Visible-Light-Mediated ipso-Carbosulfonylation of Alkynes: Synthesis of 3-Sulfonylspiro[4,5]trienones from Propiolamides and Sulfonyl Chlorides under Transition-Metal-Free Conditions

Abstract

An efficient and convenient strategy to synthesize diverse 3-sulfonylspiro[4,5]trienones has been developed. This ipso-carbosulfonylation of alkynes proceeds by visible-light catalysis under transition-metal-free conditions and represents a new sulfonylation and ipso-cyclization of alkynes. In this transformation, the O atom in the newly generated carbonyl is derived from H₂O and it features a broad substrates scope, especially for alkyl propiolamides and aliphatic sulfonyl chlorides.

Keywords

spiro compounds - difunctionalization - visible-light photoredox catalysis - propiolamides - sulfonyl chlorides

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• 19 General Procedure A Schlenk tube was charged with 1 (0.2 mmol), 2 (0.3 mmol, 1.5 equiv), Eosin Y (2 mol%, 0.004 mmol), Na₂CO₃ (0.4 mmol, 2 equiv), H₂O (0.8 mmol, 4 equiv), CH₃CN (2 mL). Then, the mixture was stirred at 100 °C (oil bath temperature) under an argon atmosphere (1 atm) under 5 W blue LED light for 20 h until complete consumption of starting material was monitored by TLC and GC-MS analysis. After the reaction was finished, the reaction mixture was washed with brine. The aqueous phase was extracted with EtOAc (3×10 mL). The combined organic extracts were dried over Na₂SO₄ and concentrated in vacuum. The residue was purified by silica gel flash column chromatography (hexane/EtOAc 5:1 to 1:1) to afford the desired products 3 which was analyzed by ¹H NMR, ¹³C NMR spectroscopy, and HRMS (see Supporting Information). 1-Methyl-4-phenyl-3-(phenylsulfonyl)-1-azaspiro[4.5]deca-3,6,9-triene-2,8-dione (3aa) Yellow solid (0.072 g, 92% yield). Mp 206.5−208.3 °C (uncorrected). ¹H NMR (400 MHz, CDCl₃): δ = 8.04 (d, J = 7.6 Hz, 2 H), 7.66 (t, J = 7.2 Hz, 1 H), 7.55 (t, J = 7.6 Hz, 2 H), 7.44 (t, J = 7.6 Hz, 1 H), 7.38 (t, J = 6.8 Hz, 2 H), 7.15 (d, J = 6.8 Hz, 2 H), 6.47−6.42 (m, 4 H), 2.83 (s, 3 H) ppm. ¹³C NMR (100 MHz, CDCl₃): δ = 183.0, 163.4, 162.1, 142.2, 139.1, 136.5, 134.3, 134.3, 130.3, 129.1, 129.0, 128.4, 127.9, 127.7, 68.2, 26.3 ppm. HRMS (ESI-TOF): m/z [M + K]⁺ calcd for C₂₂H₁₇KNO₄S: 430.0510; found: 430.0514.