Synlett 2007(6): 0964-0968  
DOI: 10.1055/s-2007-973865
LETTER
© Georg Thieme Verlag Stuttgart · New York

Gold-Catalyzed Direct Amination of Allylic Alcohols

Shenghai Guo, Feijie Song, Yuanhong Liu*
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 354 Fenglin Lu, Shanghai 200032, P. R. of China
e-Mail: yhliu@mail.sioc.ac.cn;
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Publikationsverlauf

Received 14 December 2006
Publikationsdatum:
26. März 2007 (online)

Abstract

An efficient and direct synthesis of allylic amines from allylic alcohols was developed by utilization of gold complexes as catalysts under mild reaction conditions. AuCl3 proved to be a better catalyst than a cationic gold(I) complex of AuCl(PPh3)/AgOTf.

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Typical Procedure for AuCl 3 -Catalyzed Direct Amination of Allylic Alcohols
A solution of AuCl3 in MeCN (0.05 M) was prepared. Under N2 atmosphere, 1,3-diphenylprop-2-en-1-ol (1a, 0.11 g, 0.5 mmol) and p-ClC6H4NH2 (0.13 g, 1 mmol) were added to a 25 mL round-bottomed flask containing a stirring bar, and then 5 mL MeCN was added. To the mixture, 0.2 mL AuCl3 (0.01 mmol) was added. The resulting solution was stirred at 50 °C until the reaction was completed as monitored by thin-layer chromatography (3 h). The solvent was removed in vacuo and the residue was purified by flash chromatography on silica gel (PE-EtOAc = 30:1) afforded product 2c in 92% isolated yield.
N-(E)-(4-Chlorophenyl)-(1,3-diphenylallyl)amine (2c): 1H NMR (CDCl3, TMS): δ = 4.12 (br s, 1 H), 5.02 (d, J = 5.7 Hz, 1 H), 6.35 (dd, J = 6.0, 15.9 Hz, 1 H), 6.50-6.61 (m, 3 H), 7.04-7.09 (m, 2 H), 7.19-7.41 (m, 10 H). 13C NMR (CDCl3, TMS): δ = 60.65, 114.64, 122.23, 126.48, 127.13, 127.67, 127.77, 128.56, 128.87, 128.93, 130.12, 131.25, 136.40, 141.53, 145.66. HRMS (EI): m/z calcd for C21H18ClN: 319.1128; found: 319.1121.