Tremorgenic indole alkaloids. 9. Asymmetric construction of an advanced F-G-H-ring lactone precursor for the synthesis of penitrem D

Amos B. Smith, Ernest G. Nolen, Ryuichi Shirai, Frances R. Blase, Mitsuaki Ohta, Noritaka Chida, Richard A. Hartz, Duke M. Fitch, William M. Clark, Paul A. Sprengeler

Research output: Contribution to journalArticle

38 Citations (Scopus)

Abstract

Lactone (+)-12 is envisioned as the precursor to the F-G-H rings of penitrem D (4) in our ongoing synthetic venture. The efficient, stereocontrolled introduction of the vicinal quaternary methyl groups present the major challenge in the construction of this subunit. Our first route to (±)-12 was marked by low overall yield (<2%) and the instability of several key intermediates; these deficiencies were rectified in a second-generation approach that produced optically active material (18 steps from 19a, 2.1% overall). The successful strategies exploited enolate generation via either conjugate additions to α,β-enones or the Evans oxy-Cope rearrangement as key regiochemical control elements.

Original languageEnglish
Pages (from-to)7837-7848
Number of pages12
JournalJournal of Organic Chemistry
Volume60
Issue number24
Publication statusPublished - 1995
Externally publishedYes

Fingerprint

Indole Alkaloids
Lactones
tremortin

ASJC Scopus subject areas

  • Organic Chemistry

Cite this

Smith, A. B., Nolen, E. G., Shirai, R., Blase, F. R., Ohta, M., Chida, N., ... Sprengeler, P. A. (1995). Tremorgenic indole alkaloids. 9. Asymmetric construction of an advanced F-G-H-ring lactone precursor for the synthesis of penitrem D. Journal of Organic Chemistry, 60(24), 7837-7848.

Tremorgenic indole alkaloids. 9. Asymmetric construction of an advanced F-G-H-ring lactone precursor for the synthesis of penitrem D. / Smith, Amos B.; Nolen, Ernest G.; Shirai, Ryuichi; Blase, Frances R.; Ohta, Mitsuaki; Chida, Noritaka; Hartz, Richard A.; Fitch, Duke M.; Clark, William M.; Sprengeler, Paul A.

In: Journal of Organic Chemistry, Vol. 60, No. 24, 1995, p. 7837-7848.

Research output: Contribution to journalArticle

Smith, AB, Nolen, EG, Shirai, R, Blase, FR, Ohta, M, Chida, N, Hartz, RA, Fitch, DM, Clark, WM & Sprengeler, PA 1995, 'Tremorgenic indole alkaloids. 9. Asymmetric construction of an advanced F-G-H-ring lactone precursor for the synthesis of penitrem D', Journal of Organic Chemistry, vol. 60, no. 24, pp. 7837-7848.
Smith, Amos B. ; Nolen, Ernest G. ; Shirai, Ryuichi ; Blase, Frances R. ; Ohta, Mitsuaki ; Chida, Noritaka ; Hartz, Richard A. ; Fitch, Duke M. ; Clark, William M. ; Sprengeler, Paul A. / Tremorgenic indole alkaloids. 9. Asymmetric construction of an advanced F-G-H-ring lactone precursor for the synthesis of penitrem D. In: Journal of Organic Chemistry. 1995 ; Vol. 60, No. 24. pp. 7837-7848.
@article{627c3f3d5fed4cf3934aa0c3ad14361c,
title = "Tremorgenic indole alkaloids. 9. Asymmetric construction of an advanced F-G-H-ring lactone precursor for the synthesis of penitrem D",
abstract = "Lactone (+)-12 is envisioned as the precursor to the F-G-H rings of penitrem D (4) in our ongoing synthetic venture. The efficient, stereocontrolled introduction of the vicinal quaternary methyl groups present the major challenge in the construction of this subunit. Our first route to (±)-12 was marked by low overall yield (<2{\%}) and the instability of several key intermediates; these deficiencies were rectified in a second-generation approach that produced optically active material (18 steps from 19a, 2.1{\%} overall). The successful strategies exploited enolate generation via either conjugate additions to α,β-enones or the Evans oxy-Cope rearrangement as key regiochemical control elements.",
author = "Smith, {Amos B.} and Nolen, {Ernest G.} and Ryuichi Shirai and Blase, {Frances R.} and Mitsuaki Ohta and Noritaka Chida and Hartz, {Richard A.} and Fitch, {Duke M.} and Clark, {William M.} and Sprengeler, {Paul A.}",
year = "1995",
language = "English",
volume = "60",
pages = "7837--7848",
journal = "Journal of Organic Chemistry",
issn = "0022-3263",
publisher = "American Chemical Society",
number = "24",

}

TY - JOUR

T1 - Tremorgenic indole alkaloids. 9. Asymmetric construction of an advanced F-G-H-ring lactone precursor for the synthesis of penitrem D

AU - Smith, Amos B.

AU - Nolen, Ernest G.

AU - Shirai, Ryuichi

AU - Blase, Frances R.

AU - Ohta, Mitsuaki

AU - Chida, Noritaka

AU - Hartz, Richard A.

AU - Fitch, Duke M.

AU - Clark, William M.

AU - Sprengeler, Paul A.

PY - 1995

Y1 - 1995

N2 - Lactone (+)-12 is envisioned as the precursor to the F-G-H rings of penitrem D (4) in our ongoing synthetic venture. The efficient, stereocontrolled introduction of the vicinal quaternary methyl groups present the major challenge in the construction of this subunit. Our first route to (±)-12 was marked by low overall yield (<2%) and the instability of several key intermediates; these deficiencies were rectified in a second-generation approach that produced optically active material (18 steps from 19a, 2.1% overall). The successful strategies exploited enolate generation via either conjugate additions to α,β-enones or the Evans oxy-Cope rearrangement as key regiochemical control elements.

AB - Lactone (+)-12 is envisioned as the precursor to the F-G-H rings of penitrem D (4) in our ongoing synthetic venture. The efficient, stereocontrolled introduction of the vicinal quaternary methyl groups present the major challenge in the construction of this subunit. Our first route to (±)-12 was marked by low overall yield (<2%) and the instability of several key intermediates; these deficiencies were rectified in a second-generation approach that produced optically active material (18 steps from 19a, 2.1% overall). The successful strategies exploited enolate generation via either conjugate additions to α,β-enones or the Evans oxy-Cope rearrangement as key regiochemical control elements.

UR - http://www.scopus.com/inward/record.url?scp=0028858548&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0028858548&partnerID=8YFLogxK

M3 - Article

AN - SCOPUS:0028858548

VL - 60

SP - 7837

EP - 7848

JO - Journal of Organic Chemistry

JF - Journal of Organic Chemistry

SN - 0022-3263

IS - 24

ER -