title: Remote Stereoinduction in the Organocuprate-Mediated Allylic Alkylation of Allylic gem-Dichlorides: Highly Diastereoselective Synthesis of (Z)-Chloroalkene Dipeptide Isosteres.
abstract: Highly diastereoselective synthesis of (Z)-chloroalkene dipeptide isosteres has been achieved by 1,4-asymmetric induction in the organocuprate-mediated allylic alkylation adjacent to the chiral center of allylic gem-dichlorides. The reaction proceeds with a variety of heterocuprates prepared from CuCN and various organometallic reagents. It allows rapid construction of valuable architectures of L,D-type and L,L-type (Z)-chloroalkene dipeptide isosteres from the corresponding (E)- and (Z)-allylic gem-dichlorides in high yields, with excellent (Z)-selectivity and diastereoselectivity.
authors.affiliation: †Institute of Biomaterials and Bioengineering, Tokyo Medical and Dental University, Chiyoda-ku, Tokyo 101-0062, Japan.
authors.forename: Takuya
authors.initials: T
authors.lastname: Kobayakawa
authors.affiliation: †Institute of Biomaterials and Bioengineering, Tokyo Medical and Dental University, Chiyoda-ku, Tokyo 101-0062, Japan.|‡Department of Applied Chemistry and Biochemical Engineering, Faculty of Engineering, Shizuoka University, Hamamatsu, Shizuoka, 432-8561, Japan.
authors.forename: Tetsuo
authors.initials: T
authors.lastname: Narumi
authors.affiliation: †Institute of Biomaterials and Bioengineering, Tokyo Medical and Dental University, Chiyoda-ku, Tokyo 101-0062, Japan.
authors.forename: Hirokazu
authors.initials: H
authors.lastname: Tamamura
mesh_terms: D000475:Alkenes / Q000138:chemical synthesis* / Q000737:chemistry; D000478:Alkylation; D002384:Catalysis; D004151:Dipeptides / Q000138:chemical synthesis* / Q000737:chemistry; D015394:Molecular Structure; D013237:Stereoisomerism
chemical_list: D000475:Alkenes; D004151:Dipeptides