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How Do Positions of Phosphito Units on a Calix[4]Arene Platform Affect the Enantioselectivity of a Catalytic Reaction?

Shaima Hkiri, David Sémeril

Organics · pp. 470–480 · Published 9 Nov 2022

10.3390/org3040030

Abstract

Three chiral diphosphites, (S,S)-5,17-bis(1,1′-binaphthyl-2,2′-dioxyphosphanyloxy)-25,26,27,28-tetrapropyloxycalix[4]arene (1), (S,S)-5,11,17,23-tetra-tert-butyl-25,27-dipropoxy-26,28-bis(1,1′-binaphthyl-2,2′-dioxyphosphanyloxy)calix[4]arene (2) and (S,S)-5,11,17,23-tetra-tert-butyl-25,26-dipropoxy-27,28-bis(1,1′-binaphthyl-2,2′-dioxyphosphanyloxy)calix[4]arene (3), based on conical calix[4]arene were investigated in the rhodium-catalyzed asymmetric hydrogenation of α-dehydroamino esters. High conversions were observed after 24 h under 5 bar of hydrogen whatever the employed diphosphite, and the chiral induction increases in the order 1 < 3 < 2. This may be due to the presence of the calix[4]arene moiety, which by its presence modifies the second coordination sphere of the catalytic center. The larger steric hindrance around the rhodium atom leads to the higher enantiomeric excess.

Steric effects Moiety Catalysis Chemistry Rhodium Medicinal chemistry Enantiomer Calixarene

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Cited by 3

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