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A stereodynamic phosphoramidite ligand derived from 3,3′‐functionalized ortho ‐biphenol and its rhodium(I) complex
Author(s) -
Storch Golo,
Deberle Luisa,
Menke JanMichael,
Rominger Frank,
Trapp Oliver
Publication year - 2016
Publication title -
chirality
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.43
H-Index - 77
eISSN - 1520-636X
pISSN - 0899-0042
DOI - 10.1002/chir.22655
Subject(s) - chemistry , phosphoramidite , amide , ligand (biochemistry) , rhodium , stereochemistry , non covalent interactions , enantioselective synthesis , chirality (physics) , catalysis , combinatorial chemistry , organic chemistry , molecule , hydrogen bond , receptor , oligonucleotide , dna , biochemistry , chiral symmetry breaking , physics , quantum mechanics , nambu–jona lasinio model , quark
Stereodynamic ligands and complexes bearing functional groups to attach chiral or achiral binding sites and auxiliaries are highly attractive due to the interesting opportunities for controlling the stereochemical outcome of enantioselective transformations. In this study we report the preparation of a 3,3′‐functionalized biphenol (BIPOL) phosphoramidite ligand (P Am ) bearing 3,5‐dichlorobenzoyl (3,5‐DCB) amide binding sites for noncovalent interactions. Upon coordination to [Rh(COD) 2 ]BF 4 this substitution pattern directs one of the 3,5‐DCB binding sites in close proximity of the metal center resulting in liberation of both COD ligands and the formation of a [Rh(P Am ) 2 ]BF 4 complex. Coordination of the amide carbonyl unit was found to be reversible, since the complex acted as an active catalyst in the hydrogenation of dehydroamino acid derivatives. X‐ray crystallographic investigation revealed that the second 3,5‐DCB unit is capable of forming noncovalent π–π interactions connecting both phosphoramidite ligands.