Catalytic asymmetric C-Si bond activation via torsional strain-promoted Rh-catalyzed aryl-Narasaka acylation.

Abstract:

:Atropisomers are important organic frameworks in bioactive natural products, drugs as well as chiral catalysts. Meanwhile, silanols display unique properties compared to their alcohol analogs, however, the catalytic synthesis of atropisomers bearing silanol groups is challenging. Here, we show a rhodium-catalyzed torsional strain-promoted asymmetric ring-opening reaction for the synthesis of α-silyl biaryl atropisomers. The reaction features a dynamic kinetic resolution of C(Ar)-Si bond cleavage, whose stereochemistry was controlled by a phosphoramidite ligand derived from (S)-3-methyl-1-((2,4,6-triisopropylphenyl)sulfonyl)piperazine. This work is a demonstration of an aryl-Narasaka acylation, where the C(Ar)-Si bond cleavage is promoted by the torsional strain of α, α'-disubstituted silafluorene.

journal_name

Nat Commun

journal_title

Nature communications

authors

Feng J,Bi X,Xue X,Li N,Shi L,Gu Z

doi

10.1038/s41467-020-18273-3

subject

Has Abstract

pub_date

2020-09-07 00:00:00

pages

4449

issue

1

issn

2041-1723

pii

10.1038/s41467-020-18273-3

journal_volume

11

pub_type

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