title: Remarkable beta-selectivity in the synthesis of beta-1-C-arylglucosides: stereoselective reduction of acetyl-protected methyl 1-C-arylglucosides without acetoxy-group participation.
abstract: An efficient and practical process to generate beta-C-arylglucoside derivatives was achieved. The process described involves Lewis acid mediated ionic reduction of a peracetylated 1-C-aryl methyl glucoside derived from the addition of an aryl-Li to selectively protected delta-D-gluconolactone. The reduction of the 2-acetoxy-1-C-oxacarbenium ion intermediates proceeds with a high degree of selectivity to give beta-C-arylglucosides without 2-acetoxy group participation. Furthermore, during the reduction process we also identified an unprecedented critical role of water. By changing from the usual benzyl ether protecting groups because of cost and chemical compatibility concerns, the new process is made additionally efficient and highly selective.
authors.affiliation: Process Research and Development, Bristol-Myers Squibb, 1 Squibb Drive, New Brunswick, New Jersey 08903, USA. prashant.deshpande@bms.com
authors.forename: Prashant P
authors.initials: PP
authors.lastname: Deshpande
authors.forename: Bruce A
authors.initials: BA
authors.lastname: Ellsworth
authors.forename: Frederic G
authors.initials: FG
authors.lastname: Buono
authors.forename: Annie
authors.initials: A
authors.lastname: Pullockaran
authors.forename: Janak
authors.initials: J
authors.lastname: Singh
authors.forename: Thomas P
authors.initials: TP
authors.lastname: Kissick
authors.forename: Ming-H
authors.initials: MH
authors.lastname: Huang
authors.forename: Hildegard
authors.initials: H
authors.lastname: Lobinger
authors.forename: Theodor
authors.initials: T
authors.lastname: Denzel
authors.forename: Richard H
authors.initials: RH
authors.lastname: Mueller
mesh_terms: D005960:Glucosides / Q000138:chemical synthesis* / Q000737:chemistry; D015394:Molecular Structure; D010084:Oxidation-Reduction; D013237:Stereoisomerism; D013997:Time Factors
chemical_list: D005960:Glucosides