Удосконалений синтез ROCKYPhos та його застосування для асиметричного гідрування похідних дигідроізохіноліну

An optimized approach to the multigram synthesis of [(1R,2R,3S)-(+)-1,2-dimethyl-2,3-bis(diphenylphosphinomethyl)cyclopentyl]methanol (ROCKYPhos, CatASium I®), a camphor-derived chiral diphosphine ligand, has been developed. The key improvement in the synthetic scheme involved the oxidative cleavage...

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Збережено в:
Бібліографічні деталі
Дата:2026
Автори: Bilenko, Vitalii A., Gorichko, Marian V.
Формат: Стаття
Мова:Англійська
Опубліковано: National University of Pharmacy 2026
Теми:
Онлайн доступ:https://ophcj.nuph.edu.ua/article/view/353838
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Назва журналу:Journal of Organic and Pharmaceutical Chemistry

Репозитарії

Journal of Organic and Pharmaceutical Chemistry
Опис
Резюме:An optimized approach to the multigram synthesis of [(1R,2R,3S)-(+)-1,2-dimethyl-2,3-bis(diphenylphosphinomethyl)cyclopentyl]methanol (ROCKYPhos, CatASium I®), a camphor-derived chiral diphosphine ligand, has been developed. The key improvement in the synthetic scheme involved the oxidative cleavage of 3,9-dibromocamphor with V2O5 – HNO3 or NH4VO3 – Cu(NO3)2 – HNO3 system, which gave the corresponding dicarboxylic acid in the yield of 28% and significantly reduced the reaction sequence. The NMR study of a diselenide derivative of ROCKYPhos showed that one of the PPh2 groups had strong donor properties comparable to those of trialkylphosphines. The asymmetric hydrogenation of N-acetyl-1,2-dihydroisoquinoline-4-carboxylates in the presence of ROCKYPhos provided target tetrahydroisoquinolines with up to 52% ee – an outstanding result for this substrate class.
DOI:10.24959/ophcj.26.353838