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Copper-catalyzed asymmetric hydrogenation of 2-substituted ketones via dynamic kinetic resolution.

Olga V ZatolochnayaSonia RodríguezYongda ZhangKendricks S LaoSergei TcyrulnikovGuisheng LiXiao-Jun WangBo QuSoumik BiswasHari P R MangunuruDaniel RivaltiJoshua D SieberJean-Nicolas DesrosiersJoyce C LeungNelu GrinbergHeewon LeeNizar HaddadNathan K YeeJinhua J SongMarisa C KozlowskiChris H Senanayake
Published in: Chemical science (2018)
A new class of tunable heterophosphole dimeric ligands have been designed and synthesized. These ligands have enabled the first examples of Cu-catalyzed hydrogenation of 2-substituted-1-tetralones and related heteroaryl ketones via dynamic kinetic resolution, simultaneously creating two contiguous stereogenic centers with up to >99 : 1 dr and 98 : 2 er. The ligand-Cu complexes were isolated and characterized by single crystal X-ray, and DFT calculations revealed a novel heteroligated dimeric copper hydride transition state.
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