A General Strategy for the Asymmetric Preparation of α‐Stereogenic Allyl Silanes, Germanes, and Boronate Esters via Dual Copper Hydride‐ and Palladium‐Catalysis

α‐Stereogenic allyl metalloids are versatile synthetic intermediates which can undergo various stereocontrolled transformations. Most existing methods to prepare α‐stereogenic allyl metalloids involve multi‐step sequences that curtail the number of compatible substrates and are limited to the synthe...

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Bibliographic Details
Published in:Angewandte Chemie 2022-11, Vol.134 (47), p.n/a
Main Authors: Levi Knippel, James, Ni, Anton Z., Schuppe, Alexander W., Buchwald, Stephen L.
Format: Article
Language:English
Subjects:
Allyl Boronate Ester
Allyl Metalloids
Allyl Silane
Asymmetric Catalysis
Catalysis
Chemistry
Copper
Copper Hydride
Enantiomers
Esters
Functional groups
Intermediates
Metalloids
Palladium
Sequences
Silanes
Substrates
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Summary:α‐Stereogenic allyl metalloids are versatile synthetic intermediates which can undergo various stereocontrolled transformations. Most existing methods to prepare α‐stereogenic allyl metalloids involve multi‐step sequences that curtail the number of compatible substrates and are limited to the synthesis of boronates. Here, we report a general method for the enantioselective preparation of α‐stereogenic allyl metalloids utilizing dual CuH‐ and Pd‐catalysis. This approach leverages a stereoretentive Cu‐to‐Pd transmetalation of an in situ generated alkyl copper species to allow access to enantioenriched allyl silanes, germanes, and boronate esters with broad functional group compatibility. A general method for the enantioselective preparation of α‐stereogenic allyl metalloids (M=B, Si, Ge) with broad functional group compatibility has been developed. This protocol employs dual CuH‐ and Pd‐catalysis to access a variety of allyl metalloid species from readily accessible vinyl metalloids and enol triflates.
ISSN:0044-8249
1521-3757
DOI:10.1002/ange.202212630