Asymmetric Hydrogenation of Seven‐Membered C=N‐containing Heterocycles and Rationalization of the Enantioselectivity. Issue 30 (22nd June 2016)

• Record Type: Journal Article
• Authors: Balakrishna, Bugga; Bauzá, Antonio; Frontera, Antonio; Vidal‐Ferran, Anton
• Is Part Of: Chemistry. Volume 22:Issue 30(2016)
• Page Start: 10607
• Page End: 10613
• Publication Date: 2016-06-22
• Subjects: asymmetric hydrogenation -- enantiopure heterocycles -- iridium -- phosphine–phosphites -- substrate activation; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201601464
• Languages: English
• ISSNs: 0947-6539

Abstract

Abstract: Iridium(I) complexes with phosphine–phosphite ligands efficiently catalyze the enantioselective hydrogenation of diverse seven‐membered C=N‐containing heterocyclic compounds (eleven examples; up to 97 % ee ). The P‐OP ligand L3, which incorporates an ortho ‐diphenyl substituted octahydrobinol phosphite fragment, provided the highest enantioselectivities in the hydrogenation of most of the heterocyclic compounds studied. The observed stereoselection was rationalized by means of DFT calculations. Abstract : Cl switch : Efficient enantioselective hydrogenation of seven‐membered N‐heterocycles mediated by Ir‐(P‐OP) complexes is described (11 examples, up to 97 % ee ; see figure). The position of the Cl ligand in the catalytically relevant Ir species (amongst other factors) is key for rationalizing the stereochemical outcome.