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BIPNOR: A New, Efficient Bisphosphine Having Two Chiral, Nonracemizable, Bridgehead Phosphorus Centers for Use in Asymmetric Catalysis
Author(s) -
Robin Frédéric,
Mercier François,
Ricard Louis,
Mathey François,
Spagnol Michel
Publication year - 1997
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.19970030824
Subject(s) - catalysis , diphenylacetylene , optically active , chemistry , phosphorus , alkylation , asymmetric hydrogenation , enantioselective synthesis , medicinal chemistry , palladium , combinatorial chemistry , organic chemistry
Optically active phosphorus ligands are widely used in homogeneous asymmetric catalysis. However, among the numerous available structures of this type, the subclass of optically active bisphosphines with at least one chiral phosphorus atom is rather underdeveloped. A bisphosphine with two chiral, nonracemizable bridgehead phosphorus centers, ( meso,d/l )‐2,2′,3,3′‐tetraphenyl‐4,4′,5,5′‐tetramethyl‐6,6′‐ bi s‐1‐ p hospha nor borna‐2,5‐dienyl (BIPNOR), can be obtained by thermolysis of 1,1′‐bisphospholyl with diphenylacetylene. Here, we report the resolution of the d/l isomer by means of a chiral palladium complex to give the two optically active forms of BIPNOR. We then investigate the catalytic properties of BIPNOR, incorporated in Rh I and Ru II catalysts for the hydrogenation of olefins and ketones and in a Pd II catalyst for asymmetric alkylation reactions. BIPNOR is shown to give good results in these catalytic reactions.