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Catalytic Palladium Phosphination: Modular Synthesis of C 1 ‐Symmetric Biaryl‐Based Diphosphines
Author(s) -
Bonnafoux Laurence,
GramageDoria Rafael,
Colobert Françoise,
Leroux Frédéric R.
Publication year - 2011
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.201101529
Subject(s) - diphosphines , palladium , catalysis , modular design , chemistry , combinatorial chemistry , computer science , organic chemistry , programming language
A new family of C 1 ‐symmetric bis(diphenylphosphino)biphenyls have been prepared starting from readily available ortho , ortho ′‐dihalobiphenyl precursors by a palladium‐catalyzed C–P coupling reaction. This process does not require the use of an additional ligand. To date, the synthesis of such diphosphines, by reaction of an intermediate biphenyldiyl dianion with ClPPh 2 , mainly afforded the undesired cyclic phosphafluorene derivative. So far, no synthetic pathway has been found to avoid this intramolecular reaction. Herein we report the first general and external‐ligand‐free palladium‐catalyzed phosphination reaction that allows the synthesis of a wide variety of substituted ortho , ortho ′‐bis(diphenylphosphino)biphenyls. With the aim of illustrating the scope and efficiency of this methodology, we applied it to the establishment of a straightforward access to C 1 ‐symmetrical analogues of the most powerful ligands used in homogenous catalysis and extended it to more challenging substrates.