Rhodium‐Catalyzed Synthesis of Chiral Monohydrosilanes by Intramolecular C−H Functionalization of Dihydrosilanes

The preparation of chiral monohydrosilanes remains a rarely achieved goal. To this end a Rh‐catalyzed desymmetrization of dihydrosilanes by way of intramolecular C(sp2)−H functionalization under simple and mild conditions has now been developed. This method provides easy access to a broad range of c...

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Bibliographic Details
Published in:Angewandte Chemie International Edition Vol. 60; no. 8; pp. 4245 - 4251
Main Authors: Ma, Wenpeng, Liu, Li‐Chuan, An, Kun, He, Tao, He, Wei
Format: Journal Article
Language:English
Published: WEINHEIM Wiley 19.02.2021
Wiley Subscription Services, Inc
Edition:International ed. in English
Subjects:
Chemical synthesis
Chemistry
Chemistry, Multidisciplinary
desymmetrization
dihydrosilanes
enantioselectivity
monohydrosilane
Physical Sciences
Rhodium
Science & Technology
Silicon
Silicon compounds
Stereochemistry
enantioselectivity
desymmetrization
ASYMMETRIC-SYNTHESIS
ENANTIOSELECTIVE SYNTHESIS
HYDROSILYLATION
dihydrosilanes
SILICON-STEREOGENIC SILANES
KETONES
SILACYCLOBUTANES
DEHYDROGENATIVE SILYLATION
CONSTRUCTION
monohydrosilane
BOND ACTIVATION
rhodium
ISSN:1433-7851, 1521-3773, 1521-3773
Online Access:Get full text
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Summary:The preparation of chiral monohydrosilanes remains a rarely achieved goal. To this end a Rh‐catalyzed desymmetrization of dihydrosilanes by way of intramolecular C(sp2)−H functionalization under simple and mild conditions has now been developed. This method provides easy access to a broad range of chiral monohydrosilanes in good yields with excellent enantioselectivities (up to >99 % ee). The resulting monohydrosilanes constitute a good platform to access stereogenic silicon compounds, as well as useful compounds to probe silicon stereochemistry. A Rh‐chiral diphosphine complex was found to catalyze desymmetrization of dihydrosilanes by formal intramolecular Si−H/C−H dehydrogenative coupling reactions. This simple, mild, and practical method results in unprecedently high enantioselectivity and a broad substrate scope. The chiral monohydrosilanes could be further elaborated into various stereogenic silicon compounds in a stereospecific manner.
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ISSN:1433-7851
1521-3773
1521-3773
DOI:10.1002/anie.202013041