title: Highly enantioselective regiodivergent allylic alkylations of MBH carbonates with phthalides.
abstract: Phthalides were used for the first time in the allylic alkylation reactions with MBH carbonates for the creation of chiral 3,3-disubstituted phthalides. Highly enantioselective regiodivergent synthesis of γ-selective or β-selective allylic alkylation products was achieved by employing bifunctional chiral phosphines or multifunctional tertiary amine-thioureas as the catalyst, respectively. It was demonstrated that proper selection of catalysts and reaction conditions would differentiate an S(N)2'-S(N)2' pathway and an addition-elimination process, yielding different regioisomers of the allylic alkylation products in a highly enantiomerically pure form.
authors.affiliation: Department of Chemistry & Medicinal Chemistry Program, Life Sciences Institute, National University of Singapore, 3 Science Drive 3, Singapore 117543, Singapore.
authors.forename: Fangrui
authors.initials: F
authors.lastname: Zhong
authors.forename: Jie
authors.initials: J
authors.lastname: Luo
authors.forename: Guo-Ying
authors.initials: GY
authors.lastname: Chen
authors.forename: Xiaowei
authors.initials: X
authors.lastname: Dou
authors.forename: Yixin
authors.initials: Y
authors.lastname: Lu
mesh_terms: D000478:Alkylation; D000498:Allyl Compounds / Q000737:chemistry*; D001572:Benzofurans / Q000737:chemistry*; D002254:Carbonates / Q000737:chemistry*; D013237:Stereoisomerism
chemical_list: D000498:Allyl Compounds; D001572:Benzofurans; D002254:Carbonates; C082022:phthalide