Work

Enantioselective Miyaura Reaction by Desymmetrizing C(sp 2 )–B Cross‐Coupling of 1,1′‐Biaryl‐2,6‐diyl Bis(nonaflates)

Year: 2025

Type: article

Abstract: )-B cross-coupling of achiral 1,1'-biaryl-2,6-diyl bis(nonaflates) and B-B reagents is disclosed. An in situ-formed palladium(0)-(S,S)-f-Binaphane complex discriminates between the enantiotopic nonaflate groups, and the subsequent transmetalation of the B-B reagent is enhanced by a copper co-catalyst. The enantiomeric excess of the chiral monoborylated product after reductive elimination is further improved by a downstream kinetic resolution, thereby converting the minor enantiomer into the corresponding achiral bisborylated biaryl byproduct. This enantioselective Miyaura reaction enables the synthesis of highly valuable, axially chiral boron compounds with superb enantiomeric ratios (up to e.r. = 99:1) and exhibits broad substrate scope and good functional-group tolerance.

Source: Angewandte Chemie International Edition

DOI: 10.1002/anie.202515234

Authors: Yao Xiao, Annika L. Bartelt, Elisabeth Irran, Martin Oestreich

Institution: Technische Universität Berlin

Language: English

Topic: Catalytic Cross-Coupling Reactions

Subfield: Organic Chemistry

Field: Chemistry

Domain: Physical Sciences

Open Access status: hybrid

Estimated APC paid: $5,510

Funders: China Scholarship Council, Einstein Stiftung Berlin