Cahoon Samuel B, Chapman Steven J, Fiala Tahoe A, Genzink Matthew J, Yoon Tehshik P
Department of Chemistry, University of Wisconsin-Madison, 1101 University Avenue, Madison, Wisconsin 53706, United States.
J Org Chem. 2024 Dec 6;89(23):17615-17620. doi: 10.1021/acs.joc.4c02383. Epub 2024 Nov 17.
The di-π-methane (DPM) rearrangement is an important organic photorearrangement that converts 1,4-diene-containing compounds to vinyl cyclopropanes, often resulting in extensive, synthetically valuable restructuring of the substrate's carbon framework. We investigated the influence of Lewis and Brønsted acids on the DPM rearrangement of dibenzobarrelenes. These studies have culminated in the identification of a dual chiral Brønsted acid-iridium photosensitizer system that enables the first highly enantioselective catalytic all-carbon DPM rearrangement.
二-π-甲烷（DPM）重排是一种重要的有机光重排反应，它能将含1,4-二烯的化合物转化为乙烯基环丙烷，常常导致底物碳骨架发生广泛的、具有合成价值的重排。我们研究了路易斯酸和布朗斯特酸对二苯并桶烯的DPM重排反应的影响。这些研究最终确定了一种双手性布朗斯特酸-铱光敏剂体系，该体系能够实现首例高度对映选择性催化全碳DPM重排反应。
