Department of Chemistry, State University of New York, Stony Brook, New York 11794, United States.
Department of Chemistry, University of Pittsburgh, Pittsburgh, Pennsylvania 15260, United States.
J Am Chem Soc. 2022 Mar 2;144(8):3353-3359. doi: 10.1021/jacs.1c13299. Epub 2022 Feb 21.
Excited-state palladium catalysis has emerged as a promising strategy for developing novel and valuable reactions. Herein, we report the first excited-state Pd-catalyzed 1,2-radical migratory Mizoroki-Heck reaction that enables C2-alkenylation of carbohydrates using readily available 1-bromosugars and alkenes. The reaction tolerates a wide variety of functional groups and complex molecular architectures, including derivatives of natural products and marketed drugs. Preliminary mechanistic studies and DFT calculations suggest the involvement of visible-light-induced photoexcitation of Pd species, 1,2-spin-centered-shift (SCS) process, and Heck-type cross-coupling reaction. The reaction expands the reactivity profile of excited-state Pd catalysis and provides a streamlined protocol for the preparation of a wide variety of C2-alkenylated carbohydrate mimetics to aid the discovery and development of new therapeutics, agrochemicals, and materials.
激发态钯催化已成为开发新型有价值反应的一种很有前途的策略。在此，我们报告了首例激发态 Pd 催化的 1,2-自由基迁移 Mizoroki-Heck 反应，该反应可使用易得的 1-溴代糖和烯烃实现碳水化合物的 C2-烯丙基化。该反应可耐受多种官能团和复杂分子结构，包括天然产物和市售药物的衍生物。初步的机理研究和 DFT 计算表明，可见光诱导的 Pd 物种光激发、1,2-自旋中心转移（SCS）过程和 Heck 型交叉偶联反应的参与。该反应扩展了激发态钯催化的反应性谱，并提供了一种简化的方案，用于制备各种 C2-烯丙基化的碳水化合物模拟物，以辅助新疗法、农用化学品和材料的发现和开发。
