Indium(III) Chloride Promoted Highly Efficient Tandem Rearrangement–α-Addition Strategy towards the Synthesis of α-Hydroxyamides

Abstract

A new tandem process is reported that provides access to α-hydroxyamides from epoxides for the first time. Herein, we explore ­InCl₃-mediated tandem rearrangement of epoxides to aldehydes and α-addition of TosMIC to in situ derived aldehydes. An unprecedented C–C bond-forming reaction is disclosed that features mild conditions, high yields, and shorter reaction times.

Key words

C–C bond formation - indium(III) chloride - epoxides - TosMIC - tandem rearrangement - α-addition

• References and Notes

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• 20 General Experimental Procedure (Table 3, Entry 1) A solution of styrene oxide (120 mg, 1.0 mmol), TosMIC (195 mg, 1.0 mmol), and InCl₃ (110 mg, 0.5 mmol) in THF–H₂O (9:1, 2 mL) was stirred at ambient temperature until completion (TLC). The resulting solution was partitioned between an equimolar ratio of Et₂O (2 × 20 mL), the combined organic layers were washed with brine (1 × 20 mL), dried (Na₂SO₄), evaporated under vacuum, and the residue thus obtained was purified by column chromatography (silica gel 60–120 mesh, EtOAc–n-hexane, 3.0:7.0) to afford 2a. 2-Hydroxy-3-phenyl-N-(tosylmethyl)propanamide (2a) Yellow solid (290 mg, 90% yield), mp 125–127 °C. ¹H NMR (500 MHz, CDCl₃): δ = 7.78 (d, J = 8.2 Hz, 2 H), 7.56 (br s, 1 H, NH), 7.39–7.15 (m, 7 H), 4.65 (d, J = 6.9 Hz, 1 H), 4.19 (dd, J = 9.4, 3.4 Hz, 1 H), 3.04 (dd, J = 13.9, 3.0 Hz, 1 H), 2.62 (dd, J = 14.0, 9.4 Hz, 1 H), 2.44 (s, 3 H). ¹³C NMR (125 MHz, CDCl₃): δ = 172.6, 145.5, 136.6, 133.7, 129.9, 129.4, 128.9, 128.7, 127.1, 72.8, 59.9, 40.5, 21.7. ESI-MS: m/z = 334 [M + H]⁺. HRMS: m/z calcd for C₁₇H₁₉O₄NNaS [M + Na]⁺: 356.0927; found: 356.09226.