Gold-Catalyzed Direct Amination of Allylic Alcohols

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
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.