State Key Laboratory of Coordination Chemistry, Jiangsu Key Laboratory of Advanced Organic Materials, Chemistry and Biomedicine Innovation Center (ChemBIC), School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, 210023, China.
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Shanghai, 200032, China.
Nat Commun. 2022 Jul 22;13(1):4224. doi: 10.1038/s41467-022-31956-3.
Selective deuteration of unactivated C(sp)-H bonds is a highly attractive but challenging subject of research in pharmaceutical chemistry, material science and synthetic chemistry. Reported herein is a practical, highly selective and economical efficient hydrogen/deuterium (H/D) exchange of unactivated C(sp)-H bonds by synergistic photocatalysis and hydrogen atom transfer (HAT) catalysis. With the easily prepared PMP-substituted amides as nitrogen-centered radical precursors, a wide range of structurally diverse amides can undergo predictable radical H/D exchange smoothly with inexpensive DO as the sole deuterium source, giving rise to the distal tertiary, secondary and primary C(sp)-H bonds selectively deuterated products in yields of up to 99% and excellent D-incorporations. In addition to precise monodeuteration, this strategy can also achieve multideuteration of the substrates contain more than one remote C(sp)-H bond, which opens a method to address multi-functionalization of distal unactivated C(sp)-H bonds.
未活化的 C(sp)-H 键的选择性氘代是药物化学、材料科学和合成化学中一个极具吸引力但极具挑战性的研究课题。本文报道了一种实用的、高选择性和经济高效的协同光催化和氢原子转移（HAT）催化的未活化 C(sp)-H 键的氢/氘（H/D）交换。以易于制备的 PMP 取代酰胺作为氮中心自由基前体，广泛的结构多样的酰胺可以与廉价的 DO 作为唯一的氘源平稳地进行可预测的自由基 H/D 交换，得到高达 99%的产率和优异的 D 含量的选择性取代的叔、仲和伯 C(sp)-H 键氘代产物。除了精确的单氘代外，该策略还可以对含有多个远程 C(sp)-H 键的底物进行多氘代，这为解决远程未活化 C(sp)-H 键的多功能化问题开辟了一种方法。
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