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Heterocyclic α-alkylidene cyclopentenones obtained via a Pauson-Khand reaction of amino acid derived allenynes. A scope and limitation study directed toward the preparation of a tricyclic pyrrole library

Brummond, KM and Curran, DP and Mitasev, B and Fischer, S (2005) Heterocyclic α-alkylidene cyclopentenones obtained via a Pauson-Khand reaction of amino acid derived allenynes. A scope and limitation study directed toward the preparation of a tricyclic pyrrole library. Journal of Organic Chemistry, 70 (5). 1745 - 1753. ISSN 0022-3263

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Abstract

(Chemical Equation Presented) The synthesis of a novel class of tricyclic pyrroles has been accomplished by using a Pauson-Khand/Stetter/Paal-Knorr reaction sequence. Full details of the Pauson-Khand reaction of amino acid tethered allenynes 4a-e and 9a-d are disclosed. The study of this reaction led to the discovery of an unprecedented substituent effect on the diastereoselectivity of the Mo(CO)6 mediated allenic Pauson-Khand reaction. It was found that amino acid tethered allenynes with aromatic side chains afford α-alkylidene cyclopentenones with the opposite diastereoselectivity compared to those with aliphatic side chains. This effect has been attributed to complexation of the metal mediator to the aromatic ring in the substrate. Furthermore, an isomerization of one of the diastereomers of the α-alkylidene cyclopentenones was encountered, leading to eventual decomposition. The stable diastereomers were found to react well in the Stetter reaction leading to 1,4-diketones that were converted to pyrroles. The observation that the first generation of 2-alkyl-substituted pyrroles was unstable led to a second generation of 2-carboxamide pyrroles with sufficient stability for biological tests which are in progress. © 2005 American Chemical Society.


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Details

Item Type: Article
Status: Published
Creators/Authors:
CreatorsEmailPitt UsernameORCID
Brummond, KMkbrummon@pitt.eduKBRUMMON
Curran, DPcurran@pitt.eduCURRAN
Mitasev, B
Fischer, S
Date: 4 March 2005
Date Type: Publication
Journal or Publication Title: Journal of Organic Chemistry
Volume: 70
Number: 5
Page Range: 1745 - 1753
DOI or Unique Handle: 10.1021/jo0481607
Schools and Programs: Dietrich School of Arts and Sciences > Chemistry
Refereed: Yes
ISSN: 0022-3263
MeSH Headings: Alkynes--chemical synthesis; Alkynes--chemistry; Amino Acids--chemistry; Cyclopentanes--chemical synthesis; Heterocyclic Compounds--chemical synthesis; Molecular Conformation; Pyrroles--chemical synthesis
PubMed ID: 15730297
Date Deposited: 25 Jul 2013 20:47
Last Modified: 02 Feb 2019 15:59
URI: http://d-scholarship.pitt.edu/id/eprint/19464

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