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Atropisomeric [(diphosphine)Au 2 Cl 2 ] Complexes and their Catalytic Activity Towards Asymmetric Cycloisomerisation of 1,6‐Enynes
Author(s) -
Barreiro Elena M.,
Boltukhina Ekaterina V.,
White Andrew J. P.,
Hii King Kuok Mimi
Publication year - 2015
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201404496
Subject(s) - chemistry , diphenylphosphine , catalysis , phos , substituent , enantioselective synthesis , medicinal chemistry , biphenyl , crystal structure , stereochemistry , phosphine , crystallography , organic chemistry , biochemistry
Abstract X‐ray crystal structures of two [(diphosphine)Au 2 Cl 2 ] complexes (in which diphosphine=P‐Phos and xylyl‐P‐Phos; P‐Phos=[2,2′,6,6′‐Tetramethoxy‐4,4′‐bis(diphenylphosphino)‐3,3′‐bipyridine]) were determined and compared to the reported structures of similar atropisomeric gold complexes. Correlations between the Au⋅⋅⋅Au distances and torsional angles for the biaryl series of ligands (MeOBIPHEP, SEGPhos, and P‐Phos; BIPHEP=2,2′‐bis(diphenylphosphino)‐1,1′‐biphenyl, SEGPhos=[(4,4′‐bi‐1,3‐benzodioxole)‐5,5′‐diyl]bis[diphenylphosphine]) can be made; these measurements appear to be very dependent upon the phosphorous substituent. Conversely, the same effect was not observed for ligands based on the binaphthyl (BINAP) series. The catalytic activity of these complexes was subsequently assessed in the enantioselective cycloisomerisation of 1,6‐enynes and revealed an over‐riding electronic effect: more‐electron‐rich phosphines promote greater enantioselectivity. The possibility of silver acting as a (co‐)catalyst was ruled out in these reactions.