High Reactivity of Strained Seven-Membered-Ring trans-Alkenes

Jillian R. Sanzone; K. A. Woerpel

doi:10.1002/anie.201510056

High Reactivity of Strained Seven-Membered-Ring trans-Alkenes

Jillian R. Sanzone, K. A. Woerpel

Chemistry

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

Abstract

trans-Oxasilacycloheptenes are highly reactive strained alkenes. Competition reactions showed that these seven-membered ring trans-alkenes underwent [4+2] cycloaddition reactions faster than a trans-cyclooctene. They also reacted with quinones and dimethyl acetylenedicarboxylate to form adducts with high diastereoselectivity. Kinetic studies showed that ring strain increases nucleophilicity by approximately 10⁹. trans-Oxasilacycloheptenes are strained seven-membered-ring trans-alkenes that underwent [4+2] cycloaddition reactions faster than a bicyclic trans-cyclooctene. They also reacted with quinones and dimethyl acetylenedicarboxylate to form adducts with high diastereoselectivity. Kinetic studies showed that ring strain increases nucleophilicity by approximately 10⁹.

Original language	English (US)
Pages (from-to)	790-793
Number of pages	4
Journal	Angewandte Chemie - International Edition
Volume	55
Issue number	2
DOIs	https://doi.org/10.1002/anie.201510056
State	Published - Jan 11 2016

Keywords

alkenes
cycloaddition
cycloheptenes
silicon
strained molecules

ASJC Scopus subject areas

Catalysis
General Chemistry

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10.1002/anie.201510056

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title = "High Reactivity of Strained Seven-Membered-Ring trans-Alkenes",

abstract = "trans-Oxasilacycloheptenes are highly reactive strained alkenes. Competition reactions showed that these seven-membered ring trans-alkenes underwent [4+2] cycloaddition reactions faster than a trans-cyclooctene. They also reacted with quinones and dimethyl acetylenedicarboxylate to form adducts with high diastereoselectivity. Kinetic studies showed that ring strain increases nucleophilicity by approximately 109. trans-Oxasilacycloheptenes are strained seven-membered-ring trans-alkenes that underwent [4+2] cycloaddition reactions faster than a bicyclic trans-cyclooctene. They also reacted with quinones and dimethyl acetylenedicarboxylate to form adducts with high diastereoselectivity. Kinetic studies showed that ring strain increases nucleophilicity by approximately 109.",

keywords = "alkenes, cycloaddition, cycloheptenes, silicon, strained molecules",

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

note = "Funding Information: This research was supported by the National Science Foundation (CHE-1362709). We thank Dr. Chin Lin (NYU) for assistance with NMR spectrometry and mass spectrometry. We thank Dr. Chunhua Hu (NYU) for X-ray analysis and the NYU Molecular Design Institute for purchasing a singlecrystal diffractometer. Publisher Copyright: {\textcopyright} 2016 Wiley-VCH Verlag GmbH & Co. KGaA.",

year = "2016",

month = jan,

day = "11",

doi = "10.1002/anie.201510056",

language = "English (US)",

volume = "55",

pages = "790--793",

journal = "Angewandte Chemie - International Edition",

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AU - Sanzone, Jillian R.

AU - Woerpel, K. A.

N1 - Funding Information: This research was supported by the National Science Foundation (CHE-1362709). We thank Dr. Chin Lin (NYU) for assistance with NMR spectrometry and mass spectrometry. We thank Dr. Chunhua Hu (NYU) for X-ray analysis and the NYU Molecular Design Institute for purchasing a singlecrystal diffractometer. Publisher Copyright: © 2016 Wiley-VCH Verlag GmbH & Co. KGaA.

PY - 2016/1/11

Y1 - 2016/1/11

N2 - trans-Oxasilacycloheptenes are highly reactive strained alkenes. Competition reactions showed that these seven-membered ring trans-alkenes underwent [4+2] cycloaddition reactions faster than a trans-cyclooctene. They also reacted with quinones and dimethyl acetylenedicarboxylate to form adducts with high diastereoselectivity. Kinetic studies showed that ring strain increases nucleophilicity by approximately 109. trans-Oxasilacycloheptenes are strained seven-membered-ring trans-alkenes that underwent [4+2] cycloaddition reactions faster than a bicyclic trans-cyclooctene. They also reacted with quinones and dimethyl acetylenedicarboxylate to form adducts with high diastereoselectivity. Kinetic studies showed that ring strain increases nucleophilicity by approximately 109.

AB - trans-Oxasilacycloheptenes are highly reactive strained alkenes. Competition reactions showed that these seven-membered ring trans-alkenes underwent [4+2] cycloaddition reactions faster than a trans-cyclooctene. They also reacted with quinones and dimethyl acetylenedicarboxylate to form adducts with high diastereoselectivity. Kinetic studies showed that ring strain increases nucleophilicity by approximately 109. trans-Oxasilacycloheptenes are strained seven-membered-ring trans-alkenes that underwent [4+2] cycloaddition reactions faster than a bicyclic trans-cyclooctene. They also reacted with quinones and dimethyl acetylenedicarboxylate to form adducts with high diastereoselectivity. Kinetic studies showed that ring strain increases nucleophilicity by approximately 109.

KW - alkenes

KW - cycloaddition

KW - cycloheptenes

KW - silicon

KW - strained molecules

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High Reactivity of Strained Seven-Membered-Ring trans-Alkenes

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Keywords

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