Tungsten-Catalyzed Regioselective Allylic Amination

Abstract

A highly regioselective synthesis of allylic amines based on a tungsten-catalyzed allylic amination has been developed. This protocol, which is catalyzed by commercially available W(CO)₃(MeCN)₃ and 4,4′-di-tert-butyl-2,2′-bipyridine, permits the formation of synthetically useful branched allylic N-aryl- and N-alkylamines in moderate to good yields with a >20:1 branched/linear ratio under mild conditions. The noble-metal-free catalytic system complements conventional allylic aminations catalyzed by an Ir or Rh complex.

Key words

tungsten catalysis - allylic amines - amination - regioselectivity

Publication History

Received: 29 May 2024

Accepted after revision: 17 June 2024

Accepted Manuscript online:
17 June 2024

Article published online:
24 June 2024

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• 23 N-(1-Propylprop-2-en-1-yl)aniline (3a); Typical Procedure A pressure tube equipped with a magnetic stirrer bar was charged with W(CO)₃(MeCN)₃ (10 mol%) and L6 (12 mol%). The tube was purged with argon for 3 minutes, then EtOH (2 mL) was added, followed by the allylic carbonate 1a (1.1 equiv) and aniline (2a) (1.0 equiv). The tube was sealed with a PTFE-lined cap, and the mixture was stirred in an oil bath at 80 °C for 48 h, then cooled. The crude reaction mixture was directly subjected to flash column chromatography [silica gel, PE–EtOAc (100:1)] to give a colorless oil; yield: 63.7 mg (91%). TLC R_f = 0.5 (PE–EtOAc, 100:1). ¹H NMR (400 MHz, CDCl₃): δ = 7.17 (dd, J = 8.5, 7.4 Hz, 2 H), 6.63 (t, J = 7.3 Hz, 1 H), 6.62–6.55 (m, 2 H), 5.75–5.73 (m, 1 H), 5.22 (d, J = 17.2 Hz, 1 H), 5.15 (d, J = 10.3 Hz, 1 H), 3.89–3.77 (m, 1 H), 3.61 (s, 1 H), 1.65–1.54 (m, 2 H), 1.52–1.34 (m, 2 H), 0.96 (t, J = 7.3 Hz, 3 H). ¹³C NMR (101 MHz, CDCl₃): δ = 147.6, 140.4, 129.3, 117.1, 115.1, 113.3, 55.6, 38.7, 19.2, 14.0. HRMS (ESI): m/z [M + H]⁺ calcd for C₁₂H₁₈N: 176.1434; found: 176.1439.