The improved synthesis of ROCKYPhos and its application for the asymmetric hydrogenation of dihydroisoquinoline derivatives

Vitalii A. Bilenko; Marian V. Gorichko

doi:10.24959/ophcj.26.353838

Authors

Vitalii A. Bilenko Enamine Ltd.; Taras Shevchenko National University of Kyiv, Ukraine https://orcid.org/0009-0001-4428-4821
Marian V. Gorichko Taras Shevchenko National University of Kyiv, Ukraine https://orcid.org/0000-0002-5401-9597

DOI:

https://doi.org/10.24959/ophcj.26.353838

Keywords:

asymmetric synthesis, phosphine ligands, nitrogen heterocycles, isoquinoline

Abstract

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.

Supporting Agency

The authors received no specific funding for this work.

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