Highly Substituted Pyrroles by a Gold(I)-Catalyzed Tandem Reaction of 1-(1-Alkynyl)cyclopropyl Oxime Ethers with Nucleophiles

Abstract

A gold(I)-catalyzed tandem reaction of 1-(1-alkynyl) cyclopropyl oxime ethers with nucleophiles under mild conditions has been developed, which provides a facile access to highly substituted pyrroles in moderate to excellent yields.

Key words

pyrroles - gold - nucleophiles - cyclization - cyclopropane

• References and Notes

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• 21 General Procedure for the Gold(I)-Catalyzed Tandem Reaction of 1-(1-Alkynyl)cyclopropyl Oxime Ethers with Nucleophiles A solution of PCy₃AuOTf (generated from 1:1 mol ratio of PCy₃AuCl/AgOTf, 3 mL, 0.005 M in toluene, 5 mol%) was added to a dry Schlenk tube under Ar. Oxime ether 1a (0.20 mmol, 57.8 mg) and nucleophile 2a (0.4 mmol, 43.3 mg) were added to the mixture. The resulting mixture was stirred at r.t. unless otherwise specified until the reactions were complete, as determined by TLC analysis. The residue was purified by flash column chromatography on silica gel (hexanes–EtOAc = 30:1) to afford the pure product 3a (0.17 mmol, 68.8 mg) in 87% yield; oil. ¹H NMR (400 MHz, CDCl₃): δ = 7.60–7.48 (m, 2 H), 7.30–7.04 (m, 13 H), 5.96 (s, 1 H), 4.42–4.34 (m, 2 H), 4.20 (d, J = 12.4 Hz, 1 H), 3.51 (s, 3 H), 2.92–2.86 (m, 1 H), 2.66–2.60 (m, 1 H), 1.80 (s, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 142.22, 138.69, 131.57, 128.44, 128.20, 128.13, 127.54, 127.40, 127.28, 126.88, 125.77, 125.68, 125.60, 124.06, 112.25, 104.78, 82.63, 70.43, 65.07, 35.59, 8.08 ppm. IR (neat): ν = 1602, 1517, 1493, 1452, 1351, 1263, 1238, 1218, 1068, 1026, 971, 910 cm^–1. MS (EI): m/z (%): 397 (15.33) [M]⁺, 91 (100). HRMS: m/z calcd for C₂₇H₂₇NO₂: 397.2042; found: 397.2045