Asymmetric Copper-Catalyzed C(sp)–H Bond Insertion of Carbenoids Derived from N-Tosylhydrazones

Abstract

A chiral copper(I)–phosphoramidite complex efficiently catalyzed the asymmetric insertion of the carbenoids derived from N-tosyl hydrazones into alkyne C–H bonds to give the corresponding chiral alkynylated products in up to 77% yield and with up to 74% ee.

Key words

copper catalysis - asymmetric catalysis - carbenoids - hydrazones - alkynes

• References and Notes

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• 13 Asymmetric Insertion Reactions; General ProcedureA mixture of CuI (1.9 mg, 10 μmol), (S)-Monophos (7.9 mg, 22 μmol), and Cs₂CO₃ (176 mg, 0.54 mmol) in 1,4-dioxane (2 mL) under N₂ was stirred at r.t. for 30 min. Hydrazone 1 (0.3 mmol) and alkyne 2 (0.2 mmol) were added, and the mixture was heated to 80 °C for 24 h. The resulting suspension was passed through short plug of silica gel (eluent: EtOAc), concentrated, and purified by preparative TLC and gel-permeation chromatography to give the corresponding insertion products. tert-Butyl[(3S)-3-(1-naphthyl)but-1-yn-1-yl]diphenylsilane (3aA)Colorless oil; yield: 64.5 mg (77%, 58% ee); [α]_D ²⁵ = +6.9 (c 0.37, CHCl₃). ¹H NMR (396 MHz, CDCl₃): δ = 8.15 (d, J = 8.7 Hz, 1 H), 7.80–7.89 (m, 6 H), 7.75 (d, J = 8.7 Hz, 1 H), 7.43–7.54 (m, 3 H), 7.30–7.40 (m, 6 H), 4.70 (q, J = 7.1 Hz, 1 H), 1.75 (d, J = 7.1 Hz, 3 H), 1.10 (s, 9 H). ¹³C{¹H} NMR (100 MHz, CDCl₃): δ = 138.6, 135.8, 134.2, 133.9, 130.6, 129.6, 129.2, 127.8, 127.7, 126.2, 125.8, 125.7, 124.6, 123.4, 114.2, 82.1, 30.0, 27.3, 23.7, 18.7. HRMS (APCI): m/z [M + H]⁺ calcd for C₃₀H₃₁Si: 419.2195; found: 419.2203. HPLC: ChiralPak AD-H column (hexane, flow rate 0.5 mL/min, λ = 280 nm); t _R = 13.7 min (minor isomer; integration: 322916 μV·s); t _R = 17.4 min (major isomer; integration: 1223585 μV·s).