title: Addressing the configuration stability of lithiated secondary benzylic carbamates for the development of a noncryogenic stereospecific boronate rearrangement.
abstract: A practical noncryogenic process for the Aggarwal stereospecific boronate rearrangement with chiral secondary benzylic carbamates has been developed. The use of LDA instead of sec-BuLi combined with an in situ trapping of the unstable lithiated carbamate was critical to success. Furthermore, this new process increased the substrate scope to include the versatile aryl iodide and bromide substrates. The methodology was applied to a diverse array of substrates and was demonstrated on multikilogram scale.
authors.affiliation: Department of Chemical Development, Boehringer-Ingelheim Pharmaceuticals Inc. , 900 Ridgebury Road, P.O. Box 368, Ridgefield, Connecticut 06877-0368, United States.
authors.forename: Keith R
authors.initials: KR
authors.lastname: Fandrick
authors.forename: Nitinchandra D
authors.initials: ND
authors.lastname: Patel
authors.forename: Jason A
authors.initials: JA
authors.lastname: Mulder
authors.forename: Joe
authors.initials: J
authors.lastname: Gao
authors.forename: Michael
authors.initials: M
authors.lastname: Konrad
authors.forename: Elizabeth
authors.initials: E
authors.lastname: Archer
authors.forename: Frederic G
authors.initials: FG
authors.lastname: Buono
authors.forename: Adil
authors.initials: A
authors.lastname: Duran
authors.forename: Rolf
authors.initials: R
authors.lastname: Schmid
authors.forename: Juergen
authors.initials: J
authors.lastname: Daeubler
authors.forename: Daniel R
authors.initials: DR
authors.lastname: Fandrick
authors.forename: Shengli
authors.initials: S
authors.lastname: Ma
authors.forename: Nelu
authors.initials: N
authors.lastname: Grinberg
authors.forename: Heewon
authors.initials: H
authors.lastname: Lee
authors.forename: Carl A
authors.initials: CA
authors.lastname: Busacca
authors.forename: Jinhua J
authors.initials: JJ
authors.lastname: Song
authors.forename: Nathan K
authors.initials: NK
authors.lastname: Yee
authors.forename: Chris H
authors.initials: CH
authors.lastname: Senanayake
mesh_terms: D001593:Benzyl Compounds / Q000737:chemistry*; D001897:Boronic Acids / Q000138:chemical synthesis* / Q000737:chemistry; D002219:Carbamates / Q000737:chemistry*; D004952:Esters; D015394:Molecular Structure; D013237:Stereoisomerism
chemical_list: D001593:Benzyl Compounds; D001897:Boronic Acids; D002219:Carbamates; D004952:Esters