Enantioselective synthesis of monofluorinated allylic compounds: Pd-catalyzed asymmetric allylations of dimethyl 2-fluoromalonate using new N-sulfinyl-based ligands.
New chiral S,N- and S,P-ligands starting from tert-butanesulfinamide were synthesized in four steps, applying Pd-catalyzed asymmetric allylic substitutions of dimethyl 2-fluoromalonate. The induced effect of the Pd/S,N-ligand catalyst on the enantioselectivity depends on the steric demand of the substituent at the o-position of the pyridine ring. This method produced monofluorinated allylation products in up to high yield with high enantioselectivity.
Shanghai Key Lab of Chemical Assessment and Sustainability, Department of Chemistry, Tongji University, 1239 Siping Road, 200092 Shanghai, P.R. China. xmzhao08@mail.tongji.edu.cn.
Ning
N
Gao
Xiao-Ming
XM
Zhao
Cheng-Si
CS
Cai
Jue-Wang
JW
Cai
D000498:Allyl Compounds / Q000737:chemistry*; D002384:Catalysis; D060326:Chemistry Techniques, Synthetic; D054879:Halogenation; D008024:Ligands; D008314:Malonates / Q000138:chemical synthesis* / Q000737:chemistry*; D010165:Palladium / Q000737:chemistry*; D013237:Stereoisomerism; D013452:Sulfonium Compounds / Q000737:chemistry*
D000498:Allyl Compounds; D008024:Ligands; D008314:Malonates; D013452:Sulfonium Compounds; D010165:Palladium; C030290:malonic acid