Work

Iridium-Catalyzed Stereocontrolled C(sp 3 )–C(sp 3 ) Cross-Coupling of Boronic Esters and Allylic Carbonates Enabled by Boron-to-Zinc Transmetalation

Year: 2025

Type: article

Abstract: High Resolution Image Download MS PowerPoint Slide The stereocontrolled C(sp 3 )–C(sp 3 ) cross-coupling represents a considerable challenge of great contemporary interest. While this has been achieved through the reactions of boronate complexes with π-allyl iridium complexes, such reactions suffered from a limited substrate scope. We now report that following transmetalation from boronate complexes to organozinc reagents enables previously unreactive substrates to engage in stereocontrolled C(sp 3 )–C(sp 3 ) cross-coupling. The broader substrate scope has enabled their application to the synthesis of biologically active molecules. The organozinc reagents react through a stereoinvertive coupling pathway with π-allyl iridium complexes, in contrast to reactions with other electrophiles that occur with retention of stereochemistry. The reaction uniquely combines the enantiospecific reactivity of an enantioenriched organometallic nucleophile with the enantioselective engagement of a racemic electrophile, enabling access to all stereoisomers.

Source: Journal of the American Chemical Society

DOI: 10.1021/jacs.4c17931

Authors: Hong-Cheng Shen, Varinder K. Aggarwal

Institution: University of Bristol

Language: English

Topic: Catalytic Cross-Coupling Reactions

Subfield: Organic Chemistry

Field: Chemistry

Domain: Physical Sciences

Open Access status: hybrid

Estimated APC paid: $4,500

Funders: Engineering and Physical Sciences Research Council, Biotechnology and Biological Sciences Research Council