Synlett 2015; 26(05): 671-675
DOI: 10.1055/s-0034-1379959
letter
© Georg Thieme Verlag Stuttgart · New York

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

Takeo Nakano
a   Division of Material Sciences, Graduate School of Natural Science and Technology, Kanazawa University, Kakuma, Kanazawa 920-1192, Japan   Email: kendo@se.kanazawa-u.ac.jp
,
Kohei Endo*
a   Division of Material Sciences, Graduate School of Natural Science and Technology, Kanazawa University, Kakuma, Kanazawa 920-1192, Japan   Email: kendo@se.kanazawa-u.ac.jp
b   PRESTO, Japan Science and Technology Agency (JST), 4-1-8 Honcho Kawaguchi, Saitama, 332-0012, Japan
,
Yutaka Ukaji
a   Division of Material Sciences, Graduate School of Natural Science and Technology, Kanazawa University, Kakuma, Kanazawa 920-1192, Japan   Email: kendo@se.kanazawa-u.ac.jp
› Author Affiliations
Further Information

Publication History

Received: 14 October 2014

Accepted after revision: 27 November 2014

Publication Date:
15 January 2015 (online)


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.

Supporting Information

 
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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.