Synthesis of the 1,2-seco fusicoccane diterpene skeleton by Stille coupling reaction between the highly functionalized A and C ring segments of cotylenin A

Kazuaki Kuwata, Kengo Hanaya, Shuhei Higashibayashi, Takeshi Sugai, Mitsuru Shoji

Research output: Contribution to journalArticle

3 Citations (Scopus)

Abstract

1-Hydroxy-14-isopropyl-3β-methoxymethyl-7β,11β-dimethyl-3α-[((2-trimethylsilyl)ethoxy)methoxy]-1,2-secofusicocca-8,10(14)-dien-2-one, a highly functionalized 1,2-seco fusicoccane diterpene skeleton related to cotylenin A was synthesized in a convergent manner. The A ring segment, i. e., (1′R,2S, 2′E,5S)-2-methoxymethyl-5-[1′-methyl-3’-(trimethylstannyl)prop-2-enyl]-2-[((2″-trimethylsilyl)ethoxy)methoxy]cyclopentanone, was synthesized in 20.1% yield over 18 steps from known (S)-5-isopropenyl-2-methylcyclopent-1-enecarbaldehyde. This was coupled with the C ring segment, i. e., (R)-5-hydroxymethyl-2-isopropyl-5-methylcyclopent-1-en-1-yl trifluoromethylsulfonate, which was prepared according to our previous report. The Stille coupling reaction between alkenylstannane and sterically hindered triflate proceeded successfully in the presence of PEPPSI-SIPr (85%), and the total yield of the target molecule was 17.1% over the longest linear sequences (19 steps) from (S)-5-isopropenyl-2-methylcyclopent-1-enecarbaldehyde.

Original languageEnglish
Pages (from-to)6039-6045
Number of pages7
JournalTetrahedron
Volume73
Issue number41
DOIs
Publication statusPublished - 2017 Oct 12

Fingerprint

Diterpenes
Skeleton
Molecules
cotylenin A
cyclopentanone

Keywords

  • Alkenyl triflate
  • Alkenylstannane
  • Cyclic terpenoid
  • Natural product synthesis
  • PEPPSI-SIPr
  • Seco-fusicoccane skeleton
  • Stille coupling

ASJC Scopus subject areas

  • Biochemistry
  • Drug Discovery
  • Organic Chemistry

Cite this

@article{c69b4d37e78546b8ad8b62970cf69e14,
title = "Synthesis of the 1,2-seco fusicoccane diterpene skeleton by Stille coupling reaction between the highly functionalized A and C ring segments of cotylenin A",
abstract = "1-Hydroxy-14-isopropyl-3β-methoxymethyl-7β,11β-dimethyl-3α-[((2-trimethylsilyl)ethoxy)methoxy]-1,2-secofusicocca-8,10(14)-dien-2-one, a highly functionalized 1,2-seco fusicoccane diterpene skeleton related to cotylenin A was synthesized in a convergent manner. The A ring segment, i. e., (1′R,2S, 2′E,5S)-2-methoxymethyl-5-[1′-methyl-3’-(trimethylstannyl)prop-2-enyl]-2-[((2″-trimethylsilyl)ethoxy)methoxy]cyclopentanone, was synthesized in 20.1{\%} yield over 18 steps from known (S)-5-isopropenyl-2-methylcyclopent-1-enecarbaldehyde. This was coupled with the C ring segment, i. e., (R)-5-hydroxymethyl-2-isopropyl-5-methylcyclopent-1-en-1-yl trifluoromethylsulfonate, which was prepared according to our previous report. The Stille coupling reaction between alkenylstannane and sterically hindered triflate proceeded successfully in the presence of PEPPSI-SIPr (85{\%}), and the total yield of the target molecule was 17.1{\%} over the longest linear sequences (19 steps) from (S)-5-isopropenyl-2-methylcyclopent-1-enecarbaldehyde.",
keywords = "Alkenyl triflate, Alkenylstannane, Cyclic terpenoid, Natural product synthesis, PEPPSI-SIPr, Seco-fusicoccane skeleton, Stille coupling",
author = "Kazuaki Kuwata and Kengo Hanaya and Shuhei Higashibayashi and Takeshi Sugai and Mitsuru Shoji",
year = "2017",
month = "10",
day = "12",
doi = "10.1016/j.tet.2017.08.056",
language = "English",
volume = "73",
pages = "6039--6045",
journal = "Tetrahedron",
issn = "0040-4020",
publisher = "Elsevier Limited",
number = "41",

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TY - JOUR

T1 - Synthesis of the 1,2-seco fusicoccane diterpene skeleton by Stille coupling reaction between the highly functionalized A and C ring segments of cotylenin A

AU - Kuwata, Kazuaki

AU - Hanaya, Kengo

AU - Higashibayashi, Shuhei

AU - Sugai, Takeshi

AU - Shoji, Mitsuru

PY - 2017/10/12

Y1 - 2017/10/12

N2 - 1-Hydroxy-14-isopropyl-3β-methoxymethyl-7β,11β-dimethyl-3α-[((2-trimethylsilyl)ethoxy)methoxy]-1,2-secofusicocca-8,10(14)-dien-2-one, a highly functionalized 1,2-seco fusicoccane diterpene skeleton related to cotylenin A was synthesized in a convergent manner. The A ring segment, i. e., (1′R,2S, 2′E,5S)-2-methoxymethyl-5-[1′-methyl-3’-(trimethylstannyl)prop-2-enyl]-2-[((2″-trimethylsilyl)ethoxy)methoxy]cyclopentanone, was synthesized in 20.1% yield over 18 steps from known (S)-5-isopropenyl-2-methylcyclopent-1-enecarbaldehyde. This was coupled with the C ring segment, i. e., (R)-5-hydroxymethyl-2-isopropyl-5-methylcyclopent-1-en-1-yl trifluoromethylsulfonate, which was prepared according to our previous report. The Stille coupling reaction between alkenylstannane and sterically hindered triflate proceeded successfully in the presence of PEPPSI-SIPr (85%), and the total yield of the target molecule was 17.1% over the longest linear sequences (19 steps) from (S)-5-isopropenyl-2-methylcyclopent-1-enecarbaldehyde.

AB - 1-Hydroxy-14-isopropyl-3β-methoxymethyl-7β,11β-dimethyl-3α-[((2-trimethylsilyl)ethoxy)methoxy]-1,2-secofusicocca-8,10(14)-dien-2-one, a highly functionalized 1,2-seco fusicoccane diterpene skeleton related to cotylenin A was synthesized in a convergent manner. The A ring segment, i. e., (1′R,2S, 2′E,5S)-2-methoxymethyl-5-[1′-methyl-3’-(trimethylstannyl)prop-2-enyl]-2-[((2″-trimethylsilyl)ethoxy)methoxy]cyclopentanone, was synthesized in 20.1% yield over 18 steps from known (S)-5-isopropenyl-2-methylcyclopent-1-enecarbaldehyde. This was coupled with the C ring segment, i. e., (R)-5-hydroxymethyl-2-isopropyl-5-methylcyclopent-1-en-1-yl trifluoromethylsulfonate, which was prepared according to our previous report. The Stille coupling reaction between alkenylstannane and sterically hindered triflate proceeded successfully in the presence of PEPPSI-SIPr (85%), and the total yield of the target molecule was 17.1% over the longest linear sequences (19 steps) from (S)-5-isopropenyl-2-methylcyclopent-1-enecarbaldehyde.

KW - Alkenyl triflate

KW - Alkenylstannane

KW - Cyclic terpenoid

KW - Natural product synthesis

KW - PEPPSI-SIPr

KW - Seco-fusicoccane skeleton

KW - Stille coupling

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U2 - 10.1016/j.tet.2017.08.056

DO - 10.1016/j.tet.2017.08.056

M3 - Article

VL - 73

SP - 6039

EP - 6045

JO - Tetrahedron

JF - Tetrahedron

SN - 0040-4020

IS - 41

ER -