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.
Key words
gold catalysis - allylic alcohols - amination - nucleophilic substitution - synthetic methods
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26
Typical Procedure for AuCl
3
-Catalyzed Direct Amination of Allylic Alcohols
3 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 -ClC6 H4 NH2 (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 ): 1 H 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). 13 C 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 C21 H18 ClN: 319.1128; found: 319.1121.
