Experimental and Theoretical Investigation of the Synchronicity of Ambident Silyloxypyrone-Based (5+2) Cycloadditions

被引：1

作者：

Youman, Adam J. ^{[1
]}

Rokey, Samantha N. ^{[1
]}

Grabowski, Jacob P. ^{[1
]}

Guo, Wentao ^{[2
]}

Sun, Qing ^{[2
]}

Angles, Susanna N. ^{[1
]}

Goodell, John R. ^{[1
]}

Tantillo, Dean J. ^{[2
]}

Mitchell, T. Andrew ^{[1
]}

机构：

[1] Illinois State Univ, Dept Chem, Normal, IL 61790 USA

[2] Univ Calif Davis, Dept Chem, Davis, CA 95616 USA

来源：

JOURNAL OF ORGANIC CHEMISTRY | 2023年 / 88卷 / 09期

基金：

美国国家科学基金会;

关键词：

DIELS-ALDER REACTIONS; 1.3-DIPOLARE CYCLOADDITIONEN; STEPWISE MECHANISM; GAMMA-PYRONES; OXIDOPYRYLIUM; GENERATION; PATHWAYS; ALKENES;

D O I：

10.1021/acs.joc.3c00318

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The reaction pathway of silyloxypyrone-based (5 + 2) cycloadditions was determined to be extremely dependent on the nature of the dipolarophile. Neutral alkenes were the least reactive, whereas both electron-deficient and electron-rich dipolarophiles were more reactive, thus providing evidence for ambident oxidopyrylium intermediates. Qualitative rate studies, Hammett linear free energy relationships, and theoretical calculations combined to provide evidence for a spectrum of reactivity that passes through the borderlands of concerted and stepwise.

引用

页码：5972 / 5981

页数：10

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