POTASSIUM ETHYL XANTHATE 1

Potassium Ethyl Xanthate

Br
S S Ph
+
S Ph
O SNa O S
(±)
KS OEt

[140-89-6] C3 H5 KOS2 (MW 160.30)

InChI = 1/C3H6OS2.K/c1-2-4-3(5)6;/h2H2,1H3,(H,5,6);/q;+1/ 1. crystallization H
(2)
p-1/fC3H5OS2.K/q-1;m/rC3H5KOS2/c1-2-5-3(6)7-4/ 2. morpholine HS Ph
h2H2,1H3
(+)
InChIKey = JCBJVAJGLKENNC-BDHMNWMACX

(preparation of thiols, sulfides, and disulfides; heterocycle forma- Under basic conditions thiols are particularly sensitive towards
tion; reaction with alkyl halides leads to the formation of alkyl oxidation. Substituting the tert-butyl group for ethyl in the xan-
xanthates which are versatile radical precursors; glycosidation; thate reagent obviates the need for a basic hydrolysis: the de-
esterification) composition of the intermediate is performed in situ, without its
isolation, or the addition of base (eq 3).15
Alternate Name: potassium xanthate, potassium xanthogenate,
potassium O-xanthogenate, carbonodithioic acid O-ethyl ester S
potassium salt, O-ethyl S-potassium dithiocarbonate. aliquat 336
+
Physical Data: mp 222 ◦ C;1 density 1.558.21.5 KS Ot Bu water
Br
Solubility: very soluble in cold water; decomposes in hot water;
soluble in ethanol; insoluble in ether.
Form Supplied in: pale yellow solid.
Preparative Methods: commercially available. Potassium ethyl 20 min, 75–80 °C

xanthate and its congeners can be prepared by the reaction of SC(S)OtBu –COS, –
the corresponding potassium alkoxide with carbon disulfide.2,3
Methods of purification of the commercial compound,4 as well
as for the preparation of extremely pure xanthate derivatives
have been reported.5 (3)
Handling, Storage, and Precautions: reasonably stable when SH
stored in a dark place, protected from air and moisture. 78%

The dithiocarbonate method also allows for a direct, one pot

Substitution Reactions: Preparation of Thiols, Sulfides, preparation of unsymmetrical sufides from alkyl halides, or sul-
and Heterocycle Formation. O-Alkyl dithiocarbonate salts are fonates (eq 4).16
strong and soft nucleophiles, which readily undergo SN 2 substi-
tution with alkyl halides or sulfonates.6,7 This reaction has been 1. aliquat 336, H2O, 70 °C
used for the preparation of aliphatic thiols.8,9 The advantage of n-C8H17 OMs + EtOCS2K
2. KOH, 80 °C, 30 min
this xanthate, in comparison to sodium sulfide, or sodium hydro-
gen sulfide, is that thioethers are not formed and the preparation
does not require the use of gaseous hydrogen sulfide. The con- (4)
n-C8H17 S C2H5
version of the intermediate xanthates into mercaptans can be ac-
complished by hydrolysis under basic conditions; the best reagent 80%
for this transformation is 1,2-diaminoethane,10 although aqueous
ammonia,11 ethanolamine,12 or morpholine13 have also been used SN Ar substitution with aryl halides, or diazonium salts, has been
(eq 1). Alternatively, xanthate intermediates can be reduced to used for the introduction of sulfur functionalities into aromatic
thiols with lithium aluminum hydride.14 Use of a (−)-menthol rings, in the presence of groups such as methoxyl,17 hydroxyl,18
derived xanthate allowed for the preparation of optically pure or iodide19 in the aromatic nucleus, or in the side chain. Thus,
benzylic mercaptans; the intermediary diastereomeric xanthates the reaction of the m-toluidine derived diazonium salt with potas-
could be separated by fractional crystallization (eq 2).13 sium O-ethyl xanthate affords the S-aryl xanthate, which was hy-
drolyzed to the corresponding m-thiocresol (eq 5).20 The presence
S S of trace amounts of nickel salts has been shown to enhance the
R X + reaction rate considerably,21 completely eliminating the risk of
KS OEt RS OEt explosion of the intermediate diazonium xanthate. This type of
transformation can also be accomplished with thiourea, albeit in
inferior yields. When the reaction is performed with two equiv-
hydrolysis alents of aryl halide, the diaryl sulfide is obtained in good yield
or
RSH (1) (eq 6).2 The use of sodium sulfide instead of the xanthate led to a
reduction mixture of products.22

Avoid Skin Contact with All Reagents

2 POTASSIUM ETHYL XANTHATE

Me Me 1,4-dithiine; the latter compound can be reductively dimerized into

1. KOH
EtOCS2K EtOH, ∆ bis(ethylenedithio)tetrathiafulvalene (eq 9).27
S
40–45 °C 2. H2SO4
N2 Cl S OEt H2O
S O S O H2SO4 conc.
1. NCS, CCl4, ∆ S 0 °C
Me
2. iPrOCS2K
S S S OiPr
(5)
SH
63–75% S S S S S S
P(OMe)3
from m-toluidine O (9)
∆
S S S S S S
S
EtOH 50–60% 93%
O2N Cl +
EtO SK ∆ (over 3 steps)

2 equiv

α-Halo oximes, prepared from the corresponding ketones,

O2N S NO2 (6) can be converted into xanthates with potassium ethyl xanthate.
On treatment with zinc chloride these compounds cyclize into
62–78% N-hydroxythiazole-2(3H)-thiones—a highly useful class of radi-
cal precursors (eq 10).28,29
Potassium O-ethyl xanthate can act as a double electrophilic
reagent, thus providing a convenient synthetic equivalent of thio-
phosgene. This type of reactivity, however, is restricted to fairly Br
reactive substrates, such as o-phenylenediamine which is readily
transformed into 2-mercaptobenzimidazole (eq 7).23 1,2-Amin- 1. Br2, AcOH
O N
ophenols react similarly providing fused oxazole derivatives. 2. NH2OH•HCl OH
Upon alkylation the sulfur moiety can be easily substituted by ni- Cl Cl
trogen nucleophiles, which opens up a useful entry into 2-amino 85%
substituted benzoxazoles and their congeners—an important class
of heterocyclic compounds (eq 8).24 S S
S KSC(S)OEt ZnCl2
OEt
N
1. EtO SK acetone Et2O
NH2 N OH
EtOH, H2O, ∆
SH (7) Cl
2. AcOH, H2O 90%
NH2 N
H
S
86%
(10)
N S
Cl
OH
OH O N 86%
1. KSC(S)OEt H
SMe
2. MeI
N NH2 N N

66% (over 2 steps)

Radical Reactions. S-Alkyl O-ethyl dithiocarbonates are a
synthetically useful, versatile source of alkyl radicals.30,31,32,33
O The principle of radical formation (eq 11) relies on a reversible
N (8) addition/fragmentation process, known as a group-transfer.30 In
N N order to secure the regioselectivity of the fragmentation step, ·R1
95% should be a stabilized radical. This method of radical generation
is particularly well suited for the reactions of stabilized, elec-
Vicinal aminoalkyl hydrogensulfates can be converted with trophilic, generally less reactive radicals, which can not be gener-
potassium ethyl xanthate into thiazolidine-2-thiones.25 Adducts ated in a synthetically useful manner using reagents such as trib-
obtained by radical addition of 2,4-difluorophenacyl xanthate to utyltin hydride or N-hydroxypyridine-2-thione. The experimental
alkenes (vide infra) can afford both tetrahydro-1-benzothiepine, conditions are relatively simple and involve heating of the solution
or thieno[2,3-b]-benzothiopyran systems, depending on the reac- of reactant(s) in an inert solvent (1,2-dichloroethane, toluene, cy-
tion conditions.26 Upon treatment with cold, concentrated sulfu- clohexane, etc) in the presence of a peroxide initiator (most often
ric acid, the xanthate derivative, obtained from 3-chloro-2-oxo-1, dilauroyl peroxide, DLP) under an inert atmosphere. Alternatively,
4-dithiane by nucleophilic substitution, undergoes cyclization into photolytic initiation can be used.

A list of General Abbreviations appears on the front Endpapers

 POTASSIUM ETHYL XANTHATE 3
S •R2 suitable for the creation of libraries of pleuromutilin derivatives
1
RS OEt
(eq 14).39
S
O O O O
•R1
+ R2S OEt Cl EtO(S)CS
N O + KSC(S)OEt N O
SR2

R1S • OEt O O O O
X

EtO(S)CS
N O
•
Et + R1S SR2 (11) O
HO OH 1,2-dichloroethane
The xanthate method has been successfully used for carbon- DLP, N2, ∆
carbon bond forming reactions. Intermolecular additions were
mostly performed with electron-rich alkenes (although exam- O
ples of additions to electron-deficient alkenes have also been
Pleuromutilin
reported);34,35,36 examples of such reactions are provided in (14)
O O
eqs 1237 and 13.38 It is experimentally convenient that these reac- O O
tions are performed at relatively high concentrations (0.5 M): due N
O N O
to the degenerate nature of the xanthate transfer step, there is no SC(S)OEt
need for high dilution, or slow addition techniques, as frequently O O
required with other methods of radical generation. O
O
HO DLP HO
OH i
PrOH
OH
S ∆
O O
Cl + KS O S O
F3C O O
F3C
S 75% 80%

O
Nu
O O
Nu O
S O HO OH
F3C
MeO O
S
1,2-dichloroethane
O DLP (cat.), ∆ O
O

Xanthate radical precursors can also be prepared by a hetero-

O Michael addition of potassium ethyl xanthate to enones. Subse-
SC(S)OC5H11 quent intermolecular addition of the corresponding radicals is an
F3C
efficient approach for the creation of quaternary carbon centres and
MeO O (12) cyclic systems. The product of the radical addition to vinyl acetate
is a protected aldehyde, which may take part in further transfor-
O mations (eq 15).40 Intermolecular additions of xanthate derived
O
radicals onto small, strained cycloalkenes have been reported.41,42
80% O
S AcOH
CH2Cl2
NHAc
CO2Et +
N N KS OEt
CO2Et
N X
N cyclohexane, DLP, ∆
Bn O O
AcO
KSC(S)OEt N N OAc
X=Cl DLP (cat.), ∆
N CO2Et (13) SC(S)OEt SC(S)OEt
1,2-dichloroethane
N CO2Et
X=SC(S)OEt
Bn EtO(S)CS NHAc 76% 70%

74%
O
p-TsOH, H2O
The broad tolerance of functional groups enabled the introduc- (15)
THF
tion of an activated carboxylic group into pleuromutilin, without
protection of the hydroxyl functionalities; this approach proved 82%

Avoid Skin Contact with All Reagents

4 POTASSIUM ETHYL XANTHATE

Intermolecular additions to aromatic rings are generally diffi- O

O EtO S
cult to achieve under free radical conditions. This transformation
has been successfully accomplished with a series of heterocycles
S
by means of the xanthate methodology (eqs 16 and 17).43 In order SC(S)OEt
for the intermediate adduct radicals to rearomatize, a full equiva- DLP (cat.)
lent of a peroxide initiator is required. N N ClCH2CH2Cl N N
∆
Ms Ms
65%
O
EtO(S)CS CO2Et
OEt
(16)
1,2-dichloroethane
N DLP (1 equiv.), N2, ∆ N
H DLP (1 equiv.)
H O (20)
ClCH2CH2Cl
60% ∆
N N
Ms
42%

O
O
EtO(S)CS
OMe
DLP (1 equiv.)
Ph Ph DLP (cat.)
S 1,2-dichloroethane S SC(S)OEt ClCH2CH2Cl
Br ClCH2CH2Cl ∆
O DLP (1 equiv.), N2, ∆ MeO2C
O hv, rt
75% 61%
(17)
O

H (21)
The absence of competing reactions enables the xanthate Br
method to be used effectively for slower radical processes such H
as 8-endo- (eq 18),44 or 6-exo-cyclizations with the formation of
66%
bridged bicyclic systems (eq 19).45

OAc
S
SC(S)OEt EtO(S)CS OAc
EtO(S)CS EtOCS
O O
DLP (cat.) O
O
1,2-dichloroethane (18) DLP
∆ Me Me
ClCH2CH2Cl
N N
∆
O H H
O
60% 77%

AcO

O
DLP (1 equiv.)
(22)
ClCH2CH2Cl
CO2Me Me
O ∆
N
(t-BuO)2 (cat.)
O S (19) H
t-BuPh, ∆
MeO2C SC(S)OEt 54%
S OEt
80%
Domino reactions have been successfully performed with xan-
thate precursors. Tandem cyclization (6-exo/6-exo) was exploited
Intramolecular addition onto an aromatic nucleus also works in a very efficient manner for the total synthesis of matrine
reasonably well, and provides an expedient entry into various (eq 23).49 Performing the reaction in refluxing isopropanol al-
carbo- and heteropolycyclic aromatic systems. Five- (eq 20),46 lowed for the reductive removal of the xanthate group from the
six- (eq 21),47 and even seven-membered rings (eq 22)48 can be tetracyclic product. A combination of intermolecular addition
annulated to the aromatic core; the cyclization precursors, in turn, and cyclization results in the annulation of a cyclopentane ring
can also be prepared by radical addition, as shown in the examples. (eq 24).50

A list of General Abbreviations appears on the front Endpapers

 POTASSIUM ETHYL XANTHATE 5
MeO2C CO2Me MeO2C CO2Me O
O O PMB O
PMB Ph SO2Et
H N N
N N SC(S)OEt Ph
S AIBN (cat.)
S CO2tBu H H heptane, ∆
CO2tBu
EtO DLP
N iPrOH N 63%
∆ (26)
O O
89%
With 2,2-dichlorophenylsulfone (eq 27),53 or 2-phenylsulfone
O
(eq 28),54 the analogous addition/elimination sequence affords
H vinylated derivatives. One-carbon homologation of xanthates with
N
H H (23) methanesulfonyl oxime ether, via an analogous tandem reaction,
H
has also been described.55
N Cl
matrine EtO2S Cl
PhCON SC(S)OEt PhCON
n-C7H16, C6H5Cl
DLP, ∆ Cl
Cl
hv
CO2Et + OAc 76% (27)
PhH, 15 °C
SC(S)OEt 1.5 h

Ph
EtO(S)CS OAc
EtO(S)CS
(24) H O Ph H O
MeO2S (3 equiv.)
O O
CO2Et (t-BuO)2 (3 equiv.), ∆
N N
H H
71% CO2Me CO2Me
75–80%
The introduction of allyl group into organic compounds is (28)
a very important reaction, owing to a multitude of methods
for subsequent synthetic transformations of this structural unit.
Acyl halides react with potassium ethyl xanthate to give
Allyltributylstannane is generally considered as the most efficient
S-acyl xanthates which are synthetically useful precursors of
reagent for the radical allylation.51 However, the toxicity of organ-
acyl radicals (it should be noted that even a slight excess of
otin compounds prevents its use in medicinal chemistry, or in large
the potassium O-ethyl xanthate induces the decomposition of the
scale reactions. The use of xanthates as radical precursors, in com-
initially formed S-acyl xanthate, by an ionic chain reaction).56
bination with allyl sufones, allows for a metal-free, environment
Radical generation occurs upon irradiation with visible light, and
friendly allylation procedure. In addition to a simple allyl group,
the resulting acyl radicals can be trapped inter- or intramolecu-
2-chloro-, or 2-methyl allyl derivatives can also be introduced
larly (eq 29).57 Treatment of homoallylic alcohols with phosgene,
(eq 25).52 Domino reactions are also possible, with cyclization
followed by potassium ethyl xanthate, affords S-alkoxycarbonyl
preceeding the allylation reaction (eq 26).52
xanthates; the cyclization of the corresponding alkoxycarbonyl
radicals gives rise to butanolides with a xanthate group in the β-
X
O
position. These intermediates readily undergo elimination (base-
SO2Et
catalyzed or thermally-induced), which allows for an efficient syn-
(CH2)9OAc
ButO AIBN (cat.) thesis of unsaturated lactones (eqs 30 and 31).58
heptane, ∆
SC(S)OEt
O OAc
KSC(S)OEt
PhCOCl
O CH2Cl2/acetone Ph SC(S)OEt hv, PhMe
(CH2)9OAc –35 °C
ButO (25)

O SC(S)OEt
X (29)
OAc
X=H 72% Ph
X=Me 74%
X=Cl 81% 60%

Avoid Skin Contact with All Reagents

6 POTASSIUM ETHYL XANTHATE

OH DLP, iPrOH, ∆
R H
1. COCl2 or H3PO3/Et3N
PhMe, THF or (EtO)2P(O)H

2. NaSC(S)OCH2CMe3
acetone EtSO2N3
H
R N3
S PhCl, ∆

(32)
O S OCH2CMe3 RS OEt Br
CO2Et
O S R Br
hv (visible), PhMe PhCl, ∆
NH2
H 1° H2N Br
R S
2° Br
Br
O
O Reaction of potassium ethyl xanthate, or preferably potassium
DBU neopentyl xanthate, with triphenyltin chloride affords triphenyl-
CHCl3, rt stannyl xanthate (eq 33) — a useful reagent which combines the
SC(S)OCH2CMe3
H versatility of tin hydride with the nonreductive character of the
xanthate group transfer method (eq 34).65
51% (over 3 steps) O
S S
O acetone
(30) Ph3SnCl +
KS OCH2CMe3 rt, 3 h Ph3SnS OCH2CMe3
H 72%
(33)
cinnamolide, 80%

SC(S)OCH2CMe3 Br hv (visible) Me
Me
O Ph3SnSC(S)OCH2CMe3 SC(S)OCH2CMe3
CO2Me H
PhMe Cu powder c-C6H12
CO2Me O N O N (34)
hv O distillation
RO C5H11 n-C5H11 n-C5H11
C5H11
65%
R=H 63% (overall)
COCl2
S R=COCl
O Polymer-supported Synthesis. Xanthates are excellent initia-
NaSCOC5H11
R=COSC(S)C5H11 tors for a living polymerization of radicophilic alkenes. The ease
CO2Me (31)
O of introduction of xanthate functionality into organic compounds
contributes to the applicability of this method for the preparation
C5H11
of polymeric supports “tailored” according to the substrate struc-
methylenolactocin, 62% ture and the reaction type. Submitting a bile acid xanthate deriva-
tive to the typical conditions in the presence of excess styrene
A significant advantage of the xanthate method of radical resulted in the formation of a soluble polymer, suitable for the
generation, as compared to the tributyltin hydride method, is polymer-supported synthesis (eq 35).66 After the polymerization
itsnonreductive nature, i.e., the xanthate functionality remains in is complete, the xanthate group can be removed oxidatively, or
the final products and is available for further functional trans- can be converted into a thiol and used for the placement of a label.
formations. When the reduced products are required, refluxing While maintaining all the advantages of solution chemistry, this
the S-alkyl xanthate in iso-propanol, in the presence of DLP, type of reagent can be precipitated with methanol, which allows
is a convenient, environment friendly alternative for the reduc- for a rapid purification of synthetic intermediates. This type of
tive removal of the xanthate group (eq 32).59 Hypophosphorous polymeric support has been shown to be superior to Wang resin
acid/triethylamine, or diethyl phosphite, can also be used as reduc- for free radical additions.67 The method shows promise for appli-
tants for this purpose and are especially suitable for sensitive cations in parallel synthesis.
substrates (eq 32).60 On treatment with ethanesulfonyl azide in
hot chlorobenzene, alkyl xanthates are smoothly converted into Glycosylation Reactions. Anomeric xanthates, which can be
azides (eq 32),61 a reaction that can be implemented in domino obtained from the reaction of glycosyl halides with potassium
sequences such as carboazidation.62 Exchange of bromo sub- ethyl xanthate, are valuable glycosyl donors,68,69 as well as pre-
stituent for xanthate can be accomplished under free radical con- cursors of thioglycosides.70,71 Owing to the excellent nucleophilic
ditions, in the reaction with ethyl 2-bromo-2-methylpropanoate properties of xanthates (vide supra), the substitution works well
(eq 32).63 Finally, the xanthate group can be ionically transformed even with anomeric nitrates which, in turn, can be obtained by azi-
into the sulfonium salt, which can act as a leaving group (eq 32).64 donitration of the corresponding glycals.72 Notably, attempts to

A list of General Abbreviations appears on the front Endpapers

 POTASSIUM ETHYL XANTHATE 7

triflate,79,80 phenylsulfenyl triflate,81 and iodonium species82

O (eq 37).81 The xanthate-based sialylation was the method of choice
CO2H in the synthesis of rather complex oligosaccharides,83 and some
O isotopically labeled gangliosides.84 Its successful application in
Ph
the synthesis of sialylated building blocks for glycopeptide li-
O O
10 O DLP braries has also been reported.85
H
Ph X Ph Ph
X=Br
KSC(S)OEt KSC(S)OEt
X=SC(S)OEt O NaN3, CAN
O
O O EtOH, rt, 5 h

O CH3CN, –20 °C, 3 h O

AcO AcO
N3
O ONO2
SO2Cl2, AcOH, H2O
O O 44%
Ph O
10 H
EtO(S)CS 15 Ph Ph OH
85% O BnO O
O BnO
OBn
O O OMe
1. (COCl)2 AcO SC(S)OEt
O O Cu(OTf)2, CH3CN
Ph O 2. N3 4Å, rt, 2 h
10
H
97%
Ph 14 Ph NH2

Ph
O
O
O
O O (36)
O N AcO
H N3 BnO O
BnO
KOH OBn
O MeOH OMe
H 86%
THF
O α:β=1:6
P
10

O
OAc Cl
81% AcO OAc KSC(S)OEt
O
(over 3 steps) O CO2Me acetone, rt
AcHN
AcO

OH OBn OBn
O O
HO O O
O N (35) OAc CO2Me BnO OTMSE
H AcO OAc OBn OBn
O SC(S)OEt
AcHN PhSCl, AgOTf
HO AcO di(t-Bu)pyridine
H –70 °C, 3 h
62%

substitute the nitrate group with other sulfur nucleophiles, such OAc MeO2C OH OBn OBn (37)
AcO OAc
as thiophenoxide or thioacetate anion, led only to denitration O
O O O
of the precursors.73 The anomeric xanthates thus obtained can AcHN O
OTMSE
AcO BnO
be efficiently coupled with suitable sugar derivatives to give the OBn OBn
corresponding glycosides in good yields (eq 36).73 The glycosy-
lation procedure also works well with S-furanosyl xanthates,74 78%, α:β=96:4
which can be obtained from the corresponding furanoses.75 An
alternative to potassium ethylxanthate, for the preparation of ano-
meric xanthates in both pyranose and furanose series, which Sigmatropic Rearrangements. Propargylic xanthates, read-
relies on the use of dixanthogen and tributylphosphine has ily obtainable from the corresponding propargylic halides or sul-
been reported.76 An N-acetylneuraminic acid derived xanthate77 fonates, rearrange on heating into cyclic betaines (eq 38). The
has been used for highly efficient sialylation of various sub- latter species react with electron-deficient alkenes by a tandem
strates, in the presence of various glycosylation promoters, in- addition/elimination mechanism, which results in the formation
cluding dimethyl(methylthio) sulfonium triflate,78 methylsulfenyl of the products of a formal [3+2] annulation reaction (eq 39).86

Avoid Skin Contact with All Reagents

8 POTASSIUM ETHYL XANTHATE

S S Related Reagents. Carbon Disulfide; Sodium Sulphide;

PhCl, ∆
X + Sodium Hydrogen Sulphide; Thiourea; Thiophosgene.
KS OR S OR

X=Cl, Br, OMs

1. Drawert, F.; Reuter K.-H.; Born, F., Chem. Ber. 1960, 93, 3056.
2. Price, C. C.; Stacy, G. W., Org. Synth. Coll. Vol. 1955, 3, 667.
3. Rao, S. R., Xanthates and Related Compounds, Marcel Dekker Inc.: New
S
S (38) York, 1971.
S OR 4. DeWit, C.C.; Roper, E.E., J. Am. Chem. Soc. 1932, 54, 444.
S OR
5. Stueber, D.; Patterson, D.; Mayne, C. L.; Orendt, A. M.; Grant, D. M.;
Parry, R. W., Inorg. Chem. 2001, 40, 1902.
6. Kleinpeter, E.; Pihlaja, K., In Comprehensive Organic Functional
Group Transformations; Katritzky, A. R.; Meth-Cohn, O.; Rees, C. W.;
O N O
H O Gilchrist, T. L., Eds.; Oxford: 1995, Vol. 6, p 545.
7. Degani, I.; Fochi, R., Synthesis 1978, 365.
S PhCl
+ MeO(S)CS N C6H4Br 8. Wardell, J. L. In The Chemistry of the Thiol Group; Patai, S., Ed.; Wiley-
∆
Interscience: New York, 1975, p 163.
MeO S H O 9. Schöberl, A.; Wagner, A. In Houben-Weyl Methoden der Organischen
Br
66% (39) Chemie; Müller, E., Ed. Georg Thieme Verlag: Stuttgart, 1955, Vol. 9, p
12.
Propargylic xanthates, which possess a leaving group at the 10. Mori, K.; Nakamura, Y., J. Org. Chem. 1969, 34, 4170.
distal propargylic position, give rise to dienes which are highly 11. Lehr, H.; Karlan, S.; Goldberg, M. W., J. Med. Chem. 1963, 6, 136.
reactive partners in the Diels–Alder reaction (eq 40).87 Other 12. Taguchi, T.; Kiyoshima, Y.; Komori, O.; Mori, M., Tetrahedron Lett.
reactions of the betaine intermediates include Michael addition,88 1969, 10, 3631.
Knoevenagel condensation,89 and acylation.90 13. Isola, M.; Ciuffarin, E.; Sagramora, L., Synthesis 1976, 326.
14. Djerassi, C.; Gorman, M.; Markley, F. X.; Oldenbergm, E.B., J. Am.
OBz
Chem. Soc. 1955, 77, 568.
CO2Me
15. Degani, I.; Fochi, R.; Santi, M., Synthesis 1977, 873.
PhCl S MeO2C 16. Degani, I.; Fochi, R.; Regondi, V., Synthesis 1979, 178.
O
∆ 17. Offer, J.; Boddy, C. N. C.; Dawson, P. E., J. Am. Chem. Soc. 2002, 124,
S
S 4642.
18. Jaeger, D. A.; Wang, J., J. Org. Chem. 1993, 58, 6745.
S OMe 19. Xiao, W.-J.; Alper, H., J. Org. Chem. 1999, 64, 9646.
20. Tarbell, D. S.; Fukushima, D. K., Org. Synth. Coll. Vol. 1955, 3, 809.
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A list of General Abbreviations appears on the front Endpapers

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