a
Table 3 Selective reduction of terminal double bonds
In summary, we have shown for the first time that guanidine
nitrate catalyzed diimide promoted reduction of olefins with a
remarkable chemoselectivity.
This work was supported by ARMREB, New Delhi
b
Yield
Time (h) (%)
Entry Substrate
Product
(
ARMREB/EMCB/2009/111), Indian Institute of Science
1
2
3
12
24
24
90
83
99
and RL fine Chem. The authors thank Dr A. R. Ramesha
and Prof. S. Chandrasekhar for useful discussion. ML thanks
CSIR, New Delhi, for a senior research fellowship.
Caution! Hydrazine is a suspected carcinogen and should be
handled with care in an efficient fume hood.
c,d
g
Notes and references
e
e
4
5
24
24
98
80
1
Handbook of Homogeneous Hydrogenation, ed. J. G. de Vries and
C. J. Elsevier, Wiley-VCH, New York, 2007.
2
H. S. Wilkinson, R. Hett, G. J. Tanoury, C. H. Senanayake and
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1
4
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6
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1
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g
7
(d) L. P. Samankumara, M. Zeller, J. A. Krause and C. Bruckner,
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a
Reaction conditions: olefin (1 mmol), aq. hydrazine (2 mmol),
b
2
guanidine nitrate (0.1 mmol), O (1 atm), EtOH (2 mL), RT. Isolated
c
d
yield. GCMS conversion. 4 equiv. of aq. hydrazine at 80 1C.
e
f
2
equiv. of aq. hydrazine at 80 1C. 4 equiv. of aq. hydrazine at RT.
equiv. of aq. hydrazine at RT.
g
8
(j) T. J. Donohoe, R. M. Harris, O. Williams, G. C. Hargaden,
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(
k) A. Dondoni and A. Marra, Tetrahedron Lett., 2009, 50, 3593;
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(
Catal., 2009, 351, 2271.
6
(a) E. J. Corey, W. L. Mock and D. J. Pasto, Tetrahedron Lett.,
1
961, 2, 347; (b) E. J. Corey, D. J. Pasto and W. L. Mock, J. Am.
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Scheme 1 A tentative mechanism.
presence of an internal double bond. A similar result was
obtained in the reduction of limonene (21a), the terminal double
bond was reduced, whereas the internal double bond was intact
during the reaction (entry 2, Table 3). However, this reaction was
carried out at 80 1C with 4 equiv. of aq. hydrazine. Similarly, the
reduction of a-methyl styrene (22a) required heating of the
reaction mixture at 80 1C with 4 equiv. of aq. hydrazine (99%,
entry 3). The application of this strategy is demonstrated in
reducing aryl acrylic acid to afford aryl propionic acids. As seen
in examples in entries 4 and 5, 2-(4-methoxyphenyl)acrylic acid
1
990, 55, 4117.
7 For reviews on hydrazine as reducing agent see: (a) S. Hunig,
H. R. Muller and W. Thier, Angew. Chem., Int. Ed. Engl., 1965,
4
, 271; (b) D. J. Pasto and R. T. Taylor, Org. React., 1991, 40, 91.
8
(a) Y. Imada, H. Iida and T. Naota, J. Am. Chem. Soc., 2005,
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Chem., 2008, 73, 9482; (c) B. J. Marsh and D. R. Carbery, J. Org.
Chem., 2009, 74, 3186; (d) Y. Imada, T. Kitagawa, T. Ohno,
H. Iida and H. T. Naota, Org. Lett., 2010, 12, 32 (see the support
information of this paper); (e) B. J. Marsh, E. L. Heath and
D. R. Carbery, Chem. Commun., 2011, 47, 280; (f) Y. Imada,
H. Iida, T. Kitagawa and T. Naota, Chem.–Eur. J., 2011, 17, 5908;
(
23a) and 2-(4-isobutylphenyl)acrylic acid (24a) underwent
a smooth reduction to furnish their saturated acids 23b and
4b in good to excellent yields (entries 4 and 5). To ensure the
(
g) J. F. Teichert, T. D. Hartog, M. Hanstein, C. Smit, B. T. Horst,
V. Hernandez-Olmos, B. L. Feringa and A. J. Minnaard, ACS
Catal., 2011, 1, 309; (h) Y. Imada, H. Iida and S.-I. Murahashi,
Angew. Chem., Int. Ed., 2005, 44, 1704 (see the support informa-
tion of this paper).
2
versatility of the reduction, N-allyl-N-benzyl-3-nitroaniline (25a)
and N,N-diallyl-3-nitroaniline (26a) were subjected to the
reduction and it was found that the reduction proceeded well
but needed larger amounts of aq. hydrazine to afford the reduced
products 25b and 26b respectively (entries 6 and 7, Table 3).
Regarding the reaction mechanism, we belive that the
9
1
F. G. Gelalcha, Chem. Rev., 2007, 107, 3338.
0 (a) D. Leow and C.-H. Tan, Chem.–Asian J., 2009, 4, 488;
(b) M. P. Coles, Chem. Commun., 2009, 3659.
1 (a) Y. Cheng, X. Li, Q. Wang and L. Wang, Ind. Eng. Chem. Res.,
1
2
005, 44, 7756; (b) D. Emeljanenko, J. Horn, E. Kaifer,
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2 M. Lamani, G. S. Ravikumara and K. R. Prabhu, Adv. Synth.
Catal., 2012, DOI: 10.1002/adsc201200110, in press.
8e
hydrogen bonding capability of guanidine is responsible
for the catalytic reduction (Scheme 1).
1
This journal is c The Royal Society of Chemistry 2012
Chem. Commun., 2012, 48, 6583–6585 6585