Ambimodal Trispericyclic Transition State and Dynamic Control of Periselectivity

Xiao-Song Xue; Cooper S Jamieson; Marc Garcia-Borràs; Xiaofei Dong; Zhongyue Yang; K N Houk

doi:10.1021/jacs.8b12674

Ambimodal Trispericyclic Transition State and Dynamic Control of Periselectivity

J Am Chem Soc. 2019 Jan 23;141(3):1217-1221. doi: 10.1021/jacs.8b12674. Epub 2019 Jan 14.

Authors

Xiao-Song Xue^{1

2}, Cooper S Jamieson², Marc Garcia-Borràs², Xiaofei Dong², Zhongyue Yang², K N Houk²

Affiliations

¹ State Key Laboratory of Elemento-Organic Chemistry, College of Chemistry , Nankai University , Tianjin 300071 , China.
² Department of Chemistry and Biochemistry , University of California, Los Angeles , Los Angeles , California 90095 , United States.

PMID: 30623652
DOI: 10.1021/jacs.8b12674

Abstract

We report an ambimodal trispericyclic transition state leading to [6+4]-, [4+6]-, and [8+2]-cycloadducts in the reactions of 8,8-disubstituted heptafulvenes with 6,6-dimethylfulvene. The potential energy surfaces for these reactions were explored with ωB97X-D density functional theory. Quasi-classical direct molecular dynamics simulations gave information on the ratios of products expected in these reactions.

Publication types

Research Support, Non-U.S. Gov't
Research Support, U.S. Gov't, Non-P.H.S.