Asymmetric Total Synthesis of (-)-Englerin A through Catalytic Diastereo- and Enantioselective Carbonyl Ylide Cycloaddition

Taiki Hanari; Naoyuki Shimada; Yasunobu Kurosaki; Neetipalli Thrimurtulu; Hisanori Nambu; Masahiro Anada; Shunichi Hashimoto

doi:10.1002/chem.201502009

Asymmetric Total Synthesis of (-)-Englerin A through Catalytic Diastereo- and Enantioselective Carbonyl Ylide Cycloaddition

Taiki Hanari, Naoyuki Shimada, Yasunobu Kurosaki, Neetipalli Thrimurtulu, Hisanori Nambu, Masahiro Anada^*, Shunichi Hashimoto

^*Corresponding author for this work

Synthetic and Biomolecular Organic Chemistry

Research output: Contribution to journal › Article › peer-review

49 Scopus citations

Abstract

An asymmetric total synthesis of the guaiane sesquiterpene (-)-englerin A, a potent and selective inhibitor of the growth of renal cancer cell lines, was accomplished. The basis of the approach is a highly diastereo- and enantioselective carbonyl ylide cycloaddition with an ethyl vinyl ether dipolarophile under catalysis by dirhodium(II) tetrakis[N-tetrachlorophthaloyl-(S)-tert-leucinate], [Rh₂(S-TCPTTL)₄], to construct the oxabicyclo[3.2.1]octane framework with concomitant introduction of the oxygen substituent at C9 on the exo-face. Another notable feature of the synthesis is ruthenium tetraoxide-catalyzed chemoselective oxidative conversion of C9 ethyl ether to C9 acetate.

Original language	English
Pages (from-to)	11671-11676
Number of pages	6
Journal	Chemistry - A European Journal
Volume	21
Issue number	33
DOIs	https://doi.org/10.1002/chem.201502009
State	Published - 2015/08/01

Keywords

(-)-englerin A
1,3-dipolar cycloaddition
asymmetric synthesis
carbonyl ylide
dirhodium(II) complexes
total synthesis

ASJC Scopus subject areas

Catalysis
Organic Chemistry

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

Access to Document

10.1002/chem.201502009

Cite this

@article{8f7ffe54ca2a4eaf8514982103048d9d,

title = "Asymmetric Total Synthesis of (-)-Englerin A through Catalytic Diastereo- and Enantioselective Carbonyl Ylide Cycloaddition",

abstract = "An asymmetric total synthesis of the guaiane sesquiterpene (-)-englerin A, a potent and selective inhibitor of the growth of renal cancer cell lines, was accomplished. The basis of the approach is a highly diastereo- and enantioselective carbonyl ylide cycloaddition with an ethyl vinyl ether dipolarophile under catalysis by dirhodium(II) tetrakis[N-tetrachlorophthaloyl-(S)-tert-leucinate], [Rh2(S-TCPTTL)4], to construct the oxabicyclo[3.2.1]octane framework with concomitant introduction of the oxygen substituent at C9 on the exo-face. Another notable feature of the synthesis is ruthenium tetraoxide-catalyzed chemoselective oxidative conversion of C9 ethyl ether to C9 acetate.",

keywords = "(-)-englerin A, 1,3-dipolar cycloaddition, asymmetric synthesis, carbonyl ylide, dirhodium(II) complexes, total synthesis",

author = "Taiki Hanari and Naoyuki Shimada and Yasunobu Kurosaki and Neetipalli Thrimurtulu and Hisanori Nambu and Masahiro Anada and Shunichi Hashimoto",

note = "Publisher Copyright: {\textcopyright} 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.",

year = "2015",

month = aug,

day = "1",

doi = "10.1002/chem.201502009",

language = "英語",

volume = "21",

pages = "11671--11676",

journal = "Chemistry - A European Journal",

issn = "0947-6539",

publisher = "Wiley-VCH Verlag",

number = "33",

}

TY - JOUR

T1 - Asymmetric Total Synthesis of (-)-Englerin A through Catalytic Diastereo- and Enantioselective Carbonyl Ylide Cycloaddition

AU - Hanari, Taiki

AU - Shimada, Naoyuki

AU - Kurosaki, Yasunobu

AU - Thrimurtulu, Neetipalli

AU - Nambu, Hisanori

AU - Anada, Masahiro

AU - Hashimoto, Shunichi

PY - 2015/8/1

Y1 - 2015/8/1

N2 - An asymmetric total synthesis of the guaiane sesquiterpene (-)-englerin A, a potent and selective inhibitor of the growth of renal cancer cell lines, was accomplished. The basis of the approach is a highly diastereo- and enantioselective carbonyl ylide cycloaddition with an ethyl vinyl ether dipolarophile under catalysis by dirhodium(II) tetrakis[N-tetrachlorophthaloyl-(S)-tert-leucinate], [Rh2(S-TCPTTL)4], to construct the oxabicyclo[3.2.1]octane framework with concomitant introduction of the oxygen substituent at C9 on the exo-face. Another notable feature of the synthesis is ruthenium tetraoxide-catalyzed chemoselective oxidative conversion of C9 ethyl ether to C9 acetate.

AB - An asymmetric total synthesis of the guaiane sesquiterpene (-)-englerin A, a potent and selective inhibitor of the growth of renal cancer cell lines, was accomplished. The basis of the approach is a highly diastereo- and enantioselective carbonyl ylide cycloaddition with an ethyl vinyl ether dipolarophile under catalysis by dirhodium(II) tetrakis[N-tetrachlorophthaloyl-(S)-tert-leucinate], [Rh2(S-TCPTTL)4], to construct the oxabicyclo[3.2.1]octane framework with concomitant introduction of the oxygen substituent at C9 on the exo-face. Another notable feature of the synthesis is ruthenium tetraoxide-catalyzed chemoselective oxidative conversion of C9 ethyl ether to C9 acetate.

KW - (-)-englerin A

KW - 1,3-dipolar cycloaddition

KW - asymmetric synthesis

KW - carbonyl ylide

KW - dirhodium(II) complexes

KW - total synthesis

UR - http://www.scopus.com/inward/record.url?scp=84938379137&partnerID=8YFLogxK

U2 - 10.1002/chem.201502009

DO - 10.1002/chem.201502009

M3 - 学術論文

C2 - 26356596

AN - SCOPUS:84938379137

SN - 0947-6539

VL - 21

SP - 11671

EP - 11676

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

IS - 33

ER -

Asymmetric Total Synthesis of (-)-Englerin A through Catalytic Diastereo- and Enantioselective Carbonyl Ylide Cycloaddition

Abstract

Keywords

ASJC Scopus subject areas

UN SDGs

Access to Document

Fingerprint

Cite this