HFIP-Induced Allylation Reaction of Tertiary Allylic Alcohols with Thiols or Sulfonyl Hydrazines to Access Allylic Organosulfurs

Abstract

A simple and transition-metal-free HFIP-induced allylation reaction of tertiary allylic alcohols with thiols or sulfonyl hydrazine derivatives was reported for the efficient and highly selective synthesis of allylic sulfides and allylic sulfones. Herein, HFIP played a vital role in not only activating the allylic alcohol, but also stabilizing the allylic cation intermediate to accelerate the subsequent transformations.

Key words

organosulfurs - HFIP - allylation - allylic alcohol

Publication History

Received: 18 July 2022

Accepted after revision: 02 August 2022

Accepted Manuscript online:
02 August 2022

Article published online:
21 September 2022

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• 17 Cyclohexyl(3,3-diphenylallyl)sulfane (c1) – Typical Procedure1,1-Diphenylprop-2-en-1-ol (60.0 mg, 0.3 mmol), cyclohexyl mercaptan (50.0 mg, 0.45 mmol), HFIP (500.0 mg, 3.0 mmol), and magnetic stirring bar was added in a 10.0 mL flask. The reaction mixture stirred at the room temperature for 10 h, after which time TLC indicated complete consumption of starting substrate 1,1-diphenylprop-2-en-1-ol. The solvent was concentrated and purified by flash chromatography on silica gel (Hex/EtOAc = 60:1) to give the desired product c1 as a white solid (78.6 mg, 85% yield). ¹H NMR (400 MHz, CDCl₃): δ = 7.39–7.31 (m, 3 H), 7.30–7.23 (m, 5 H), 7.21–7.19 (m, 2 H), 6.15 (t, J = 7.8 Hz, 1 H), 3.25 (d, J = 7.8 Hz, 2 H), 2.61–2.55 (m, 1 H), 1.80–1.57 (m, 5 H), 1.23–1.17 (m, 5 H). ¹³C NMR (100 MHz, CDCl₃): δ = 143.1, 142.1, 139.2, 130.0, 128.2, 128.1, 127.5, 127.4, 127.3, 125.9, 42.8, 33.6, 29.4, 26.2, 25.8. HRMS (ESI): m/z calcd for C₂₁H₂₅S [M + H⁺]