Enantioselective synthesis of tunable chiral Clickphine P,N-ligands and their application in Ir-catalyzed asymmetric hydrogenation

The Journal of Organic Chemistry
Jeroen WassenaarJoost N H Reek

Abstract

A small library of highly tunable chiral Clickphine P,N-ligands has been prepared in an enantioselective fashion by Cu(I)-catalyzed asymmetric propargylic amination using a single chiral complex and a subsequent in situ cycloaddition click reaction. The scope of the propargylic amination to yield optically active triazolyl amines is described. The amines are transformed in a one-pot procedure to the corresponding Ir-Clickphine complexes, which serve as catalysts for the asymmetric hydrogenation of di-, tri-, and tetrasubstituted unfunctionalized alkenes. Enantioselectivities of up to 90% ee were obtained in these hydrogenations, which are among the best reported in the case of the tetrasubstituted substrate 2-(4'-methoxyphenyl)-3-methylbut-2-ene (9) (87% ee). This is a demonstration of the effective use of the chiral pool, as from one chiral catalyst a library of chiral Ir complexes has been synthesized that can hydrogenate various alkenes with high selectivity.

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Citations

Jan 10, 2017·Journal of the American Chemical Society·Cristiana Margarita, Pher G Andersson
Apr 11, 2017·Journal of the American Chemical Society·Veronika M Shoba, James M Takacs
Dec 4, 2019·Angewandte Chemie·Raphael BiglerFrancis Gosselin
Apr 8, 2020·Beilstein Journal of Organic Chemistry·Wisdom A MunzeiwaVincent O Nyamori

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