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Copper(I) Complexes of P ‐Stereogenic Josiphos and Related Ligands
Author(s) -
Arthurs Ross A.,
Dean Alice C.,
Hughes David L.,
Richards Christopher J.
Publication year - 2021
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.202100146
Subject(s) - chemistry , stereocenter , diastereomer , conjugate , amine gas treating , ferrocene , copper , phosphine , ligand (biochemistry) , stereochemistry , medicinal chemistry , enantioselective synthesis , catalysis , organic chemistry , receptor , mathematical analysis , biochemistry , mathematics , electrode , electrochemistry
Starting from ( R )‐Ugi's amine, diastereoselective lithiation followed by Ar'PCl 2 and then Ar’’MgBr led to the generation, as single diastereoisomers, of ( R , S p , S phos ) [Ar’=Ph, Ar’’= o ‐Tol] and ( R , S p , R phos ) [Ar’= o ‐Tol, Ar’’=Ph] PPFA ligand derivatives. Amine substitution of both with HPCy 2 gave P ‐stereogenic Josiphos ligands, and then addition of CuCl, the corresponding copper(I) complexes. The latter were also generated by using borane P and N protecting groups and in situ Cu(I) complexation, avoiding the isolation of air‐sensitive phosphine intermediates. This protection methodology was also applied to the synthesis of Josiphos/CuCl complexes derived from PCl 3 . In addition, related bulky cobalt‐sandwich complex‐based derivatives were also obtained. Preliminary investigation revealed isolated CuCl complexes as competent catalyst precursors for enantioselective conjugate addition reactions.