Carbene Transfer and Carbene Insertion Reactions Catalyzed by a Mixed‐Ligand Copper(I) Complex. Issue 25 (27th June 2018)

• Record Type: Journal Article
• Authors: Brenna, Stefano; Ardizzoia, G. Attilio
• Is Part Of: European journal of organic chemistry. Issue 25(2018)
• Page Start: 3336
• Page End: 3342
• Publication Date: 2018-06-27
• Subjects: Carbenes -- Homogeneous catalysis -- Cyclopropanation -- Copper -- Phosphines; Chemistry, Organic -- Periodicals; Organic compounds -- Synthesis -- Periodicals; Bioorganic chemistry -- Periodicals; Chemistry, Physical organic -- Periodicals; 547
• DOI: 10.1002/ejoc.201800863
• Languages: English
• ISSNs: 1434-193X

Abstract

Abstract : The catalytic activity of the mixed‐ligand copper(I) complex [Cu(PPh3 )2 (κ 2 ‐O, O"‐lact)] (1 ) {lact =l ‐(+)‐lactate} has been investigated in carbene transfer and carbene insertion reactions. Complex1 catalytically promoted the diastereoselective cyclopropanation of olefins in the presence of ethyl diazoacetate (EDA), under mild conditions, and with a low catalyst loading (1 mol‐%). In the case of internal alkenes, a trans/cis ratio of up to 93:7 was reached. Moreover, compound1 easily promoted the insertion of the carbene fragment deriving from the decomposition of ethyl diazoacetate into O–H (alcohols and phenols) and N–H (amine) bonds, with formation of the corresponding ethyl 2‐alkoxyacetate, ethyl 2‐phenoxyacetate, and ethyl 2‐aminoacetate derivatives in good to high yields. Abstract : An easily prepared low‐cost copper(I) homogeneous catalyst has been investigated in carbene transfer reactions. High yields and selectivities were achieved in olefin cyclopropanation and O–H and N–H insertions.