title: Addition of optically pure H-phosphinate to ketones: selectivity, stereochemistry and mechanism.
abstract: Aromatic methyl ketones and cyclic asymmetric ketones underwent hydrophosphorylation with P-stereogenic H-P species in the presence of potassium carbonate to produce P,C-stereogenic tertiary α-hydroxyl phosphinates in excellent yields with up to 99 : 1 dr. The diastereoselectivity was induced by a reversible conversion of less stable stereomer of product to that of a more stable one via an equilibrium, which was confirmed by aldehyde/ketone exchanging reaction. Toward the exchange, aliphatic or aldehyde carbonyl were more active than aromatic or ketone carbonyls, respectively. The stability difference between the two diastereomers was controlled by the sizes of substituents linking to phosphorus or α-carbon.
authors.affiliation: College of Chemistry and Chemical Engineering, Liaocheng University, Liaocheng, Shandong 252059, China. literabc@hotmail.com.
authors.forename: Yong-Ming
authors.initials: YM
authors.lastname: Sun
authors.forename: Nana
authors.initials: N
authors.lastname: Xin
authors.forename: Zhong-Yuan
authors.initials: ZY
authors.lastname: Xu
authors.forename: Li-Juan
authors.initials: LJ
authors.lastname: Liu
authors.forename: Fan-Jie
authors.initials: FJ
authors.lastname: Meng
authors.forename: He
authors.initials: H
authors.lastname: Zhang
authors.forename: Bao-Ci
authors.initials: BC
authors.lastname: Fu
authors.forename: Qiu-Ju
authors.initials: QJ
authors.lastname: Liang
authors.forename: Hong-Xing
authors.initials: HX
authors.lastname: Zheng
authors.forename: Li-Jun
authors.initials: LJ
authors.lastname: Sun
authors.forename: Chang-Qiu
authors.initials: CQ
authors.lastname: Zhao
authors.forename: Li-Biao
authors.initials: LB
authors.lastname: Han
mesh_terms: D000447:Aldehydes / Q000737:chemistry*; D002244:Carbon / Q000737:chemistry; D002254:Carbonates / Q000737:chemistry; D002384:Catalysis; D007659:Ketones / Q000737:chemistry*; D015394:Molecular Structure; D010721:Phosphinic Acids / Q000737:chemistry*; D010758:Phosphorus / Q000737:chemistry; D011188:Potassium / Q000737:chemistry; D013237:Stereoisomerism
chemical_list: D000447:Aldehydes; D002254:Carbonates; D007659:Ketones; D010721:Phosphinic Acids; D010758:Phosphorus; D002244:Carbon; C037593:potassium carbonate; D011188:Potassium