Formation of Highly Substituted Indenes through Acid Promoted Cyclodehydration with Nucleophile Incorporation

Annaliese S. Dillon, Daniel J. Kerr, Bernard L. Flynn

Research output: Contribution to journalArticleResearchpeer-review

Abstract

Readily accessible 3-aryl-2-carboxypropenones (by Knoevenagel condensation) undergo acid promoted cyclodehydration with nucleophile incorporation to form highly substituted indenes. For stronger nucleophiles, nucleophile incorporation precedes cyclodehydration in a nucleophilic-addition-cyclodehydration (NAC) sequence. For weaker nucleophiles, cyclodehydration precedes nucleophile incorporation in a cyclodehydrative-nucleophilic-trapping (CNT) sequence, involving a reactive allyl cation intermediate. The substrate scope and preferred cyclization pathway (NAC or CNT) has been studied with respect to 3-aryl-2-carboxypropenone and the nature of the nucleophile. Also, for 1,3-diaryl-2-carboxypropenones, which can also undergo Nazarov cyclization, delineation between competing Nazarov and CNT pathways is controlled by the nature of the acid catalyst.

Original languageEnglish
Pages (from-to)2756-2767
Number of pages12
JournalJournal of Organic Chemistry
Volume84
Issue number5
DOIs
Publication statusPublished - 1 Mar 2019

Cite this

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title = "Formation of Highly Substituted Indenes through Acid Promoted Cyclodehydration with Nucleophile Incorporation",
abstract = "Readily accessible 3-aryl-2-carboxypropenones (by Knoevenagel condensation) undergo acid promoted cyclodehydration with nucleophile incorporation to form highly substituted indenes. For stronger nucleophiles, nucleophile incorporation precedes cyclodehydration in a nucleophilic-addition-cyclodehydration (NAC) sequence. For weaker nucleophiles, cyclodehydration precedes nucleophile incorporation in a cyclodehydrative-nucleophilic-trapping (CNT) sequence, involving a reactive allyl cation intermediate. The substrate scope and preferred cyclization pathway (NAC or CNT) has been studied with respect to 3-aryl-2-carboxypropenone and the nature of the nucleophile. Also, for 1,3-diaryl-2-carboxypropenones, which can also undergo Nazarov cyclization, delineation between competing Nazarov and CNT pathways is controlled by the nature of the acid catalyst.",
author = "Dillon, {Annaliese S.} and Kerr, {Daniel J.} and Flynn, {Bernard L.}",
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language = "English",
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journal = "Journal of Organic Chemistry",
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publisher = "American Chemical Society",
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Formation of Highly Substituted Indenes through Acid Promoted Cyclodehydration with Nucleophile Incorporation. / Dillon, Annaliese S.; Kerr, Daniel J.; Flynn, Bernard L.

In: Journal of Organic Chemistry, Vol. 84, No. 5, 01.03.2019, p. 2756-2767.

Research output: Contribution to journalArticleResearchpeer-review

TY - JOUR

T1 - Formation of Highly Substituted Indenes through Acid Promoted Cyclodehydration with Nucleophile Incorporation

AU - Dillon, Annaliese S.

AU - Kerr, Daniel J.

AU - Flynn, Bernard L.

PY - 2019/3/1

Y1 - 2019/3/1

N2 - Readily accessible 3-aryl-2-carboxypropenones (by Knoevenagel condensation) undergo acid promoted cyclodehydration with nucleophile incorporation to form highly substituted indenes. For stronger nucleophiles, nucleophile incorporation precedes cyclodehydration in a nucleophilic-addition-cyclodehydration (NAC) sequence. For weaker nucleophiles, cyclodehydration precedes nucleophile incorporation in a cyclodehydrative-nucleophilic-trapping (CNT) sequence, involving a reactive allyl cation intermediate. The substrate scope and preferred cyclization pathway (NAC or CNT) has been studied with respect to 3-aryl-2-carboxypropenone and the nature of the nucleophile. Also, for 1,3-diaryl-2-carboxypropenones, which can also undergo Nazarov cyclization, delineation between competing Nazarov and CNT pathways is controlled by the nature of the acid catalyst.

AB - Readily accessible 3-aryl-2-carboxypropenones (by Knoevenagel condensation) undergo acid promoted cyclodehydration with nucleophile incorporation to form highly substituted indenes. For stronger nucleophiles, nucleophile incorporation precedes cyclodehydration in a nucleophilic-addition-cyclodehydration (NAC) sequence. For weaker nucleophiles, cyclodehydration precedes nucleophile incorporation in a cyclodehydrative-nucleophilic-trapping (CNT) sequence, involving a reactive allyl cation intermediate. The substrate scope and preferred cyclization pathway (NAC or CNT) has been studied with respect to 3-aryl-2-carboxypropenone and the nature of the nucleophile. Also, for 1,3-diaryl-2-carboxypropenones, which can also undergo Nazarov cyclization, delineation between competing Nazarov and CNT pathways is controlled by the nature of the acid catalyst.

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