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Structural Requirements in Chiral Diphosphine–Rhodium Complexes. XIV. Heptagonal Chelating Ring Flexibility in Rhodium(I) Complexes of Trans ‐1,2‐bis(Diphenylphosphinomethyl)cycloalkanes
Author(s) -
Glaser Robert,
Geresh Shimona,
Twaik Menachem
Publication year - 1980
Publication title -
israel journal of chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.908
H-Index - 54
eISSN - 1869-5868
pISSN - 0021-2148
DOI - 10.1002/ijch.198000058
Subject(s) - rhodium , chemistry , diastereomer , moiety , adduct , ring (chemistry) , stereochemistry , chelation , catalysis , medicinal chemistry , organic chemistry
Z ‐N‐acyldehydroamino acids and esters were hydrogenated with in‐situ prepared rhodium(I) complexes, containing trans‐4,5‐bis(diphenylphosphinomethyl)‐2,2‐dimethyl‐1,3‐dioxolan (DIOP) or its carbocyclic analogues — trans‐1,2‐bis(diphenylphosphinomethyl)cycloalkanes. The optical purities of the N‐acylamino acid and ester products do not reflect a simple correlation with the PCH 2 –C–C–CH 2 P torsional angle within the diphosphine moiety of the catalytic complex, but are related to the flexibility of the heptagonal chelating ring. The relationship between the chiral sense of the major reduction product and the structure of the diastereomeric enamide adduct complexes is also discussed.