Diastereoselective Substitution Reactions of Acyclic Acetals Controlled by Remote Participation of an Acyloxy Group

Khoi B. Luu; Amanda Ramdular; Eli Finkelstein; Alexander G. Shtukenberg; K. A. Woerpel

doi:10.1021/acs.orglett.4c03766

Diastereoselective Substitution Reactions of Acyclic Acetals Controlled by Remote Participation of an Acyloxy Group

Khoi B. Luu, Amanda Ramdular, Eli Finkelstein, Alexander G. Shtukenberg, K. A. Woerpel

Chemistry

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

Abstract

A remote carbonyl group up to six atoms away from the acetal group can induce 1,2-asymmetric induction in nucleophilic substitution reactions of acyclic acetals. Isolation of a cyclic carbonate under Lewis acidic conditions and computational studies suggested that the remote carbonyl group participated through the formation of a cyclic dioxocarbenium ion intermediate. The stereochemical outcomes depended on the size of the alkyl substituent and that of the nucleophile employed.

Original language	English (US)
Pages (from-to)	10470-10474
Number of pages	5
Journal	Organic Letters
Volume	26
Issue number	49
DOIs	https://doi.org/10.1021/acs.orglett.4c03766
State	Published - Dec 13 2024

ASJC Scopus subject areas

Biochemistry
Physical and Theoretical Chemistry
Organic Chemistry

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abstract = "A remote carbonyl group up to six atoms away from the acetal group can induce 1,2-asymmetric induction in nucleophilic substitution reactions of acyclic acetals. Isolation of a cyclic carbonate under Lewis acidic conditions and computational studies suggested that the remote carbonyl group participated through the formation of a cyclic dioxocarbenium ion intermediate. The stereochemical outcomes depended on the size of the alkyl substituent and that of the nucleophile employed.",

author = "Luu, {Khoi B.} and Amanda Ramdular and Eli Finkelstein and Shtukenberg, {Alexander G.} and Woerpel, {K. A.}",

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doi = "10.1021/acs.orglett.4c03766",

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AU - Finkelstein, Eli

AU - Shtukenberg, Alexander G.

AU - Woerpel, K. A.

PY - 2024/12/13

Y1 - 2024/12/13

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AB - A remote carbonyl group up to six atoms away from the acetal group can induce 1,2-asymmetric induction in nucleophilic substitution reactions of acyclic acetals. Isolation of a cyclic carbonate under Lewis acidic conditions and computational studies suggested that the remote carbonyl group participated through the formation of a cyclic dioxocarbenium ion intermediate. The stereochemical outcomes depended on the size of the alkyl substituent and that of the nucleophile employed.

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Diastereoselective Substitution Reactions of Acyclic Acetals Controlled by Remote Participation of an Acyloxy Group

Abstract

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