American Chemical Society
ol5b00611_si_001.pdf (7.78 MB)

Remote Stereoinduction in the Organocuprate-Mediated Allylic Alkylation of Allylic gem-Dichlorides: Highly Diastereoselective Synthesis of (Z)‑Chloroalkene Dipeptide Isosteres

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journal contribution
posted on 2015-05-15, 00:00 authored by Takuya Kobayakawa, Tetsuo Narumi, Hirokazu Tamamura
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.