Photocatalytic [2,3]-Sigmatropic Rearrangement Reactions of Ethyl Diazoacetate

Abstract

We describe a photocatalytic reaction of diazo compounds with allyl sulfides under visible-light reaction conditions. In the presence of Ru(bpy)₃Cl₂ as a photocatalyst, a [2,3]-sigmatropic rearrangement reaction occurs that leads to the formation of homoallylic sulfides. This reaction proceeds in acetone as the solvent, which is unusual in carbene-transfer reactions, and it shows a broad substrate scope in the rearrangement reaction of allylic sulfides.

Key words

diazo compounds - photocatalysis - carbenes - rearrangement - homoallylic sulfides - allylic sulfides

Publication History

Received: 30 September 2023

Accepted after revision: 30 October 2023

Accepted Manuscript online:
30 October 2023

Article published online:
20 December 2023

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• 16 Photocatalytic Rearrangement Reactions: General Procedure The appropriate diazoalkane (0.2 mmol, 1.0 equiv) and allyl aryl sulfide (0.6 mmol, 3.0 equiv) were dissolved in acetone (2 mL), and the solution was irradiated with a module containing two blue LEDs (2 × 40 W, λ = 467 nm) overnight under Ar. When the reaction was complete, the solvent was removed under reduced pressure, and the product was purified by column chromatography (silica gel, hexane–EtOAc). Ethyl 2-(Phenylsulfanyl)pent-4-enoate (9a) Prepared according to the general procedure and purified by column chromatography [silica gel, hexane–EtOAc (80:1 to 60:1 to 40:1)] as a colorless oil; yield: 45.4 mg (96%). ¹H NMR (600 MHz, CDCl₃): δ = 7.33–7.23 (m, 2 H), 7.19–7.03 (m, 3 H), 5.66 (ddt, J = 27.3, 17.1, 10.2, 6.9 Hz, 1 H), 5.00–4.84 (m, 2 H), 3.93 (qd, J = 7.1, 1.7 Hz, 2 H), 3.52 (dd, J = 8.7, 6.4 Hz, 1 H), 2.49–2.41 (m, J = 14.4, 8.4, 7.0, 1.3 Hz, 1 H), 2.38–2.29 (m, 1 H), 0.98 (t, J = 7.1 Hz, 3 H). ¹³C NMR (151 MHz, CDCl₃): δ = 171.6, 133.9, 133.1, 128.9, 128.0, 118.0, 61.1, 50.2, 35.8, 14.0. These data agree with those reported in the literature.^13h