Enantiospecific Brook Rearrangement of Tertiary Benzylic α‐Hydroxysilanes

The Brook rearrangement of simple, chiral tertiary benzylic α‐hydroxysilanes is presented. The rearrangement followed by proton trapping is enantiospecific and proceeds with inversion of the configuration at the carbon center. Importantly, the [1,2]‐Brook rearrangement can be followed by trapping of...

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Bibliographic Details
Published inEuropean journal of organic chemistry Vol. 2018; no. 29; pp. 3900 - 3903
Main Authors Collados, Juan F., Ortiz, Pablo, Pérez, Juana M., Xia, Yiyin, Koenis, Mark A. J., Buma, Wybren J., Nicu, Valentin P., Harutyunyan, Syuzanna R.
Format Journal Article
LanguageEnglish
Published WEINHEIM Wiley 07.08.2018
Wiley Subscription Services, Inc
Subjects
Chemistry
Chemistry, Organic
Chirality
Enantiospecific
Hydroxysilanes
Physical Sciences
Rearrangement
Science & Technology
Synthetic methods
Trapping
Enantiospecific
CARBON
ACYLATION
STEREOCHEMISTRY
ALKOXYSILANE
SILYLCARBINOL
CHIRAL MOLECULES
ANIONIC REARRANGEMENTS
ABSOLUTE-CONFIGURATION
Chirality
Synthetic methods
Hydroxysilanes
Rearrangement
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Summary:The Brook rearrangement of simple, chiral tertiary benzylic α‐hydroxysilanes is presented. The rearrangement followed by proton trapping is enantiospecific and proceeds with inversion of the configuration at the carbon center. Importantly, the [1,2]‐Brook rearrangement can be followed by trapping of methyl or allyl electrophiles even in the protic environment, although with minimal retention of chirality. Chiral tertiary benzylic α‐hydroxysilanes, upon treatment with LiOtBu, undergo Brook rearrangement, which is enantiospecific and proceeds with inversion of the configuration.
ISSN:1434-193X
1099-0690
DOI:10.1002/ejoc.201701469