Reactivity and Mechanism of a Mechanically Activated anti-Woodward-Hoffmann-DePuy Reaction

被引:58
作者
Wang, Junpeng [1 ]
Kouznetsova, Tatiana B. [1 ]
Craig, Stephen L. [1 ]
机构
[1] Duke Univ, Dept Chem, Durham, NC 27708 USA
基金
美国国家科学基金会;
关键词
MOLECULE FORCE SPECTROSCOPY; POLYMER MECHANOCHEMISTRY; ORBITAL SYMMETRY; METATHESIS CATALYST; OLEFIN METATHESIS; COVALENT BONDS; KINETICS; MECHANOPHORES; POLYBUTADIENE; CONSERVATION;
D O I
10.1021/jacs.5b06168
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Mechanical forces, applied via covalent polymer mechanochemistry, have been used to bias reaction pathways and activate otherwise inaccessible reactions. Here, single-molecule polymer mechanochemistry is used to induce the disrotatory outward ring opening of a cis-dialkyl substituted syn-chloro-gem-chlorofluorocyclopropane, in violation of the Woodward-Hoffmann-DePuy (WHD) rule. The forces required to trigger the anti-WHD pathway on the similar to 100 ms time scale of the experiment are about 200 pN greater than those involved in the WHD favored process (1290 vs 1500 pN). The kinetics are complemented by tension trapping experiments that suggest that the reaction proceeds along a reaction pathway that generates substantial diradicaloid character.
引用
收藏
页码:11554 / 11557
页数:4
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