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Palladium‐Catalyzed Diorganozinc Conjugate Additions to Enones: Preparative and Computational Studies
Author(s) -
Lorenzo Paula,
Aurrecoechea José M.,
de Lera Angel R.,
Álvarez Rosana
Publication year - 2013
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.201201519
Subject(s) - chemistry , transmetalation , reductive elimination , conjugate , reagent , palladium , oxidative addition , catalysis , alkyl , aryl , ligand (biochemistry) , medicinal chemistry , enone , combinatorial chemistry , conjugated system , organic chemistry , mathematical analysis , biochemistry , receptor , mathematics , polymer
The Pd‐catalyzed conjugate addition of diorganozinc reagents to α,β‐unsaturated carbonyl compounds has been applied to a variety of enone substrates, both cyclic and acyclic, encompassing various combinations of aryl and alkyl substitution, in combination with diorganozinc reagents incorporating alkyl (Me, linear and branched) or Ph groups. While both Pd 0 and Pd II complexes have been found to be competent precatalysts, reaction yields are strongly dependent on the relative amounts of Pd to phosphane ligand. Thus, a 1:1 Pd/P ratio is well tolerated, but going to Pd/P = 1:2 leads to poor conversions and yields. A calculated Pd 0 ‐mediated pathway involving an unusual oxidative addition step with simultaneous transmetalation, followed by reductive elimination, has been found to be compatible with the observed phosphane effect.