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Evaluation of phosphinoamidoester‐derived Pd catalysts in the asymmetric allylic alkylation reaction : Theoretical studies and mechanistic insights
Author(s) -
Marinho Vanda R. D.,
Ramalho J.P.Prates,
Rodrigues Ana Isabel,
Burke Anthony J.
Publication year - 2011
Publication title -
chirality
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.43
H-Index - 77
eISSN - 1520-636X
pISSN - 0899-0042
DOI - 10.1002/chir.20936
Subject(s) - chemistry , tsuji–trost reaction , catalysis , ligand (biochemistry) , chirality (physics) , allylic rearrangement , alkylation , alcohol , medicinal chemistry , stereochemistry , combinatorial chemistry , computational chemistry , organic chemistry , receptor , biochemistry , chiral symmetry breaking , physics , quantum mechanics , nambu–jona lasinio model , quark
Two simple hemilabile P,O‐coordinating phosphinoamidoester ligands 6a and 6b were synthesized and studied in the Pd(0)‐catalyzed asymmetric allylic alkylation of rac ‐1,3‐diphenylpropenyl acetate affording a highest ee of 83% ee with 6a . To gain an insight into the actual mechanism of this catalytic reactions , which had previously been investigated with a first generation family of P,O‐coordinating phosphinoamido‐alcohol ligands— 4a and 4b —a semiempirical computational study was carried out with the Pd‐allyl complexes formed from both 4a and 6a including Hitchcock's phosphinoamido‐alcohol ligand 5 (R 1 = H, R 2 = Ph). The results of this study substantiate a working model that has previously been proposed for this reaction using hemilabile P,O‐coordinating phosphinoamido‐type ligands . Chirality 2011 © 2011 Wiley‐Liss, Inc