Participation of Alkoxy Groups in Reactions of Acetals: Violation of the Reactivity/Selectivity Principle in a Curtin-Hammett Kinetic Scenario

Angie Garcia; Jillian R. Sanzone; K. A. Woerpel

doi:10.1002/anie.201503525

Participation of Alkoxy Groups in Reactions of Acetals: Violation of the Reactivity/Selectivity Principle in a Curtin-Hammett Kinetic Scenario

Angie Garcia, Jillian R. Sanzone, K. A. Woerpel

Chemistry

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

Abstract

Nucleophilic substitution reactions of acetals having benzyloxy groups four carbon atoms away can be highly diastereoselective. The selectivity in several cases increased as the reactivity of the nucleophile increased, in violation of the reactivity/selectivity principle. The increase in selectivity with reactivity suggests that multiple conformational isomers of reactive intermediates can give rise to the products.

Original language	English (US)
Pages (from-to)	12087-12090
Number of pages	4
Journal	Angewandte Chemie - International Edition
Volume	54
Issue number	41
DOIs	https://doi.org/10.1002/anie.201503525
State	Published - Oct 1 2015

Keywords

allylic compounds
carbocations
nucleophilic substitution
synthetic methods
through-space interactions

ASJC Scopus subject areas

Catalysis
General Chemistry

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10.1002/anie.201503525

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abstract = "Nucleophilic substitution reactions of acetals having benzyloxy groups four carbon atoms away can be highly diastereoselective. The selectivity in several cases increased as the reactivity of the nucleophile increased, in violation of the reactivity/selectivity principle. The increase in selectivity with reactivity suggests that multiple conformational isomers of reactive intermediates can give rise to the products.",

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author = "Angie Garcia and Sanzone, {Jillian R.} and Woerpel, {K. A.}",

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AU - Woerpel, K. A.

PY - 2015/10/1

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AB - Nucleophilic substitution reactions of acetals having benzyloxy groups four carbon atoms away can be highly diastereoselective. The selectivity in several cases increased as the reactivity of the nucleophile increased, in violation of the reactivity/selectivity principle. The increase in selectivity with reactivity suggests that multiple conformational isomers of reactive intermediates can give rise to the products.

KW - allylic compounds

KW - carbocations

KW - nucleophilic substitution

KW - synthetic methods

KW - through-space interactions

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Participation of Alkoxy Groups in Reactions of Acetals: Violation of the Reactivity/Selectivity Principle in a Curtin-Hammett Kinetic Scenario

Abstract

Keywords

ASJC Scopus subject areas

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