Zirconium Borohydride Piperazine Complex, An e Cient, Air and Thermally Stable Reducing Agent

Tetrahedron
Letters
Tetrahedron Letters 45 (2004) 32953299
Zirconium borohydride piperazine complex, an ecient, air and

thermally stable reducing agent
M. Tajbakhsh,a,* M. M. Lakouraj,a,* F. Shirini,b S. Habibzadeha and A. Nikdoosta
a
Department of Chemistry, Mazandaran University, Niroo Havaei Street, Babolsar 47416-1467, Iran
b
Department of Chemistry, Guilan University, Rasht 41335, Iran
Received 10 November 2003; revised 2 February 2004; accepted 20 February 2004
AbstractA zirconium borohydride piperazine complex (Ppyz)Zr(BH4 )2 Cl2 , obtained by the reaction of an ethereal solution of
ZrCl4 and LiBH4 with piperazine is a stable, selective and ecient reducing agent. (Ppyz)Zr(BH4 )2 Cl2 reduces aldehydes, ketones,
silylethers, a,b-unsaturated carbonyl compounds and esters. The reactions were performed in diethyl ether at room temperature or
under reux, and the yields of the corresponding alcohols were excellent. The selective reduction of aldehydes in the presence of
ketones and complete regioselectivity in the reduction of a,b-unsaturated carbonyl groups were observed.
2004 Elsevier Ltd. All rights reserved.
A number of covalent transition-metal borohydride

complexes are known, which are volatile, unstable
materials and which cannot be used as reducing agents,1
without modication, in organic synthesis. There are
only a few reports in the literature of the use of modied, stable forms of these compounds for reductive
transformations including, (Ph3 P)2 CuBH4 ,2 [(Ph3 P)2 CuBH3 CN]2 ,3 (C5 H5 )2 Zr(Cl)BH4 ,4 Zn(BH4 )2 ,5 DABCO
and (pyz)Zn(BH4 )2 ,6;7 [Zr(BH4 )2 Cl2 (dabco)2 ]8 and
Zr(BH4 )2 -crown ethers.9 Zirconium borohydride is a
highly volatile solid, which decomposes around room
temperature, inames in air, and which hydrolyses
explosively.10
Polymer supported zirconium borohydride complexes
have received considerable attention in recent years and
while exhibiting the advantages of polymeric reagents,
have been used for the mild and selective reduction of
organic compounds.11
Herein we report a coordination polymer of zirconium
borohydride with a bidentate ligand, piperazine, as a
new, air and thermally stable and ecient bench top
reducing agent for the reduction of a variety of organic
compounds. The zirconium borohydride piperazine
complex was easily prepared by treatment of ZrCl4 and
Keywords: Zirconium borohydride; Piperazine; Reducing agent.

* Corresponding authors. Tel.: +98-1125234338; fax: +98-1125242002;
e-mail: tajbaksh@umz.ac.ir
0040-4039/$ - see front matter 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tetlet.2004.02.140
an ethereal solution of LiBH4 with piperazine at 05 C.

It is a white powder, which can be stored in a vacuum
dessicator for months without signicant change in its
activity. Based on data obtained by atomic absorption
spectroscopy and borohydride content by an iodometric
titration,12 together with elemental analysis, (Ppyz)
Zr(BH4 )2 Cl2 was conrmed as its empirical formula.
This reagent reduces both aliphatic and aromatic aldehydes readily at room temperature in diethyl ether and
ketones at reux (Tables 1 and 2). A comparison of
these data showed that aldehydes are reduced rapidly
and more conveniently than ketones. Therefore the
chemoselective reduction of an aldehyde in the presence
of a ketone was achieved at room temperature and the
unreacted ketone was recovered (Table 3). Numerous
methods exist for the chemoselective reduction of an
aldehyde in the presence of a ketone,13 but each has its
limitations and therefore this new methodology should
be of interest. Deprotection of aliphatic and phenolic
trimethylsilyl ethers to the corresponding alcohols and
phenols was achieved using (Ppyz)Zr(BH4 )2 Cl2 in
diethyl ether at ambient temperature (Table 4). a,bUnsaturated carbonyl compounds undergo regioselective 1,2-reduction to the corresponding allylic alcohols
at room temperature or under reux conditions in
diethyl ether in the presence of (Ppyz)Zr(BH4 )2 Cl2
(Table 5).
An improved procedure for the reduction of the carbonyl group of a,b-unsaturated carbonyl compounds to
3296
M. Tajbakhsh et al. / Tetrahedron Letters 45 (2004) 32953299
Table 1. Reduction of aldehydes with (Ppyz)Zr(BH4 )2 Cl2 in diethyl ethera

Entry
Substrate
Product
Time (min)
Yield (%)b
Reagent/substrate
OH
CH2
60
97
45
98
45
96
75
90
240
95
20
98
45
30
1
1
95
100c
OH
CH2
H
Cl
Cl
OH
CH2
Br
Br
OH
CH2
H
OMe
OMe
OH
CH2
H
OH
OH
OH
CH2
H
NO2
NO2
7
8
PhCH2 CHO
CH3 (CH2 )4 CHO
PhCH2 CH2 OH
CH3 (CH2 )4 CH2 OH
Reductions were performed at room temperature.

The yields refer to isolated products.
c
GC yield.
b
Table 2. Reduction of ketones with (Ppyz)Zr(BH4 )2 Cl2 a

Entry
Substrate
Product
Time (h)
Reagent/substrate
Yield (%)b
1
2
3
PhCOPh
PhCOCH3
(PhCH2 )2 CO
PhCHOHPh
PhCHOHCH3
(PhCH2 )2 CHOH
5
8
2.5
3
1
1
90
95
95
2.5
90c
2.5
95c
4
5
OH
O
CH3 (CH2 )5 COCH3
CH3 (CH2 )5 CHOHCH3
Reactions were performed in diethyl ether under reux.

Yields refer to isolated products.
c
GC yields.
b
allylic alcohols has long been a desired synthetic transformation, since this reaction frequently results in
undesired 1,4-reduction products.14 Several methods are

known to bring about such a conversion but these

Table 3.
Reduction
of
aldehydes
(Ppyz)Zr(BH4 )2 Cl2 in diethyl ethera
versus
ketones
Starting mixture
Time (min)
Yield (%)b
2-Nitrobenzaldehyde
Acetophenone
Hexanal
Benzophenone
4-Bromobenzaldehyde
Cyclohexanone
25
100
0
100
0
100
0
2
3
30
45
methods call for the use of an excess of the reagents

and can result in over-reduction products.15;16
with
Entry
3297
In addition, aliphatic and aromatic carboxylic acid

esters are also reduced to the corresponding alcohols in
excellent yields (Table 6). Nitriles, amides and nitro
compounds are completely unaected by this reagent.
In order to show the advantages and the drawbacks
of (Ppyz)Zr(BH4 )2 Cl2 for the reduction of carbonyl
groups, we compared our results with examples reported
for other modied borohydride reagents (Table 7).
Reactions were performed under room temperature using a 1:1 molar

ratio of substrate to reducing agent.
b
Yields refer to isolated product alcohols.
Table 4. Deprotection of trimethylsilyl ethers with (Ppyz)Zr(BH4 )2 Cl2 a

Entry
Substrate
Product
Time (h)
Yield (%)b
1
2
PhCH2 CH2 OSiMe3

ClCH2 CH2 OSiMe3
PhCH2 CH2 OH
ClCH2 CH2 OH
3
8
93
90
Ph
Ph
8
88
98c
98
95
OSiMe3
OH
Ph
Ph
Cl
Cl
OSiMe3
OH
Cl
Cl
OSiMe3
OH
OSiMe3
OH
Reactions were carried out at room temperature using a 1:1 molar ratio of substrate to reducing agent.
c
The reaction was conducted at reux temperature.
b
Table 5. Regioselective reduction of a,b-aldehydes and ketones with (Ppyz)Zr(BH4 )2 Cl2 a

Entry
Substrate
Product
Time (h)
Yield (%)b
0.25
93c
95c
90c
85
86
O
CH
1
2
CH
CH
Citral
CH2OH
(CH3 )2 C@CH(CH2 )2 C(CH3 )@CHCH2 OH
OH
OH
O
4
CH
Me
Cl
Me
Cl
OH
O
5
PhCH
CH
CH3
PhCH
CH
CH
CH3
(continued on next page)
3298
Table 5. (continued)
Entry
Substrate
Yield (%)b
CH
82
CH )2 CHOH
80
OH
O
CH
Time (h)
Product
( PhCH
(PhCH
CH )2 CO
Reactions were conducted in diethyl ether under reux using a 1:1 molar ratio of substrate to reducing agent.
c
Room temperature.
b
Table 6. Reduction of esters with (Ppyz)Zr(BH4 )2 Cl2 a

Entry
Ester
Product
Time (h)
Yield (%)b
1
2
3
4
5
6
7
8
CH3 COO(CH2 )3 CH3

CH3 COOC2 H5
PhCH2 COOC2 H5
PhCH2 COOCH2 Ph
PhCH(COOC2 H5 )2
PhCOOPh
CH3 CH2 COOCH3
CH3 CH@CHCOOCH3
CH3 CH2 OH
CH3 CH2 OH
PhCH2 CH2 OH
PhCH2 CH2 OH
PhCH(CH2 OH)2
PhCH2 OH
CH3 CH2 CH2 OH
CH3 CH@CHCH2 OH
4
4
8
8
9
8
4
5
95
94
90
92
90c
50
90
92
Reactions were conducted in diethyl ether under reux using a 1:1 molar ratio of substrate to reducing agent.
c
Using a 1:2 mole ratio.
b
Table 7. Comparison of (Ppyz)Zr(BH4 )2 Cl2 with other zirconium borohydride reagents for the reduction of aldehydes and ketones to the corresponding alcohols
Entry
1
2
3
Substrate
Benzaldehyde
4-Chlorobenzaldehyde
Cyclohexanone
ZrBDCa
(Ppyz)Zr(BH4 )2 Cl2
Time (h)/
yield (%)
Conditions
Time (h)/
yield (%)
Conditions
1/97
Et2 O, rt
3.5/80
2/79
2.2/92
Cp2 Zr(BH4 )Clb

Time (h)/
yield (%)
Conditions
i-C3 H7 OH (Ref. 8)
H2 O (Ref. 8)
i-C3 H7 OH (Ref. 8)
/96
C6 H6 , rt
[XP4 Zr(BH4 )4 ]c
Time (h)/
yield (%)
Conditions
4/96
THF, rt
0.75/98
Et2 O, rt
2.5/90
Et2 O,
reux
Et2 O, rt
2.8/86
i-C3 H7 OH (Ref. 8)
15/80
THF, rt
2.7/92
0.7/90
i-C3 H7 OH (Ref. 8)
H2 O (Ref. 8)
/49
C6 H6 , rt
6/95
THF, rt
Et2 O,
reux
8/90
H2 O (Ref. 8)
0.2/98
C6 H6 , rt
12/80
THF, rt
Phenylcinnamaldehyde
0.75/90
Acetophenone
8/95
Dichlorobis[1,4-diazabicyclo(2,2,2)octane]-(tetrahydroborato)zirconium.8
Bis(cyclopentadienyl)chlorotetrahydroborato zirconium(IV).4
c
Polyvinylpyridinium supported zirconium borohydride.11
b
In conclusion, (Ppyz)Zr(BH4 )2 Cl2 , unlike its unmodied

form, zirconium borohydride, is a stable bench top
reducing agent. Its mildness, chemo- and regio-selectivity and high reaction yields make this new reagent
useful for organic synthesis.
Preparation of the zirconium borohydridepiperazine
complex: A 500 mL round bottomed ask equipped with
a magnetic pellet and tted with a reux condenser was
ame dried under a stream of nitrogen. To this cooled

assembly, a solution of zirconium tetrachloride (2.5 g,
8.91 mmol) in diethyl ether (15 mL) was added followed
by a solution of lithium borohydride (1.2 g, 44.8 mmol)
in diethyl ether (30 mL). The resulting mixture was
stirred for 1 h at 05 C and then centrifuged to give a
clear ethereal solution. To this clear solution piperazine
(0.6 g, 6.6 mmol) in dichloromethane (10 mL) was added
dropwise. The white precipitate, which formed imme-
diately was ltered and washed several times with diethyl ether and dried to give a white stable powder in
96% yield.
General procedure for reduction of various organic compounds: To a solution of the substrate (1.0 mmol) in
diethyl ether (10 mL) the reagent (1.0 mmol) was added
and the mixture stirred at room temperature or under
reux for the specied time (Tables 1, 2, 4, 5 and 6).6
The progress of the reaction was followed by TLC
(eluent: CCl4 /diethyl ether). On completion of the
reaction, the mixture was ltered and evaporated to
obtain the pure product.
In a few cases, the crude products were puried by
chromatography. The products were identied by comparison of their spectra and physical data with those
of authentic samples.
Reduction of aldehydes versus ketones: To an equimolar
amount of aldehydes and ketones (4.0 mmol) in diethyl
ether (10 mL), the reagent (1.0 g, 4 mmol) was added and
the reaction mixture was stirred at room temperature for
the specied time (Table 3). The progress of the reaction
was monitored by TLC or GC. On completion of
the reaction, the mixture was puried on a silica gel
plate.
References and notes

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21, 8386.
4. Sorrell, T. N. Tetrahedron Lett. 1978, 50, 49854986.
5. Ranu, B. C.; Basu, M. K. Tetrahedron Lett. 1991, 32,
32433246.
6. Firouzabadi, H.; Adibi, N.; Zeynizadeh, B. Synth. Commun. 1998, 28, 12571273.
7. Tamami, B.; Mansour Lakouraj, M. Synth. Commun.
1995, 25, 30893096.
8. Firouzabadi, H.; Iranpoor, N.; Alinejad, H. Synth. Commun. 2002, 32, 35753586.
9. Maltseva, N. N.; Kedrova, N. S.; Gorobiskii, L. V.;
Kuznetzof, N. T. Russ. J. Coord. Chem. 2000, 26, 232234.
10. Narasimhan, S.; Balakumar, R. Synth. Commun. 2000, 30,
941946.
11. Tamami, B.; Goudarzian, N. J. Chem. Soc., Chem.
Commun. 1994, 1079.
12. Lattle, D. A.; Jensen, E. H.; Sturck, W. A. Anal. Chem.
1952, 24, 1843.
13. (a) Rao, C. S.; Deshmuleh, A. A.; Patel, B. J. Ind. J. Chem.
1986, 25B, 626; (b) Bordaruah, M.; Barua, N. C.; Sharma,
R. P. Tetrahedron Lett. 1987, 28, 57415742; (c) Ranu, B.
C.; Chakraborty, R. Tetrahedron Lett. 1990, 31, 7663
7664; (d) Nakano, T.; Umano, S.; Kino, Y.; Ishii, Y.;
Ogawa, M. J. Org. Chem. 1988, 53, 37523757.
14. (a) Ashbi, E. C.; Lin, J. J. Tetrahedron Lett. 1976, 17,
38653868; (b) Kim, S.; Moon, Y. C.; Ahn, K. H. J. Org.
Chem. 1984, 49, 1720.
15. (a) Krishnamurthy, S.; Brown, H. C. J. Am. Chem. Soc.
1976, 94, 71597162; (b) Fortunato, J. M.; Ganem, B.
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Zirconium Borohydride Piperazine Complex, An e Cient, Air and Thermally Stable Reducing Agent

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Tetrahedron

Zirconium borohydride piperazine complex, an ecient, air and

A number of covalent transition-metal borohydride

Keywords: Zirconium borohydride; Piperazine; Reducing agent.

an ethereal solution of LiBH4 with piperazine at 05 C.

M. Tajbakhsh et al. / Tetrahedron Letters 45 (2004) 32953299

Table 1. Reduction of aldehydes with (Ppyz)Zr(BH4 )2 Cl2 in diethyl ethera

Reductions were performed at room temperature.

Table 2. Reduction of ketones with (Ppyz)Zr(BH4 )2 Cl2 a

CH3 (CH2 )5 CHOHCH3

Reactions were performed in diethyl ether under reux.

undesired 1,4-reduction products.14 Several methods are

M. Tajbakhsh et al. / Tetrahedron Letters 45 (2004) 32953299

methods call for the use of an excess of the reagents

In addition, aliphatic and aromatic carboxylic acid

Reactions were performed under room temperature using a 1:1 molar

Table 4. Deprotection of trimethylsilyl ethers with (Ppyz)Zr(BH4 )2 Cl2 a

PhCH2 CH2 OSiMe3

Table 5. Regioselective reduction of a,b-aldehydes and ketones with (Ppyz)Zr(BH4 )2 Cl2 a

(CH3 )2 C@CH(CH2 )2 C(CH3 )@CHCH2 OH

(continued on next page)

M. Tajbakhsh et al. / Tetrahedron Letters 45 (2004) 32953299

Table 6. Reduction of esters with (Ppyz)Zr(BH4 )2 Cl2 a

CH3 COO(CH2 )3 CH3

Cp2 Zr(BH4 )Clb

In conclusion, (Ppyz)Zr(BH4 )2 Cl2 , unlike its unmodied

ame dried under a stream of nitrogen. To this cooled

M. Tajbakhsh et al. / Tetrahedron Letters 45 (2004) 32953299

References and notes

3. Hutchins, R. O.; Marcowitz, M. Tetrahedron Lett. 1980,

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