Stereoselective formation of trisubstituted (Z)-chloroalkenes adjacent to a tertiary carbon stereogenic center by organocuprate-mediated reduction/alkylation.
A robust and efficient method for the synthesis of trisubstituted (Z)-chloroalkenes is described. A one-pot reaction of γ,γ-dichloro-α,β-enoyl sultams involving organocuprate-mediated reduction/asymmetric alkylation affords α-chiral (Z)-chloroalkene derivatives in moderate to high yields with excellent diastereoselectivity, and allylic alkylation of internal allylic gem-dichlorides is also demonstrated. This study provides the first examples of the use of allylic gem-dichlorides adjacent to the chiral center for novel 1,4-asymmetric induction.
Department of Medicinal Chemistry, Institute of Biomaterials and Bioengineering, Tokyo Medical and Dental University, 2-3-10 Kandasurugadai, Tokyo 101-0062, Japan.
Tetsuo
T
Narumi
Takuya
T
Kobayakawa
Haruo
H
Aikawa
Shunsuke
S
Seike
Hirokazu
H
Tamamura
D000475:Alkenes / Q000138:chemical synthesis* / Q000737:chemistry; D000498:Allyl Compounds / Q000737:chemistry; D002244:Carbon / Q000737:chemistry*; D002384:Catalysis; D006843:Hydrocarbons, Chlorinated / Q000138:chemical synthesis* / Q000737:chemistry; D015394:Molecular Structure; D010084:Oxidation-Reduction; D013237:Stereoisomerism
D000475:Alkenes; D000498:Allyl Compounds; D006843:Hydrocarbons, Chlorinated; D002244:Carbon