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; Yuichiro Ashida; Daisuke Yoshitake; Mayuko Hoshino; Taichi Takemoto; Yoo Tanabe

doi:10.1055/s-0037-1610652

Synthesis, Inhaltsverzeichnis

Synthesis 2018; 50(23): 4659-4667
DOI: 10.1055/s-0037-1610652

paper

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

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Abstract

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Dedicated to Professor Teruaki Mukaiyama on the celebration of his 90^th 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

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Referenzen

References

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