Accelerating a Mechanically Driven anti-Woodward鈥揌offmann Ring Opening with a Polymer Lever Arm Effect

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• 作者：Junpeng Wang ; Tatiana B. Kouznetsova ; Zhenbin Niu ; Arnold L. Rheingold ; Stephen L. Craig
• 刊名：Journal of Organic Chemistry
• 出版年：2015
• 出版时间：December 4, 2015
• 年：2015
• 卷：80
• 期：23
• 页码：11895-11898
• 全文大小：248K
• ISSN：1520-6904

文摘

Mechanical forces have previously been used to drive reactions along pathways that violate the orbital symmetry effects captured in the Woodward鈥揌offmann rules. Here, we show that a polymer 鈥渓ever arm effect鈥?can provide a mechanical advantage in accelerating the symmetry forbidden disrotatory ring opening of benzocyclobutene (BCB). Addition of an 伪-E-alkene to the BCB mechanophore drops the force required to induce reactions on the 鈭?.1 s time scale of single-molecule force spectroscopy experiments from 1370 to 920 pN.