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Synthesis 2018; 50(23): 4659-4667
DOI: 10.1055/s-0037-1610652
paper
© Georg Thieme Verlag Stuttgart · New York

Stereoretentive Suzuki–Miyaura and Kumada–Tamao–Corriu Cross-Couplings for Preparing (E)- and (Z)-Stereodefined, Fully Substituted α,β-Unsaturated Esters: Application for a Pharmacophore Synthesis

Yuka Sato
Department of Chemistry, School of Science and Technology, Kwansei Gakuin University, 2-1 Gakuen, Sanda, Hyogo 669-1337, Japan   eMail: tanabe@kwansei.ac.jp
,
Yuichiro Ashida
Department of Chemistry, School of Science and Technology, Kwansei Gakuin University, 2-1 Gakuen, Sanda, Hyogo 669-1337, Japan   eMail: tanabe@kwansei.ac.jp
,
Daisuke Yoshitake
Department of Chemistry, School of Science and Technology, Kwansei Gakuin University, 2-1 Gakuen, Sanda, Hyogo 669-1337, Japan   eMail: tanabe@kwansei.ac.jp
,
Mayuko Hoshino
Department of Chemistry, School of Science and Technology, Kwansei Gakuin University, 2-1 Gakuen, Sanda, Hyogo 669-1337, Japan   eMail: tanabe@kwansei.ac.jp
,
Taichi Takemoto
Department of Chemistry, School of Science and Technology, Kwansei Gakuin University, 2-1 Gakuen, Sanda, Hyogo 669-1337, Japan   eMail: tanabe@kwansei.ac.jp
,
Yoo Tanabe*
Department of Chemistry, School of Science and Technology, Kwansei Gakuin University, 2-1 Gakuen, Sanda, Hyogo 669-1337, Japan   eMail: tanabe@kwansei.ac.jp
› InstitutsangabenThis research was partially supported by Grants-in-Aid for Scientific Research on Basic Areas (B) ‘18350056’, Priority Areas (A) ‘17035087’ and ‘18037068’, (C) ‘15K05508’, and Exploratory Research ‘17655045’ from the Ministry of Education, Culture, Sports, Science and Technology (MEXT).
Weitere Informationen

Publikationsverlauf

Received: 05. Juni 2018

Accepted after revision: 12. Juli 2018

Publikationsdatum:
23. August 2018 (online)

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Dedicated to Professor Teruaki Mukaiyama on the celebration of his 90th birthday (Sotuju)

Abstract

Substrate-general stereocomplementary Suzuki–Miyaura (SM) cross-coupling and relevant Kumada–Tamao–Corriu (KTC) cross-coupling reactions for preparing (E)- and (Z)-stereodefined, fully substituted α,β-unsaturated esters are described. The SM cross-coupling reactions were performed under Pd(OAc)2/SPhos/iPr2NEt catalysis (24 examples, 66–99% yield). The KTC cross-coupling reactions were also performed under similar Pd(OAc)2/SPhos conditions (11 examples, 50–98% yield). Application to a useful pharmacophore containing a cyclopropane structure was investigated, wherein distinctive (E)- and (Z)-stereochemical difference between XPhos and SPhos was observed. A plausible mechanism for the stereoretention and stereoinversion cross-coupling reactions is proposed.

Key words

Suzuki–Miyaura cross-coupling - Kumada–Tamao–Corriu cross-coupling - fully substituted α,β-unsaturated esters - pharmaco­phore - stereoretention - XPhos - SPhos

Supporting Information

    Supporting information for this article is available online at https://doi.org/10.1055/s-0037-1610652.
  • Supporting Information
 

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