Highly Diastereoselective Synthesis of Spirocyclopropane-oxindoles Using InCl₃ as a Catalyst in Water

Abstract

A highly diastereoselective method to synthesize a series of spiro[cyclopropane-1,3-oxindoles] from 3-diazooxindoles and chalcones using InCl₃ as the catalyst in water is demonstrated.

Key words

3-diazooxindoles - diastereoselectivity - indium(III) chloride - spirocyclopropanes - water

• References and Notes


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• 13 Typical Procedure for the Preparation of Spiro-cyclopropaneoxindoles To a solution of InCl₃ (15 mg, 20 mol%) in H₂O (5 mL) was added diazoamide 1e (100 mg, 0.35 mmol) and (E)-3-(4-methoxyphenyl)-1-phenylprop-2-en-1-one (100 mg, 0.42 mmol) under an air atmosphere. The reaction mixture was stirred at ambient temperature for 16 h and extracted with EtOAc (3 × 25 mL). The organic phase was dried over Na₂SO₄, filtered, and concentrated in vacuo. The residue was purified by column chromatography using silica gel (hexanes–EtOAc) to afford cyclopropane 3d (126 mg, 73%) as a colorless solid. 2-Benzoyl-1′-benzyl-5′-chloro-3-phenylspiro[cyclopropane-1,3′-indol]-2′(1′H)-one (3d) Colorless solid; yield 68%; mp 173–175 °C. IR (ATR): ν_max = 2928, 2855, 1731, 1608, 1468, 1353, 1300, 1188, 1163, 1094, 753 cm^–1. ¹H NMR (400 MHz, CDCl₃): δ = 3.79 (s, 3 H, OCH₃), 4.09 (d, 1 H, J = 8.0 Hz, CH), 4.25 (d, 1 H, J = 8.0 Hz, CH), 4.89 (d, 1 H, J = 15.6 Hz, CHH), 4.96 (d, 1 H, J = 15.2 Hz, CHH),6.76 (d, 1 H, J = 7.2 Hz, ArH), 6.86 (d, 2 H, J = 8.0 Hz, ArH), 6.94 (t, 1 H, J = 6.8 Hz, ArH), 7.12 (t, 1 H, J = 6.8 Hz, ArH), 7.21–7.36 (m, 10 H, ArH), 7.86 (d, 2 H, J = 8.0 Hz, ArH). ¹³C NMR (100 MHz, CDCl₃): δ = 39.3 (CH₃), 41.6 (quat-C) 41.6 (CH), 44.1, (CH₂), 55.2 (OCH₃), 109.0 (=CH), 113.7 (=CH), 121.8 (=CH), 122.5 (=CH), 125.1 (quat-C), 125.9 (quat-C), 127.3 (=CH), 127.6 (=CH), 127.7 (=CH), 128.8 (=CH), 129.1 (=CH), 129.8 (=CH), 130.3 (=CH), 135.4 (quat-C), 136.1 (quat-C), 140.2 (quat-C), 142.8 (quat-C), 159.1 (quat-C), 172.1 (C=O), 191.9 (C=O). HRMS (ESI⁺): m/z calcd for C₃₁H₂₄ClNO₃ [M + H]⁺: 494.1523; found: 494.1529.

3-Diazooxindole 1 and the alkenes could not be dissolved in water, however, the reaction proceeded smoothly. For discussions about transformations ‘in water’ or ‘on water’, see:
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