130866-09-0Relevant articles and documents
Development of Chiral Phosphine Ligands Bearing a Carboxyl Group and Their Application to Catalytic Asymmetric Reaction
Minami, Toru,Okada, Yoshiharu,Otaguro, Tsuneyuki,Tawaraya, Seiji,Furuichi, Tomohiro,Okauchi, Tatsuo
, p. 2469 - 2474 (1995)
A new chiral phosphine ligand bearing a carboxyl group, 3-(diphenylphosphino)butanoic acid, was developed and used for palladium catalyzed asymmetric allylic alkylation of cyclic cis-allylic acetates such as 2-cyclopentenyl, 2-cyclohexenyl, and 2-cyclohep
Synthesis of a novel type of chiral phosphinocarboxylic acids. The phosphine-palladium complexes catalyzed asymmetric allylic alkylation
Okada,Minami,Umezu,Nishikawa,Mori,Nakayama
, p. 667 - 682 (2007/10/02)
A novel type of chiral cycloalkylphosphines bearing the carboxy group at the β-position were developed, and used for palladium catalyzed asymmetric allylic alkylation of allylic substrates such as 2-cyclohexenylacetate and 1,3-disubstituted-propenyl acetates (R1CH=CHCH(OAc)R2:R1=R2=Ph; R1=Ph, R2=(CH2)4OAc; R1=Ph, R2=(CH2)6OAc; R1=Ph, R2=(CH2)10OAc). Reaction of the propenyl acetates with soft carbon nucleophiles such as triethyl sodiophosphonoacetate and sodiomalonic acid esters in the presence of a palladium catalyst prepared in situ from Pd(OAc)2 and chiral (2-diphenylphospino)cycloalkanecarboxylic acids (7a,b) gave high yields of alkylation products (PhCH=CHCH(X)Ph: > 77%ee for X=CH(CO2Et)P(O)(OEt)2 and >72 %ee for X=CH(CO2Me)2. The alkylation products 15 and 28a-c were converted into optically active α-methylene-γ-lactone and α-methylene macrolide derivatives. The high stereoselectivity demonstrated by the chiral phosphinocarboxylic acid-palladium catalyzed allylic alkylation suggested to be caused by an electronic repulsion between the carboxy group on the ligand and the incoming soft carbon nucleophile, which directs the nucleophilic attack on one of the π-allyl carbons.
The first synthesis of chiral phosphinocarboxylic acid ligands, trans-2-(diphenylphosphino) cycloalkanecarboxylic acids. The phosphine-palladium complexes catalyzed asymmetric allylic alkylation
Okada, Yoshiharu,Minami, Toru,Sasaki, Yoritaka,Umezu, Yasuo,Yamaguchi, Masahiko
, p. 3905 - 3908 (2007/10/02)
The first synthesized chiral phosphinocarboxylic acids were effective as ligand for the palledium-catalyzed asymmetric allylic alkylation of 3-acetoxy-1,3-diphenyl-1-propene and 2-cyclohexenyl acetate with soft carbanion from dimethyl malonate or triethyl phosphonoacetate and sodium hydride to give the alkylation products of up to 83% ee.
