Second-generation total synthesis of aplyronine A featuring Ni/Cr-mediated coupling reactions

Ichiro Hayakawa, Keita Saito, Sachiko Matsumoto, Shinichi Kobayashi, Ayaka Taniguchi, Kenichi Kobayashi, Yusuke Fujii, Takahiro Kaneko, Hideo Kigoshi

Research output: Contribution to journalArticle

4 Citations (Scopus)

Abstract

Second-generation total synthesis of aplyronine A, a potent antitumor marine macrolide, was achieved using Ni/Cr-mediated coupling reactions as key steps. The overall yield of the second-generation synthetic pathway of aplyronine A was 1.4%, obtained in 38 steps based on the longest linear sequence. Compared to our first-generation synthetic pathway of aplyronine A, the second-generation synthesis greatly improved both the yield and number of steps. In particular, we improved the stereoselectivity in the construction of the C13 stereogenic center and the C14-C15 (E)-trisubstituted double bond using the asymmetric Ni/Cr-mediated coupling reaction. Furthermore, we established efficient reaction conditions for the asymmetric Ni/Cr-mediated coupling reaction between the C21-C28 segment and C29-C34 segment. Thus, this coupling reaction proceeded with an equimolar ratio of each segment.

Original languageEnglish
Pages (from-to)124-131
Number of pages8
JournalOrganic and Biomolecular Chemistry
Volume15
Issue number1
DOIs
Publication statusPublished - 2017

Fingerprint

synthesis
Stereoselectivity
Macrolides
aplyronine A

ASJC Scopus subject areas

  • Biochemistry
  • Physical and Theoretical Chemistry
  • Organic Chemistry

Cite this

Hayakawa, I., Saito, K., Matsumoto, S., Kobayashi, S., Taniguchi, A., Kobayashi, K., ... Kigoshi, H. (2017). Second-generation total synthesis of aplyronine A featuring Ni/Cr-mediated coupling reactions. Organic and Biomolecular Chemistry, 15(1), 124-131. https://doi.org/10.1039/c6ob02241c

Second-generation total synthesis of aplyronine A featuring Ni/Cr-mediated coupling reactions. / Hayakawa, Ichiro; Saito, Keita; Matsumoto, Sachiko; Kobayashi, Shinichi; Taniguchi, Ayaka; Kobayashi, Kenichi; Fujii, Yusuke; Kaneko, Takahiro; Kigoshi, Hideo.

In: Organic and Biomolecular Chemistry, Vol. 15, No. 1, 2017, p. 124-131.

Research output: Contribution to journalArticle

Hayakawa, I, Saito, K, Matsumoto, S, Kobayashi, S, Taniguchi, A, Kobayashi, K, Fujii, Y, Kaneko, T & Kigoshi, H 2017, 'Second-generation total synthesis of aplyronine A featuring Ni/Cr-mediated coupling reactions', Organic and Biomolecular Chemistry, vol. 15, no. 1, pp. 124-131. https://doi.org/10.1039/c6ob02241c
Hayakawa, Ichiro ; Saito, Keita ; Matsumoto, Sachiko ; Kobayashi, Shinichi ; Taniguchi, Ayaka ; Kobayashi, Kenichi ; Fujii, Yusuke ; Kaneko, Takahiro ; Kigoshi, Hideo. / Second-generation total synthesis of aplyronine A featuring Ni/Cr-mediated coupling reactions. In: Organic and Biomolecular Chemistry. 2017 ; Vol. 15, No. 1. pp. 124-131.
@article{5ab761ff01b140599525801bf3aed75d,
title = "Second-generation total synthesis of aplyronine A featuring Ni/Cr-mediated coupling reactions",
abstract = "Second-generation total synthesis of aplyronine A, a potent antitumor marine macrolide, was achieved using Ni/Cr-mediated coupling reactions as key steps. The overall yield of the second-generation synthetic pathway of aplyronine A was 1.4{\%}, obtained in 38 steps based on the longest linear sequence. Compared to our first-generation synthetic pathway of aplyronine A, the second-generation synthesis greatly improved both the yield and number of steps. In particular, we improved the stereoselectivity in the construction of the C13 stereogenic center and the C14-C15 (E)-trisubstituted double bond using the asymmetric Ni/Cr-mediated coupling reaction. Furthermore, we established efficient reaction conditions for the asymmetric Ni/Cr-mediated coupling reaction between the C21-C28 segment and C29-C34 segment. Thus, this coupling reaction proceeded with an equimolar ratio of each segment.",
author = "Ichiro Hayakawa and Keita Saito and Sachiko Matsumoto and Shinichi Kobayashi and Ayaka Taniguchi and Kenichi Kobayashi and Yusuke Fujii and Takahiro Kaneko and Hideo Kigoshi",
year = "2017",
doi = "10.1039/c6ob02241c",
language = "English",
volume = "15",
pages = "124--131",
journal = "Organic and Biomolecular Chemistry",
issn = "1477-0520",
publisher = "Royal Society of Chemistry",
number = "1",

}

TY - JOUR

T1 - Second-generation total synthesis of aplyronine A featuring Ni/Cr-mediated coupling reactions

AU - Hayakawa, Ichiro

AU - Saito, Keita

AU - Matsumoto, Sachiko

AU - Kobayashi, Shinichi

AU - Taniguchi, Ayaka

AU - Kobayashi, Kenichi

AU - Fujii, Yusuke

AU - Kaneko, Takahiro

AU - Kigoshi, Hideo

PY - 2017

Y1 - 2017

N2 - Second-generation total synthesis of aplyronine A, a potent antitumor marine macrolide, was achieved using Ni/Cr-mediated coupling reactions as key steps. The overall yield of the second-generation synthetic pathway of aplyronine A was 1.4%, obtained in 38 steps based on the longest linear sequence. Compared to our first-generation synthetic pathway of aplyronine A, the second-generation synthesis greatly improved both the yield and number of steps. In particular, we improved the stereoselectivity in the construction of the C13 stereogenic center and the C14-C15 (E)-trisubstituted double bond using the asymmetric Ni/Cr-mediated coupling reaction. Furthermore, we established efficient reaction conditions for the asymmetric Ni/Cr-mediated coupling reaction between the C21-C28 segment and C29-C34 segment. Thus, this coupling reaction proceeded with an equimolar ratio of each segment.

AB - Second-generation total synthesis of aplyronine A, a potent antitumor marine macrolide, was achieved using Ni/Cr-mediated coupling reactions as key steps. The overall yield of the second-generation synthetic pathway of aplyronine A was 1.4%, obtained in 38 steps based on the longest linear sequence. Compared to our first-generation synthetic pathway of aplyronine A, the second-generation synthesis greatly improved both the yield and number of steps. In particular, we improved the stereoselectivity in the construction of the C13 stereogenic center and the C14-C15 (E)-trisubstituted double bond using the asymmetric Ni/Cr-mediated coupling reaction. Furthermore, we established efficient reaction conditions for the asymmetric Ni/Cr-mediated coupling reaction between the C21-C28 segment and C29-C34 segment. Thus, this coupling reaction proceeded with an equimolar ratio of each segment.

UR - http://www.scopus.com/inward/record.url?scp=85006910789&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85006910789&partnerID=8YFLogxK

U2 - 10.1039/c6ob02241c

DO - 10.1039/c6ob02241c

M3 - Article

C2 - 27824201

AN - SCOPUS:85006910789

VL - 15

SP - 124

EP - 131

JO - Organic and Biomolecular Chemistry

JF - Organic and Biomolecular Chemistry

SN - 1477-0520

IS - 1

ER -