield is better but remains
unsatisfactory (entry 2). Finally, the best results are obtained
by adding both TMEDA and lithium iodide (entry 5). It is
the first example of such a beneficial influence of iodide
anion on the course of a cobalt-catalyzed cross-coupling
reaction.
Various alkyl-alkyl couplings were performed under these
conditions (Table 24). Acyclic or cyclic secondary alkyl
bromides (entries 1-8) gave moderate to good yields of
cross-coupling product. It is important to note that the
influence of steric effects is determinant. Thus, 2-bromopentane gave a better yield than 3-bromopentane (entries 5 and
6). Similarly, the results obtained with various 2-bromoalkanes clearly depend on the length of the alkyl chain (entries
1, 3, and 7). It is possible to use alkyl iodides in place of
bromides, but the corresponding chlorides do not react
(entries 2-4).
The reaction has been successfully extended to primary
alkyl bromides (entries 9 and 10). On the other hand, tertiary
alkyl bromides do not react (entry 11). Finally, it should be
noted that secondary or tertiary alkyl Grignard reagents
cannot be used (entries 12 and 13).
The reaction is chemoselective (Table 25), thus, an ester
(entries 1 and 2), a nitrile (entry 3), or even a keto group
(entry 4) are tolerated. It should be underlined that func-

Table 25. Cobalt-Catalyzed Coupling between Functionalized
Alkyl Halides and Aliphatic Grignard Reagents
Scheme 56. Cobalt-Catalyzed Chemoselective Alkyl-Alkyl

Coupling Reaction from Functionalized Secondary Alkyl
Halides
Scheme 57. Cobalt-Catalyzed Acylation of Methyl- and

Phenylmagnesium Bromides
tionalized secondary alkyl halides can also be used successfully (Scheme 56).
It is the first example of chemoselective alkyl-alkyl
coupling from a functionalized secondary alkyl bromide.
7. Acylation
7.1. From Organometallic Compounds
In 1943, Kharasch showed that methyl- or phenylmagnesium bromides react with mesitoyl chloride in the presence
of cobalt chloride to give the expected ketones in moderate
yields (Scheme 57).51 It is the first report of a cobalt-catalyzed
acylation of organometallic compounds.
Fifty years later, Knochel showed that diorganozincs react
with carboxylic acid chlorides in the presence of cobalt
bromide in a THF/NMP mixture as a solvent (Scheme 58).48
Excellent yields are obtained with aromatic and aliphatic
carboxylic acid chlorides as well as with oxalyl chloride and
trifluoroacetic anhydride. It is however important to note that
three equivalents of diorganozinc compound have to be used
(i.e., 6 equiv of organometallic reagent).

Scheme 58. Cobalt-Catalyzed Acylation of Diorganozincs
Table 26. Cobalt-Mediated Reaction between Aryl Bromides

and Carboxylic Acid Anhydrides
Entry
Aryl bromide
Yield (%)
1
2
3
4
5
6
7
8
9
10
11
12
13
14
p-MeO-C6H4Br
p-MeO-C6H4Br
p-MeO-C6H4Br
p-NC-C6H4Br
p-NC-C6H4Br
p-NC-C6H4Br
p-EtO2C-C6H4Br
p-EtO2C-C6H4Br
p-EtO2C-C6H4Br
p-F-C6H4Br
p-F3C-C6H4Br
m-MeO-C6H4Br
m-NC-C6H4Br
m-F3C-C6H4Br
Me
n-Bu
Ph
Me
n-Bu
Ph
Me
n-Bu
Ph
Me
Me
Me
Me
Me
67
79
46
54
76
30a
62
78
33b
69a
61a
72
34b
71a
10 mol % CoBr2 was used. b 7.5 mol % CoBr2 was used.
Various para- (entries 1-11) or meta-substituted (entries

12-14) functionalized aryl bromides react successfully. As
a rule, aliphatic acid anhydrides give good results whereas
aromatic acid anhydrides only lead to moderate yields (entries
3, 6, and 9).
8. Reductive Cyclization and Heck-Type

Reactions
8.1. Radical Cyclization
It is well-known that various cobalt(II) complexes react
with alkyl or aryl halides via a halogen atom transfer to lead
to the corresponding alkyl or aryl radicals.53,54 Cyclization
via an inter- or an intramolecular trapping of the radical thus
generated provides an easy access to various cyclic
compounds.
8.1.1. Intramolecular Radical Cyclization
7.2. Cobalt-Mediated Acylation of Aryl Bromides

The cobalt-mediated synthesis of aromatic ketones from
aryl bromides and carboxylic acid anhydrides was reported
by Perichon52 in 2004 (Table 26). The reaction is performed
in the presence of a catalytic amount of cobalt bromide by
using a stoichiometric amount of zinc as a reductant.
8.1.1.1. Radical-Mediated Aryl-Aryl Coupling. Cobaltcatalyzed reductive cyclization has been reported for the first
time by Tiecco55 in 1965 (Scheme 59).
8.1.1.2. From -Halogeno Acetylenic Compounds. In
1982, Tada56 reported the reductive cyclization of 2-propargyloxyalkyl bromides in the presence of bis(dimethylgly-
Cahiez and Moyeux
Scheme 59. Cobalt-Catalyzed Cyclization via a

Radical-Mediated Aryl-Aryl Coupling
Scheme 61. Cobaloxime(I)- or Vitamin B12-Catalyzed

Radical Cyclization of 2-Allyloxyalkyl Bromides
Table 27. Cobaloxime(I)-Catalyzed Reductive Cyclization of

2-Propargyloxyalkyl Bromides
Entry
R1
R2
Yield (%)
1
2
3
4
5
Ph
Ph
Ph
H
H
Ph
Me
H
-(CH2)4-(CH2)3-
H
H
H
64
48
85
73
78
Scheme 62. Radical Cyclization Catalyzed by

Cobalt(I)-Salen
Table 28. Radical Cyclization Catalyzed by Cobalt(I)-Salen:

Influence of the Nature of the Reducing System on the Outcome
of the Reaction
* Cobaloxime(I) ) [bis(dimethylglyoximato)(pyridine)cobalt(I)].
Scheme 60. Cobaloxime(I)-Catalyzed Reductive Cyclization

of Halogeno Propargyl Acetals 16
Ratio 19/20 (yield %)

Reaction conditions
oximato)(pyridine)cobalt(I), generally called cobaloxime(I),

by using a stoichiometric amount of sodium borohydride as
a reductant. Results are reported in Table 27.
Good yields of exomethylenefuranes are obtained from
primary alkyl halides (entries 1-3). Cyclic alkyl halides lead
to bicyclic compounds in satisfactory yields (entries 4 and
5).
In 1989, Hoffmann57 applied the reaction to the synthesis
of various heterocyclic compounds (Scheme 60).
8.1.1.3. From -Halogeno Ethylenic Compounds. In
1984, Pattenden58 described the radical cyclization of 2-allyloxyalkyl bromides using cobaloxime or Vitamin B1259
as a catalyst under the conditions described by Tada (Table
27) for 2-propargyloxyalkyl bromides.56 The organocobalt
species resulting from the cyclization undergoes a -hydrogen elimination to give a bicyclic product in good yields
(Scheme 61).
A few years later, Jones60 reported a similar reaction
catalyzed by a cobalt-salen complex. A mixture of saturated
and unsaturated products 17 and 18 is obtained in all cases
(Scheme 62).
Thereafter, Giese61 showed that it is possible to form
selectively the saturated or the unsaturated products 19 and
20 by changing the reaction conditions (Table 28).
Entry
20 mol % catalyst,
Zn, DMF, h
1
2
H
Ph
81/19(80)
99/1 (90)
1 mol % catalyst,
Zn/NH4Cl, DMF
1/99(80)
3/97(88)
Scheme 63. Tandem Radical Cyclization and Michael

Addition Reaction
Interestingly, the radical (or the organocobalt species)

obtained after the cyclization step can be trapped by using a
reactive Michael acceptor such as an acrylic ester (Scheme
63).61
In 1994, Jones62 performed the reductive cyclization of
ortho-amidoiodobenzenes 21 in moderate to good yields in
the presence of cobalt chloride by using methylmagnesium
iodide as a reductant (Scheme 64). A large amount of catalyst
is required (50 mol %).

Scheme 64. Cobalt-Catalyzed Radical Cyclization of
ortho-Amidoiodobenzenes 21

Table 29. Cobalt-Catalyzed Carbocyclization of ortho-Iodoaryl
Ketones and Aldehydes with Alkynes
Scheme 65. CoCl2dppb-Catalyzed Radical Cyclization of

-Halogeno Ethylenic Compounds
It is possible to lower the amount of catalyst by using a

complex cobalt CoCl2(dppb). Thus, Oshima63 achieved the
radical cyclization of -halogeno ethylenic compounds in
the presence of CoCl2(dppb) by using trimethylsilylmethylmagnesium chloride as a reductant (Scheme 65). Various
cyclopentane derivatives were prepared in good yields.
8.1.2. Cyclization via an Intermolecular Radical Addition

In 2003, Cheng64 reported the reaction of various oiodoaryl ketones and aldehydes with alkynes or conjugated
alkenes in the presence of CoI2dppe and a stoichiometric
amount of zinc as a reductant. The cyclization reaction
proceeds via a tandem carbometalation and intramolecular
1,2-addition to the ketone.
Such a reaction had been previously described under
palladium65 or nickel66 catalysis. Nevertheless, the cobaltcatalyzed reaction gives higher yields and better regioselectivities under milder conditions. In addition, the reaction
times are shorter (Table 29).
Good to excellent yields are obtained from o-iodoaryl
ketones (Table 29, entries 1-5) or aldehydes (entries 6-9).
When unsymmetrical alkynes are used, a mixture of two
regioisomers 22 and 23 is obtained (entries 2 and 7).
Interestingly, with trimethylsilylpropyne or ethyl trimethylsilylpropiolate, the regioselectivity is excellent, since only
compound 22 is formed (entries 3-5 and 8).
A similar reaction takes place by using various acrylic
esters instead of alkynes (Table 30).
It is noteworthy that it is possible to perform a threecomponent reaction between o-iodobenzaldehyde, p-toluidine, and alkynes to form heteroatom-substituted derivatives67
(Scheme 66).
8.2. Cobalt-Catalyzed Heck-Type Reactions

The Heck reaction68,69 is a powerful tool for the
elaboration of carbon-carbon bonds. However, the reaction still suffers some limitations. Thus, the use of alkyl
halides having hydrogen(s) atom(s) in the -position to
the halide atom leads to poor results, since the intermediate
catalytic alkylpalladium species undergoes a very fast
Ratio 22/23.
Table 30. Intermolecular Cyclization of ortho-Iodoaryl Ketones

and Aldehydes with Acrylic Esters
-hydrogen elimination. Interestingly, the cobalt-catalyzed

Heck type reaction is complementary to the classical
palladium-catalyzed reaction, since it allows avoidance
of this drawback.
In 1991, Branchaud70 reported the first cobalt-catalyzed
Heck-type reaction between styrene and various alkyl halides
(Table 31) in the presence of cobaloxime(II) and a stoichiometric amount of zinc as a reductant. It should be noted that
exposure to daylight is necessary.

Scheme 66. Cobalt-Catalyzed Three-Component Cyclization
Reaction
Table 31. Cobaloxime-Catalyzed Heck-Type Reaction
Cahiez and Moyeux

Table 32. CoCl2(dpph)-Catalyzed Heck-Type Reaction
Scheme 67. Cobalt-Catalyzed Diastereoselective Heck-Type

Reaction
Scheme 68. Mechanism of the CoCl2(dpph)-Catalyzed

Heck-Type Reaction
Primary (Table 31, entries 1-3 and 6) and secondary

(entry 4) alkyl bromides lead to moderate yields whereas
the reaction failed with tertiary alkyl bromides (entry 5).
Later, Oshima reported that excellent yields were obtained
by using CoCl2dpph as a catalyst and trimethylsilylmethylmagnesium chloride as a reducing agent (Table 32).71a
Primary (Table 32, entries 1-3), secondary (entries 4-5
and 8-10), and even tertiary (entry 6) alkyl halides react to
give good to excellent yields. As a rule, alkyl bromides afford
better yields than the corresponding iodides or chlorides
(entries 1-3). Functionalized styrene derivatives can be
coupled efficiently (entries 7-10). It is interesting to note
that the reaction can be achieved stereoselectively (Scheme
67).
A detailed mechanistic study was performed (Scheme
68).
At first, CoCl2dpph [A] reacts with Me3SiCH2MgCl
to give Co0dpph [B], which is the real catalyst. A single
monoelectronic transfer to the alkyl halide leads to the
CoI species [C] that reacts with Me3SiCH2MgCl to give
the intermediate [D]. This one reacts with the benzylic
radical accruing from RX to produce the diorganocobalt
[E]. The Heck product RCHdCHPh is then obtain from

[E] by -hydrogen elimination. Finally, Co0dpph [B] is
regenerated from the hydridocobalt species [F] by reductive elimination.
It is important to note that a mechanism involving a
CoI/CoIII couple like this one proposed for the vitamin
B12- or the cobaloxime-mediated reaction60,61 cannot be
discarded.
The cobalt-catalyzed Heck-type reaction between an
epoxide and styrene has also been described (Table 33).72
Table 33. Cobalt-Catalyzed Heck-Type Reaction between

Epoxides and Styrene
Entry
Yield (%)
24/25
1
2
3
4
Me
n-Bu
c-C6H11
t-Bu
57
58
48
26
79:21
57:43
63:37a
>99:1
Toluene is used as solvent.
Scheme 71. Enantioselective Cobalt-Catalyzed Michael

Addition to Chalcone
Scheme 72. Cobalt-Catalyzed Michael Addition to Various

Activated Alkenes
Scheme 69. Vitamin B12-Catalyzed Michael-like Addition
Scheme 70. Enantioselective Cobalt-Mediated Michael

Addition to Chalcone
Table 34. Cobalt-Mediated Michael Reaction between Aryl
Halides or Triflates and Activated Alkenes
Entry
FG
EWG
Yield (%)
1
2
3
4
5
6
7
p-CO2Et
p-CO2Et
p-CO2Et
p-CN
p-CN
p-CN
p-CN
Br
Br
OTf
Br
Br
Cl
OTf
CO2Et
CN
CO2Et
CO2Et
CN
CO2Et
CO2Et
80
85
72a
70a
77a
66
69a
The reaction leads to moderate yields, and a mixture of

isomers is obtained. Thus, except in the case of a hindered
epoxide, the stereoselectivity of the reaction is very poor
(Table 33, entry 4).
a
9. Miscellaneous Reactions
9.1. Cobalt-Mediated Michael Addition
As mentioned above, alkyl and aryl radicals are generated
by reacting an alkyl or an aryl halide with various cobalt(II)
complexes (see section 8).
Diastereoselective conjugate addition of the radicals thus
obtained to activated alkenes has been studied for the first
time by Giese73 in 1992 (Scheme 69). The reaction is
performed by using a catalytic amount of vitamin B12 and
zinc as a reductant.
In 1998, Pfaltz74 obtained a poor yield, but a promising
high enantiomeric excess, by reacting tert-butyl malonate
with chalcone in the presence of cobalt acetate and the chiral
macroheterocyclic ligand 28 (Scheme 70).
A better yield, but a moderate enantiomeric excess, was
obtained by Wu and Zhou75 by reacting ethyl malonate in
the presence of a similar catalytic system (Scheme 71).
20 mol % of catalyst was used.
In 2006, a cobalt-mediated Michael addition was performed with alkyl bromides and activated alkenes in the
presence of CoI2(dppe) and zinc as a reductant.76 Good to
excellent yields are obtained (Scheme 72).
Finally, a cobalt-mediated Michael addition from aryl
halides or triflates and activated alkenes has also been
described by Perichon (Table 34).77 Aryl bromides (entries
1, 2, 4, and 5), chlorides (entry 6), or triflates (entries 3 and
7) give similar yields. The reaction is chemoselective; thus,
ester and cyano groups are tolerated.
9.2. Allylation of 1,3-Dicarbonyl Compounds

The allylation of 1,3-dicarbonyl compounds under cobalt
catalysis has been reported by Iqbal.78 The reaction can be
performed under neutral conditions, contrary to the palladium-79 or the molybdenum-catalyzed80 reactions. Therefore, the use of base-sensitive substrates like 30 is possible.
Selected examples are given in Table 35.
Cahiez and Moyeux
Table 35. Cobalt-Catalyzed Allylation of 1,3-Dicarbonyl

Compounds with Allylic Acetates
Scheme 73. Cobalt-Catalyzed Allylic C-H Bond Amination
Scheme 74. Cobalt-Catalyzed Benzylic C-H Bond

Amination
Table 36. Cobalt-Catalyzed Allylation of 1,3-Dicarbonyl

Compounds with Allylic Alcohol
Entry
R1
R2
Catalyst
33/34
Yield (%)
1
2
3
4
5
6
H
Ac
H
Ac
H
Ac
Me
Me
OMe
OMe
OMe
OMe
Me
Me
Ph
Ph
Me
Me
Pr
Pr
Et
Et
Bu
Bu
CoIIIDMG
CoCl2
CoIIIDMG
CoCl2
CoIIIDMG
CoCl2
1/8
1/3
1/9
1/3
100/0
1/1.5
61
68
64
55
53
24
Table 37. Benzylic C-H Amination (see Scheme 74)

Yield (%)
Moderate to good yields are obtained. Regio- and stereoselectivity heavily depend on the nature of the substrate; a
mixture of isomers is often obtained.
This reaction has then been extended to allylic alcohols81
(Table 36).
Entry
Substrate
Catalysta
Amine
1
2
3
4
5
6
Toluene
Isopropylbenzene
Cyclohexylbenzene
Ethylbenzene
Diphenylmethane
Fluorene
A
A
B
A
B
C
53
28
25
55
Imine
25
19
11
41
9.3. Activation of C-H Bonds: C-N Coupling

Reactions
a
CoII porphyrin A: R2 ) H, R3 ) p-Cl-C6H4; B: R2 ) H, R3 ) Ph;
C: R2 ) Et, R3 ) H.
Transition metal-mediated activation and functionalization

of C-H bonds is currently a very challenging research area.82
9.4.1. Synthesis of -Acetamido Ketones
Cobalt-porphyrin-catalyzed C-H bond aminations have

been widely investigated by Cenini.83 In 1999, the amination
of an allylic C-H bond was described84a (Scheme 73).
However, only moderate yields are obtained and the scope
of the reaction is limited to cyclohexene.
The reaction has then been extended to benzylic C-H
bonds.84b,c According to the nature of the substrate, an amine
or an imine can be obtained in moderate yields (Scheme 74
and Table 37).
9.4. Three-Component Reactions

Multicomponent reactions have emerged as a useful
synthetic tool in the past decade.84 As illustrated above, cobalt
salts can be employed as catalysts to achieve such reactions.
In 1994, Iqbal85 described a three component reaction

between a ketone, an aldehyde, and acetonitrile. Various
-acetamido ketones were prepared in moderate to good
yields (Scheme 75).
Similarly, the reaction between a 1,3-dicarbonyl compound, an aldehyde, and acetonitrile86 affords -acetamidodiketones in moderate to good yields (Scheme 76).
It should be noted that aromatic aldehydes lead to
acetamidodiketones when the reaction is performed under
an inert atmosphere whereas the Knoevenagel adduct is
formed in the presence of atmospheric oxygen (Scheme 77).
On the other hand, aliphatic aldehydes behave differently,
since the acetamidodiketones are obtained only in the
presence of atmospheric oxygen. A complex mixture of
products is formed when the reaction takes place under an
inert atmosphere (Scheme 77).

Scheme 75. Synthesis of -Acetamido Ketones via a
Cobalt-Catalyzed Three-Component Reaction

Scheme 78. Synthesis of Furans and -Lactams via a
Scheme 79. Synthesis of Homoallylsilanes via a

Scheme 76. Synthesis of -Acetamido Diketones via a

Scheme 80. Tentative Mechanism for the Formation of

Homoallylsilanes via a Cobalt-Catalyzed Three-Component
Reaction
Scheme 77. Cobalt-Catalyzed Reaction between

1,3-Dicarbonyl Compounds, Aldehydes, and Acetonitrile:
Influence of the Presence of Oxygen on the Course of the
Reaction
This methodology has been applied to the synthesis of

furans and -lactams (Scheme 78).
9.4.2. Synthesis of Homoallylsilanes

In 2003, Oshima87 described a cobalt-catalyzed threecomponent reaction between an alkyl halide, a 1,3-diene, and
trimethylsilylmethylmagnesium chloride. Various homoallylsilanes have been synthesized in good to excellent yields
from primary, secondary, or tertiary alkyl halides (Scheme
79).
The following catalytic cycle was proposed (Scheme 80).
At first, Me3SiCH2MgCl reduces cobalt(II) chloride into

an active Co0 species [A]. This one reacts with the alkyl
halide via a single electron transfer to form the corresponding
alkyl radical and the CoI complex [B]. Afterward, the alkyl
radical adds to the diene to give a new radical, which
combines with [B] to form the CoII complex [C].
Me3SiCH2MgCl then reacts with [C] to afford the diorganocobalt [D], which undergoes a reductive elimination,
leading to the homosilane [E] and to the complex [A].
9.5. Coupling of Alkenes and Alkynes

Copper-mediated reactions have been extensively used for
the preparation of conjugated diynes.88 The Glaser89 and
Eglington90 procedures for the homocoupling of terminal
alkynes, or the Cadiot-Chodkiewicz91 procedure for the

Scheme 81. Cobalt-Catalyzed Dimerization of Terminal
Alkynes
Scheme 82. Cobalt-Catalyzed Reductive Dimerization of

Activated Alkenes
Cahiez and Moyeux

Scheme 83. Cobalt-Catalyzed Reductive Coupling of
Internal Alkynes with Conjugated Alkenes
Scheme 84. Cobalt-Catalyzed Alder-Ene Reaction
Scheme 85. Cobalt-Catalyzed Intramolecular Reductive

Coupling of Activated Alkenes and Alkynes
coupling of a terminal alkyne with a 1-halo-1-alkyne, are

probably the most popular coupling reactions for the
synthesis of 1,3-diynes. A cobalt-catalyzed reaction can also
be used to prepare diynes.92 Thus, in 2001, Krafft93 reported
the cobalt-catalyzed dimerization of terminal alkynes in
excellent yields (Scheme 81). It is noteworthy that, in the
case of conjugated enynes, no trace of the Pauson-Khand94
product is detected.
The cobalt-catalyzed reductive dimerization of conjugated
alkenes was described by Cheng in 2004.95 Excellent results
are obtained from various activated alkenes or styrenes
(Scheme 82). It should be noted that such reactions have
been previously performed in the presence of stoichiometric96
or catalytic97 amounts of cobalt salts, but the yields are very
poor.
The same methodology can be successfully applied to the
reductive coupling of internal alkynes with conjugated
alkenes.98 Interestingly, the reaction can be highly regio- and
stereoselective. Thus, only one product is obtained from
conjugated acetylenic esters and phenylacetylene derivatives
(Scheme 83).
Nonactivated terminal olefins were also used.99 As a rule,
good yields and satisfactory stereoselectivities can be
obtained under mild conditions (Scheme 84).
Very recently, Cheng100 extended the reaction to the
intramolecular reductive coupling of activated alkenes with
alkynes (Scheme 85). This reaction allows the synthesis of
various exomethylenecyclopentane derivatives in good to

excellent yields.
It is noteworthy that it is possible to perform a cobaltcatalyzed intramolecular reductive coupling/lactonization of
acrylates with propargyl alcohols (Scheme 86).
When propargyl amine derivatives are used, the reaction
leads to the formation of six-membered cyclic lactams
(Scheme 87).
9.6. Various Reactions

In 2005, Oshima101 reported the syn-hydrophosphination
of alkynes under cobalt catalysis. It should be noted that
lanthanide-,102 palladium-, or nickel-catalyzed103 reactions

Coupling/Lactonization of Acrylates with Propargyl Alcohols

Coupling/Lactonization of Acrylates with Propargyl Amines
Derivatives
Scheme 88. Cobalt-Catalyzed syn-Hydrophosphination of

Alkynes: Application to the Wittig Reaction
Scheme 89. Cobalt-Catalyzed Synthesis of 1,2-Di- and

1,1,2-Trisilylethylenes
Scheme 90. Synthesis of Thioethers via Cobalt-Catalyzed

C-S Coupling Reaction
Table 38. Cobalt-Catalyzed syn-Hydrophosphination of

Alkynes
Entry
R1
Yield (%)
35/36
1
2
3
4
5
6
pent
Ph
o-anisyl
t-Bu
Ph
Et3Si
Me
Me
Me
H
H
H
82
74
41
81
70
62
66/34
82/18
80/20
100/0
89/11
94/6
have also been described. However, the stereoselectivity of

these reactions is highly dependent on the nature of the
substrate. On the contrary, the cobalt-catalyzed reaction
mainly leads to the syn-addition product 35 (Table 38).
This reaction is of particular interest, since the resulting
alkenylphosphine can be used for performing Wittig reactions
(Scheme 88).
The same year, Oshima104 reported the preparation of 1,2di- and 1,1,2-trisilylethylenes via a cobalt-mediated reaction
of dibromomethylsilanes with trialkylsilylmethylmagnesium
reagents. Disilylethylenes are usually synthesized by hydrosilylation of silylacetylenes105 or disilylation of acetylenes.106 Contrary to these reactions, the cobalt-mediated
procedure is highly regioselective and stereoselective (Scheme
89).
In 2006, Cheng107 reported the cobalt-mediated synthesis
of thioethers from thiols and aryl halides (Scheme 90). This
coupling method is advantageous compared to copper-,
palladium-, and nickel-mediated reactions,108 since mild
reaction conditions and low catalyst loading are necessary.

Moreover, the use of sophisticated phosphine ligand is
avoided.
Under these conditions, ethyl 2-iodoacrylate can also be
coupled successfully (Scheme 91).
10. Conclusion
Sustainable development prompted organic chemists to
look for more ecocompatible and more economical transition
metal-catalyzed procedures. Thus, in the last ten years, a
growing number of iron- or manganese-catalyzed reactions

Thiophenol and 2-Iodoethyl Acrylate
were proposed to replace the older palladium and nickelcatalyzed cross-coupling procedures. Of course, in the
framework of sustainable development, cobalt is less interesting than iron or manganese; however, it compares
favorably to nickel and palladium. Thus, cobalt can be an
interesting alternative when iron or manganese cannot be
used. On the other hand, it should be underlined that several
reactions performed under cobalt catalysis are specific to this
metal. For instance, iron-catalyzed cross coupling between
aryl Grignard reagents and functionalized secondary alkyl
bromides generally failed whereas excellent yields are
obtained under cobalt catalysis. Thus, in the future, it should
be possible to develop more distinct reactions using cobaltbased catalytic systems.
In spite of the numerous interesting reports mentioned in
this review, cobalt-catalyzed reactions are still in their
infancy. In the future, they should be more extensively
developed and could take a significant place in the renewal
of transition metal-catalyzed reactions.
11. Acknowledgments
We thank the CNRS for financial support. Gerard Cahiez
thanks current and former members of his laboratory for their
contribution to the development of cobalt-catalyzed coupling
reactions. Their names appear in the list of references. We
also thank Julien Buendia and Dr. Olivier Gager for
proofreading.
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