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.

中文翻译：

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高对映选择性催化二-π-甲烷重排的开发


二π甲烷 （DPM） 重排是一种重要的有机光重排，可将含 1,4-二烯的化合物转化为乙烯基环丙烷，通常会导致基材碳框架的广泛、具有合成价值的重组。我们研究了 Lewis 和 Brønsted 酸对二苯并巴烯 DPM 重排的影响。这些研究最终确定了双手性 Brønsted 酸-铱光敏剂系统，该系统实现了第一个高对映选择性催化全碳 DPM 重排。