1006
P. K. Patra et al.
PAPER
Reduction of Methyl Phenylacetate Using the Mixture of 4 and
5; Typical Procedure
References
(1) (a) Solladie, G. Synthesis of Sulfides, Sulfoxides and
Sulfones, In Comprehensive Organic Synthesis, Vol. 6;
Trost, B. M.; Fleming, I., Eds.; Pergamon Press: Oxford UK,
1991, 133–170. (b) Procter, D. J. J. Chem. Soc., Perkin
Trans. 1 2001, 335. (c) Roy, K.-M. Thiols and Organic
Sulfides, In Ullmann’s Encyclopedia of Industrial
To a solution of methyl phenylacetate (100 mg, 0.67 mmol) in THF
(2 mL) was added a solution of the mixture of 4 and 5 (4:1, 377 mg,
0.99 mmol of 4) in THF (2 mL) and the mixture was stirred for 24
h. After completion of the reaction (TLC), MeOH (2 mL) and 1 N
HCl (2 mL) were added and the mixture was refluxed for 6 h to
quench the amine-borane. After cooling the mixture, the solvent
was removed. The residue was taken up in Et2O (75 mL) and
washed with 1 N HCl (2 × 30 mL). The ethereal layer was washed
once each with water (20 mL) and brine (20 mL), dried (Na2SO4)
and concentrated to afford phenethyl alcohol as a colorless oil (76.7
mg, 94%, >98% pure in NMR).
Chemistry; Wiley-VCH: Weinheim, 2002.
(2) (a) Harris, J. M.; Liu, Y.; Chai, S.; Andrews, M. D.; Vederas,
J. C. J. Org. Chem. 1998, 63, 2407. (b) Cole, C. D.; Stock,
J. R.; Kappel, J. A. Bioorg. Med. Chem. Lett. 2002, 12,
1791. (c) Crich, D.; Neelamkavil, S. J. Am. Chem. Soc.
2001, 123, 7449. (d) Crich, D.; Neelamkavil, S.
Tetrahedron 2002, 58, 3865.
Reduction of 4-Methoxyphenylacetonitrile Using 2; Typical
Procedure
(3) (a) Nishide, K.; Ohsugi, S.; Fudesaka, M.; Kodama, S.;
Node, M. Tetrahedron Lett. 2002, 43, 5177. (b) Ohsugi, S.;
Nishide, K.; Oono, K.; Okuyama, K.; Fudesaka, M.;
Kodama, S.; Node, M. Tetrahedron 2003, 59, 8393. (c) For
the references related to odorless thiols, see the following:
Nishide, K.; Ohsugi, S.; Shiraki, H.; Tamakita, H.; Node, M.
Org Lett. 2001, 3, 3121. (d) Node, M.; Kumar, K.; Nishide,
K.; Ohsugi, S.; Miyamoto, T. Tetrahedron Lett. 2001, 42,
9207. (e) Nishide, K.; Miyamoto, T.; Kumar, K.; Ohsugi, S.;
Node, M. Tetrahedron Lett. 2002, 43, 8569.
To a solution of 4-methoxyphenylacetonitrile (100 mg, 0.68 mmol)
in THF (2 mL) was added a solution of 2 (233.6 mg, 1.02 mmol) in
THF (2 mL). The reaction mixture was refluxed for 5 h and cooled
to r.t. To the reaction mixture, was added slowly 6 N HCl (1 mL)
and refluxed for 30 min. The mixture was poured into water and
basified (pH 9) using 3 M NaOH, extracted with Et2O (3 × 30 mL)
followed by a short column chromatography using hexane and
EtOAc (10:1) to CHCl3 and MeOH (20:1) as the eluents to afford 4-
methoxyphenethyl amine (87 mg, 79%) and 1 (216 mg, 98%).
(4) (a) Zaidlewicz, M.; Brown, H. C. Encyclopedia of Reagents
for Organic Synthesis, Vol. 1; J. Wiley: New york, 1995,
634. (b) Brown, H. C. Organic Syntheses via Boranes;
Aldrich Chemical Co. Inc.: Milwaukee, 1997.
Reduction of N-Benzyl-2-(4-methoxyphenyl)acetamide Using 2;
Typical Procedure
To a solution of N-benzyl-2-(4-methoxyphenyl) acetamide (85.9
mg, 0.34 mmol) in THF (2 mL) was added a solution of 2 (232 mg,
1.01 mmol) in THF (2 mL). The reaction mixture was refluxed for
8 h and cooled to r.t. The solvent was evaporated in vacuo and the
residue was taken up in MeOH (2 mL) followed by the addition of
6 N HCl (1 mL). The reaction mixture was refluxed for 30 min and
then poured into water and basified (pH 9) using 3 M NaOH, ex-
tracted with Et2O (3 × 30 mL), dried (Na2SO4). Purification by a
short column chromatography using hexane and EtOAc (10:1) to
CHCl3 and MeOH (20:1) as the eluents afforded benzyl-4-methox-
yphenethyl amine (80 mg, 99%) and 1 (209 mg, 96%).
(5) (a) 1,2-Bis(tert-butylthio)ethane and 1,4-bis(benzyl-
thio)butane: Follet, M. Chem. Ind. 1986, 123. (b) 1,4-Thio-
xane: Brown, H. C.; Mandal, A. K. J. Org. Chem. 1992, 57,
4970. (c) Diisoamyl sulfide and bis(2-methoxyethyl)sulfide:
Zaidlewicz, M.; Kanth, J. V. B.; Brown, H. C. J. Org. Chem.
2000, 65, 6697. (d) Bis(2-hydroxyethyl)sulfide: Brown, H.
C.; Zaidlewicz, M.; Dalvi, P. K.; Biswas, G. K. J. Org.
Chem. 2001, 66, 4795. (e) 2-(Perfluorooctyl)ethyl methyl
sulfide: Crich, D.; Neelamkavil, S. Org Lett. 2002, 4, 4175.
(6) Nishide, K.; Patra, P. K.; Matoba, M.; Shanmugasundaram,
K.; Node, M. Green Chem. 2004, 4, 142.
(7) Zwifel, G.; Brown, H. C. Org. React. 1963, 13, 1.
(8) Brown, H. C.; Kanth, J. V. B.; Dalvi, P. K.; Zaidlewicz, M.
J. Org. Chem. 1999, 64, 6263.
Acknowledgment
We are grateful for Grant-in-Aid (No. 15659005 to KN and No.
13470474 to MN) from the Ministry of Education, Science, Sports
and Culture of Japan, in partial financial support of this research.
PKP acknowledges the JSPS for a postdoctoral fellowship.
Synthesis 2004, No. 7, 1003–1006 © Thieme Stuttgart · New York