Diastereoselective synthesis of psi[(E)-CH=CMe]- and psi[(Z)-CH=CMe]-type dipeptide isosteres by organocopper-mediated anti-S(N)2' reaction.
[reaction: see text] Acyclic psi[(E)-CH=CMe]- and psi[(Z)-CH=CMe]-type dipeptide isosteres were efficiently synthesized. In a key reaction, alpha-alkylation of gamma-mesyloxy-beta-methyl-alpha,beta-unsaturated esters with organocyanocuprates in diethyl ether or tetrahydrofuran preferentially afforded the psi[(E)-CH=CMe]- or psi[(Z)-CH=CMe]-isomer, respectively, via anti-S(N)2' mechanism.
Oishi
Shinya
S
Graduate School of Pharmaceutical Sciences, Kyoto University, Sakyo-ku, Kyoto, 606-8501, Japan.
Kamano
Takae
T
Niida
Ayumu
A
Odagaki
Yoshihiko
Y
Tamamura
Hirokazu
H
Otaka
Akira
A
Hamanaka
Nobuyuki
N
Fujii
Nobutaka
N
D000478:Alkylation; D003300:Copper; D004151:Dipeptides / Q000138:chemical synthesis / Q000737:chemistry*; D007202:Indicators and Reagents; D009942:Organometallic Compounds / Q000737:chemistry*; D013237:Stereoisomerism
D004151:Dipeptides; D007202:Indicators and Reagents; D009942:Organometallic Compounds; D003300:Copper