Copper(I)-Catalyzed Carbometalation of Nonfunctionalized Cyclopropenes Using Organozinc and Grignard Reagents

Abstract

A highly efficient method was developed for the copper(I)-catalyzed carbometalation of various nonfunctionalized and functionalized cyclopropenes. Electrophilic trapping of the cyclopropylmetal intermediates gave multifunctionalized cyclopropanes.

Key words

alkenes - catalysis - copper - magnesium - metalation - nucleophilic additions - organometallic reagents - zinc

• References

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• 17 Carbozincation and Subsequent Trapping; Typical Procedures
  1,1′-(2-Ethylcyclopropane-1,1-diyl)dibenzene (2a-Et); Typical Procedure A 1.0 M solution of Et₂Zn in toluene (0.6 mL) was added to a solution of CuI (2.9 mg, 0.015 mmol) in toluene (1.5 mL) at r.t., and the mixture was stirred for 30 min. L1 (5.4 mg, 0.023 mmol) and 3,3-diphenylcyclopropene (1a; 57.7 mg, 0.3 mmol) were added at r.t., and the mixture was stirred for 16 h. The reaction was quenched with sat. aq NH₄Cl (2 mL), and the aqueous layer was separated and extracted with EtOAc (3 × 3 mL). The organic layers were combined, dried (Na₂SO₄), concentrated, and purified by column chromatography (silica gel, hexane) to give a colorless oil; yield: 57.2 mg (86%). 1,1′-(2-Ethyl-3-iodocyclopropane-1,1-diyl)dibenzene (3a-Et-I); Typical Procedure A 1.0 M soln of Et₂Zn in toluene (0.6 mL) was added to a solution of CuI (2.9 mg, 0.015 mmol) in toluene (1.5 mL) at r.t. and the mixture was stirred for 30 min. L1 (5.4 mg, 0.023 mmol) and 3,3-diphenylcyclopropene (1a; 57.7 mg, 0.3 mmol) were added at r.t. and the mixture was stirred for 6 h. CuI (116 mg, 0.6 mmol) and a solution of I₂ (228 mg, 0.9 mmol) in CH₂Cl₂ (1.5 mL) were then added, and the mixture was stirred for additional 15 h at 60 °C. The reaction was quenched with sat. aq NH₄Cl (3 mL), and the aqueous layer was separated and extracted with EtOAc (5 × 3 mL). The organic layers were combined, dried (Na₂SO₄), concentrated, and purified by column chromatography (silica gel, hexane) to give a colorless oil; yield 95.6 mg (86%)
• 18 Spontaneous decomposition of product 2g occurred under neutral, acidic, or basic conditions; the reason is unclear.
• 19 When cyclopropene 1f was used as a substrate, ring opening of the cyclopropylzinc intermediate also did not occur.
• 20 The relative configuration of products 5a and 5b could not be determined; see the Supporting Information.