Catalytic Iron-Mediated Enediene Carbocyclizations: Investigations into the Stereoselective Formation of Bicyclic Ring Systems

James M. Takacs, John J. Weidner, Peter W. Newsome, Beckie E. Takacs, Ramakrishnan Chidambaram, Richard Shoemaker

Research output: Contribution to journalArticle

29 Citations (Scopus)

Abstract

Trienes in which the requisite 1,3-diene and allylic ether moieties are appended to a pre-existing ring system afford bicyclic ring systems upon iron-catalyzed cyclization. The efficiency and stereoselectivity of the cyclization are dramatically influenced by the nature of the ring system to which the diene and alkene subunits are appended. Certain bicyclic ring systems are formed in good yield; most notably, substrates bearing a basic nitrogen are well-tolerated and certain indolizidine and quinolizidine ring systems are accessible using this methodology. The efficiency and stereoselectivity of the cyclization is also markedly dependent on the ligand used to modify the iron catalyst, and in this regard, a bisoxazoline-modified iron catalyst system is generally superior to what was the standard bipyridine-modified catalyst. In the course of these studies a difference spin polarization transfer (DSPT) experiment proved very useful for the stereochemical analysis of compounds that exhibit very crowded high field NMR spectra.

Original languageEnglish (US)
Pages (from-to)3473-3486
Number of pages14
JournalJournal of Organic Chemistry
Volume60
Issue number11
DOIs
StatePublished - Jun 1 1995

Fingerprint

Cyclization
Stereoselectivity
Iron
Catalysts
Bearings (structural)
Indolizidines
Quinolizidines
Spin polarization
Alkenes
Ether
Nitrogen
Nuclear magnetic resonance
Ligands
Substrates
Experiments

ASJC Scopus subject areas

  • Organic Chemistry

Cite this

Catalytic Iron-Mediated Enediene Carbocyclizations : Investigations into the Stereoselective Formation of Bicyclic Ring Systems. / Takacs, James M.; Weidner, John J.; Newsome, Peter W.; Takacs, Beckie E.; Chidambaram, Ramakrishnan; Shoemaker, Richard.

In: Journal of Organic Chemistry, Vol. 60, No. 11, 01.06.1995, p. 3473-3486.

Research output: Contribution to journalArticle

Takacs, James M. ; Weidner, John J. ; Newsome, Peter W. ; Takacs, Beckie E. ; Chidambaram, Ramakrishnan ; Shoemaker, Richard. / Catalytic Iron-Mediated Enediene Carbocyclizations : Investigations into the Stereoselective Formation of Bicyclic Ring Systems. In: Journal of Organic Chemistry. 1995 ; Vol. 60, No. 11. pp. 3473-3486.
@article{cbd63082a21c4735a6941fc36c28a53e,
title = "Catalytic Iron-Mediated Enediene Carbocyclizations: Investigations into the Stereoselective Formation of Bicyclic Ring Systems",
abstract = "Trienes in which the requisite 1,3-diene and allylic ether moieties are appended to a pre-existing ring system afford bicyclic ring systems upon iron-catalyzed cyclization. The efficiency and stereoselectivity of the cyclization are dramatically influenced by the nature of the ring system to which the diene and alkene subunits are appended. Certain bicyclic ring systems are formed in good yield; most notably, substrates bearing a basic nitrogen are well-tolerated and certain indolizidine and quinolizidine ring systems are accessible using this methodology. The efficiency and stereoselectivity of the cyclization is also markedly dependent on the ligand used to modify the iron catalyst, and in this regard, a bisoxazoline-modified iron catalyst system is generally superior to what was the standard bipyridine-modified catalyst. In the course of these studies a difference spin polarization transfer (DSPT) experiment proved very useful for the stereochemical analysis of compounds that exhibit very crowded high field NMR spectra.",
author = "Takacs, {James M.} and Weidner, {John J.} and Newsome, {Peter W.} and Takacs, {Beckie E.} and Ramakrishnan Chidambaram and Richard Shoemaker",
year = "1995",
month = "6",
day = "1",
doi = "10.1021/jo00116a039",
language = "English (US)",
volume = "60",
pages = "3473--3486",
journal = "Journal of Organic Chemistry",
issn = "0022-3263",
publisher = "American Chemical Society",
number = "11",

}

TY - JOUR

T1 - Catalytic Iron-Mediated Enediene Carbocyclizations

T2 - Investigations into the Stereoselective Formation of Bicyclic Ring Systems

AU - Takacs, James M.

AU - Weidner, John J.

AU - Newsome, Peter W.

AU - Takacs, Beckie E.

AU - Chidambaram, Ramakrishnan

AU - Shoemaker, Richard

PY - 1995/6/1

Y1 - 1995/6/1

N2 - Trienes in which the requisite 1,3-diene and allylic ether moieties are appended to a pre-existing ring system afford bicyclic ring systems upon iron-catalyzed cyclization. The efficiency and stereoselectivity of the cyclization are dramatically influenced by the nature of the ring system to which the diene and alkene subunits are appended. Certain bicyclic ring systems are formed in good yield; most notably, substrates bearing a basic nitrogen are well-tolerated and certain indolizidine and quinolizidine ring systems are accessible using this methodology. The efficiency and stereoselectivity of the cyclization is also markedly dependent on the ligand used to modify the iron catalyst, and in this regard, a bisoxazoline-modified iron catalyst system is generally superior to what was the standard bipyridine-modified catalyst. In the course of these studies a difference spin polarization transfer (DSPT) experiment proved very useful for the stereochemical analysis of compounds that exhibit very crowded high field NMR spectra.

AB - Trienes in which the requisite 1,3-diene and allylic ether moieties are appended to a pre-existing ring system afford bicyclic ring systems upon iron-catalyzed cyclization. The efficiency and stereoselectivity of the cyclization are dramatically influenced by the nature of the ring system to which the diene and alkene subunits are appended. Certain bicyclic ring systems are formed in good yield; most notably, substrates bearing a basic nitrogen are well-tolerated and certain indolizidine and quinolizidine ring systems are accessible using this methodology. The efficiency and stereoselectivity of the cyclization is also markedly dependent on the ligand used to modify the iron catalyst, and in this regard, a bisoxazoline-modified iron catalyst system is generally superior to what was the standard bipyridine-modified catalyst. In the course of these studies a difference spin polarization transfer (DSPT) experiment proved very useful for the stereochemical analysis of compounds that exhibit very crowded high field NMR spectra.

UR - http://www.scopus.com/inward/record.url?scp=0029033822&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0029033822&partnerID=8YFLogxK

U2 - 10.1021/jo00116a039

DO - 10.1021/jo00116a039

M3 - Article

AN - SCOPUS:0029033822

VL - 60

SP - 3473

EP - 3486

JO - Journal of Organic Chemistry

JF - Journal of Organic Chemistry

SN - 0022-3263

IS - 11

ER -