Stereocontrolled Asymmetric Total Synthesis of Protomycinolide IV

Keisuke Suzuki, Katsuhiko Tomooka, Eiji Katayama, Takashi Matsumoto, Gen ichi Tsuchihashi

Research output: Contribution to journalArticle

76 Citations (Scopus)

Abstract

Stereocontrolled asymmetric total synthesis of protomycinolide IV (1) was achieved, based on the organo-aluminum-promoted stereospecific pinacol-type 1,2-rearrangement. Two chiral fragments, C(1)–C(9) and C(11)–(17) portions, were constructed from a common chiral starting material, (S)-ethyl lactate. High diastereoselectivity of the nucleophilic attack on the Me3Si-bearing α-methyl-β,γ-unsaturated carbonyl compounds was fully utilized for establishing the chiral centers at C(5) and C(6) relative to C(4) and C(15) relative to C(14). For the stereocontrol of the Me substituent at C(8), two methods were newly devised: (i) thermodynamic equilibration of δ-lactone 16 and (ii) acid-catalyzed stereoselective cyclization of ketene dithioacetal possessing an internal hydroxyl group.

Original languageEnglish
Pages (from-to)5221-5229
Number of pages9
JournalJournal of the American Chemical Society
Volume108
Issue number17
DOIs
Publication statusPublished - Jan 1 1986
Externally publishedYes

Fingerprint

Bearings (structural)
Carbonyl compounds
Cyclization
Lactones
Aluminum
Thermodynamics
Hydroxyl Radical
Acids
protomycinolide IV
ketene
ethyl lactate

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Stereocontrolled Asymmetric Total Synthesis of Protomycinolide IV. / Suzuki, Keisuke; Tomooka, Katsuhiko; Katayama, Eiji; Matsumoto, Takashi; Tsuchihashi, Gen ichi.

In: Journal of the American Chemical Society, Vol. 108, No. 17, 01.01.1986, p. 5221-5229.

Research output: Contribution to journalArticle

Suzuki, Keisuke ; Tomooka, Katsuhiko ; Katayama, Eiji ; Matsumoto, Takashi ; Tsuchihashi, Gen ichi. / Stereocontrolled Asymmetric Total Synthesis of Protomycinolide IV. In: Journal of the American Chemical Society. 1986 ; Vol. 108, No. 17. pp. 5221-5229.
@article{b16c26135c1f4935a5981ae87b7d14af,
title = "Stereocontrolled Asymmetric Total Synthesis of Protomycinolide IV",
abstract = "Stereocontrolled asymmetric total synthesis of protomycinolide IV (1) was achieved, based on the organo-aluminum-promoted stereospecific pinacol-type 1,2-rearrangement. Two chiral fragments, C(1)–C(9) and C(11)–(17) portions, were constructed from a common chiral starting material, (S)-ethyl lactate. High diastereoselectivity of the nucleophilic attack on the Me3Si-bearing α-methyl-β,γ-unsaturated carbonyl compounds was fully utilized for establishing the chiral centers at C(5) and C(6) relative to C(4) and C(15) relative to C(14). For the stereocontrol of the Me substituent at C(8), two methods were newly devised: (i) thermodynamic equilibration of δ-lactone 16 and (ii) acid-catalyzed stereoselective cyclization of ketene dithioacetal possessing an internal hydroxyl group.",
author = "Keisuke Suzuki and Katsuhiko Tomooka and Eiji Katayama and Takashi Matsumoto and Tsuchihashi, {Gen ichi}",
year = "1986",
month = "1",
day = "1",
doi = "10.1021/ja00277a028",
language = "English",
volume = "108",
pages = "5221--5229",
journal = "Journal of the American Chemical Society",
issn = "0002-7863",
publisher = "American Chemical Society",
number = "17",

}

TY - JOUR

T1 - Stereocontrolled Asymmetric Total Synthesis of Protomycinolide IV

AU - Suzuki, Keisuke

AU - Tomooka, Katsuhiko

AU - Katayama, Eiji

AU - Matsumoto, Takashi

AU - Tsuchihashi, Gen ichi

PY - 1986/1/1

Y1 - 1986/1/1

N2 - Stereocontrolled asymmetric total synthesis of protomycinolide IV (1) was achieved, based on the organo-aluminum-promoted stereospecific pinacol-type 1,2-rearrangement. Two chiral fragments, C(1)–C(9) and C(11)–(17) portions, were constructed from a common chiral starting material, (S)-ethyl lactate. High diastereoselectivity of the nucleophilic attack on the Me3Si-bearing α-methyl-β,γ-unsaturated carbonyl compounds was fully utilized for establishing the chiral centers at C(5) and C(6) relative to C(4) and C(15) relative to C(14). For the stereocontrol of the Me substituent at C(8), two methods were newly devised: (i) thermodynamic equilibration of δ-lactone 16 and (ii) acid-catalyzed stereoselective cyclization of ketene dithioacetal possessing an internal hydroxyl group.

AB - Stereocontrolled asymmetric total synthesis of protomycinolide IV (1) was achieved, based on the organo-aluminum-promoted stereospecific pinacol-type 1,2-rearrangement. Two chiral fragments, C(1)–C(9) and C(11)–(17) portions, were constructed from a common chiral starting material, (S)-ethyl lactate. High diastereoselectivity of the nucleophilic attack on the Me3Si-bearing α-methyl-β,γ-unsaturated carbonyl compounds was fully utilized for establishing the chiral centers at C(5) and C(6) relative to C(4) and C(15) relative to C(14). For the stereocontrol of the Me substituent at C(8), two methods were newly devised: (i) thermodynamic equilibration of δ-lactone 16 and (ii) acid-catalyzed stereoselective cyclization of ketene dithioacetal possessing an internal hydroxyl group.

UR - http://www.scopus.com/inward/record.url?scp=0022457825&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0022457825&partnerID=8YFLogxK

U2 - 10.1021/ja00277a028

DO - 10.1021/ja00277a028

M3 - Article

AN - SCOPUS:0022457825

VL - 108

SP - 5221

EP - 5229

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

SN - 0002-7863

IS - 17

ER -