On the Configurational Stability and Reactivity of Tertiary Silyloxy Carbanions Derived from Stereoselective Brook Rearrangement

Juan F. Collados; Pablo Ortiz; Syuzanna R. Harutyunyan

doi:10.1002/ejoc.201600493

On the Configurational Stability and Reactivity of Tertiary Silyloxy Carbanions Derived from Stereoselective Brook Rearrangement

Juan F. Collados, Pablo Ortiz, Syuzanna R. Harutyunyan^*

^*Corresponding author for this work

Bioeconomy and CO2

University of Groningen

Research output: Contribution to journal › Article › peer-review

13 Citations (Scopus)

Abstract

Here we report a stereospecific Brook rearrangement/trapping sequence, initiated by the formation of a zinc alkoxide from an enantioenriched (hydroxyallyl)silane. The chiral carbanion resulting from the Brook rearrangement is trapped intermolecularly by carbonyl electrophiles with complete transfer of chirality. A concerted mechanism is proposed to rationalize the stereospecificity observed in the reaction sequence.

Original language	English
Pages (from-to)	3065-3069
Number of pages	5
Journal	European Journal of Organic Chemistry
Volume	2016
Issue number	18
DOIs	https://doi.org/10.1002/ejoc.201600493
Publication status	Published - Jun 2016

Keywords

Alcohols
Brook rearrangement
Carbanions
Chirality
Enantioselectivity
Hydroxysilanes
Trapping reactions

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10.1002/ejoc.201600493

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title = "On the Configurational Stability and Reactivity of Tertiary Silyloxy Carbanions Derived from Stereoselective Brook Rearrangement",

abstract = "Here we report a stereospecific Brook rearrangement/trapping sequence, initiated by the formation of a zinc alkoxide from an enantioenriched (hydroxyallyl)silane. The chiral carbanion resulting from the Brook rearrangement is trapped intermolecularly by carbonyl electrophiles with complete transfer of chirality. A concerted mechanism is proposed to rationalize the stereospecificity observed in the reaction sequence.",

keywords = "Alcohols, Brook rearrangement, Carbanions, Chirality, Enantioselectivity, Hydroxysilanes, Trapping reactions",

author = "Collados, \{Juan F.\} and Pablo Ortiz and Harutyunyan, \{Syuzanna R.\}",

note = "Publisher Copyright: {\textcopyright} 2016 WILEY-VCH Verlag GmbH \& Co. KGaA, Weinheim",

year = "2016",

month = jun,

doi = "10.1002/ejoc.201600493",

language = "English",

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pages = "3065--3069",

journal = "European Journal of Organic Chemistry",

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publisher = "Wiley-VCH Verlag",

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T1 - On the Configurational Stability and Reactivity of Tertiary Silyloxy Carbanions Derived from Stereoselective Brook Rearrangement

AU - Collados, Juan F.

AU - Ortiz, Pablo

AU - Harutyunyan, Syuzanna R.

PY - 2016/6

Y1 - 2016/6

N2 - Here we report a stereospecific Brook rearrangement/trapping sequence, initiated by the formation of a zinc alkoxide from an enantioenriched (hydroxyallyl)silane. The chiral carbanion resulting from the Brook rearrangement is trapped intermolecularly by carbonyl electrophiles with complete transfer of chirality. A concerted mechanism is proposed to rationalize the stereospecificity observed in the reaction sequence.

AB - Here we report a stereospecific Brook rearrangement/trapping sequence, initiated by the formation of a zinc alkoxide from an enantioenriched (hydroxyallyl)silane. The chiral carbanion resulting from the Brook rearrangement is trapped intermolecularly by carbonyl electrophiles with complete transfer of chirality. A concerted mechanism is proposed to rationalize the stereospecificity observed in the reaction sequence.

KW - Alcohols

KW - Brook rearrangement

KW - Carbanions

KW - Chirality

KW - Enantioselectivity

KW - Hydroxysilanes

KW - Trapping reactions

UR - https://www.scopus.com/pages/publications/84977090506

U2 - 10.1002/ejoc.201600493

DO - 10.1002/ejoc.201600493

M3 - Article

AN - SCOPUS:84977090506

SN - 1434-193X

VL - 2016

SP - 3065

EP - 3069

JO - European Journal of Organic Chemistry

JF - European Journal of Organic Chemistry

IS - 18

ER -

On the Configurational Stability and Reactivity of Tertiary Silyloxy Carbanions Derived from Stereoselective Brook Rearrangement

Abstract

Keywords

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