Diiodine–Triethylsilane System: Reduction of N-Sulfonyl Aldimines to N-Alkylsulfonamides

Abstract

Because molecular iodine and hydrosilanes are stable to both air and moisture, reactions using these reagents are easy to operate and require mild reaction conditions. Molecular iodine and a hydrosilane were used to reduce N-sulfonyl aldimines to the corresponding N-alkylsulfonamides. This transformation is a practical method for the synthesis of N-alkylsulfonamides.

Key words

imines - iodine - reduction - hydrosilanes - sulfonamides

Publication History

Received: 25 August 2020

Accepted after revision: 24 September 2020

Article published online:
19 October 2020

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• 20 N-Benzyl-4-methylbenzenesulfonamide (2a); Typical ProcedureA flask was successively charged with HSiEt₃ (232.6 mg, 2.0 mmol, 2.0 equiv), N-sulfonyl aldimine 1a (259.3 mg, 1.0 mmol, 1.0 equiv), DCM (2.0 mL), and I₂ (126.9 mg, 0.5 mmol, 0.5 equiv), and the mixture was stirred at rt for 30 min. DCM (20.0 mL) and 0.5 M aq Na₂S₂O₃ (10 mL) were added to the flask, and the organic layer was separated, washed with brine, dried (Na₂SO₄), filtered, concentrated, and purified by flash column chromatography [silica gel (200–300 mesh), PE–EtOAc (4:1)] to give a white solid; yield: 178.2 mg (68%); mp 117–118 °C.¹H NMR (600 MHz, CDCl₃): δ = 7.75 (d, J = 8.4 Hz, 2 H), 7.30 (d, J = 8.4 Hz, 2 H), 7.28–7.23 (m, 3 H), 7.22–7.16 (m, 2 H), 4.93–4.80 (m, 1 H), 4.11 (d, J = 6.6 Hz, 2 H), 2.44 (s, 3 H). ¹³C NMR (150 MHz, CDCl₃): δ = 143.6, 136.9, 136.4, 129.9, 128.8, 128.0, 127.3, 47.4, 21.7.