Phosphine-Catalyzed Enantioselective Intramolecular [3+2] Annulations to Generate Fused Ring Systems

Sarah Yunmi Lee, Yuji Fujiwara, Atsuko Nishiguchi, Marcin Kalek, Gregory C. Fu

Research output: Contribution to journalArticle

72 Citations (Scopus)

Abstract

Substantial progress has been described in the development of asymmetric variants of the phosphine-catalyzed intermolecular [3+2] annulation of allenes with alkenes; however, there have not been corresponding advances for the intramolecular process, which can generate a higher level of complexity (an additional ring and stereocenter(s)). In this study, we describe the application of chiral phosphepine catalysts to address this challenge, thereby providing access to useful scaffolds that are found in bioactive compounds, including diquinane and quinolin-2-one derivatives, with very good stereoselectivity. The products of the [3+2] annulation can be readily transformed into structures that are even more stereochemically rich. Mechanistic studies are consistent with β addition of the phosphepine to the allene being the turnover-limiting step of the catalytic cycle, followed by a concerted [3+2] cycloaddition to the pendant olefin. (Chemical Equation Presented)

Original languageEnglish
Pages (from-to)4587-4591
Number of pages5
JournalJournal of the American Chemical Society
Volume137
Issue number13
DOIs
Publication statusPublished - 2015 Mar 27

Fingerprint

phosphine
Alkenes
Olefins
Stereoselectivity
Cycloaddition
Cycloaddition Reaction
Scaffolds
Derivatives
Catalysts
propadiene

All Science Journal Classification (ASJC) codes

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

Cite this

Lee, Sarah Yunmi ; Fujiwara, Yuji ; Nishiguchi, Atsuko ; Kalek, Marcin ; Fu, Gregory C. / Phosphine-Catalyzed Enantioselective Intramolecular [3+2] Annulations to Generate Fused Ring Systems. In: Journal of the American Chemical Society. 2015 ; Vol. 137, No. 13. pp. 4587-4591.
@article{63b51f2821fb4a45a91bfc009de5925a,
title = "Phosphine-Catalyzed Enantioselective Intramolecular [3+2] Annulations to Generate Fused Ring Systems",
abstract = "Substantial progress has been described in the development of asymmetric variants of the phosphine-catalyzed intermolecular [3+2] annulation of allenes with alkenes; however, there have not been corresponding advances for the intramolecular process, which can generate a higher level of complexity (an additional ring and stereocenter(s)). In this study, we describe the application of chiral phosphepine catalysts to address this challenge, thereby providing access to useful scaffolds that are found in bioactive compounds, including diquinane and quinolin-2-one derivatives, with very good stereoselectivity. The products of the [3+2] annulation can be readily transformed into structures that are even more stereochemically rich. Mechanistic studies are consistent with β addition of the phosphepine to the allene being the turnover-limiting step of the catalytic cycle, followed by a concerted [3+2] cycloaddition to the pendant olefin. (Chemical Equation Presented)",
author = "Lee, {Sarah Yunmi} and Yuji Fujiwara and Atsuko Nishiguchi and Marcin Kalek and Fu, {Gregory C.}",
year = "2015",
month = "3",
day = "27",
doi = "10.1021/jacs.5b01985",
language = "English",
volume = "137",
pages = "4587--4591",
journal = "Journal of the American Chemical Society",
issn = "0002-7863",
publisher = "American Chemical Society",
number = "13",

}

Phosphine-Catalyzed Enantioselective Intramolecular [3+2] Annulations to Generate Fused Ring Systems. / Lee, Sarah Yunmi; Fujiwara, Yuji; Nishiguchi, Atsuko; Kalek, Marcin; Fu, Gregory C.

In: Journal of the American Chemical Society, Vol. 137, No. 13, 27.03.2015, p. 4587-4591.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Phosphine-Catalyzed Enantioselective Intramolecular [3+2] Annulations to Generate Fused Ring Systems

AU - Lee, Sarah Yunmi

AU - Fujiwara, Yuji

AU - Nishiguchi, Atsuko

AU - Kalek, Marcin

AU - Fu, Gregory C.

PY - 2015/3/27

Y1 - 2015/3/27

N2 - Substantial progress has been described in the development of asymmetric variants of the phosphine-catalyzed intermolecular [3+2] annulation of allenes with alkenes; however, there have not been corresponding advances for the intramolecular process, which can generate a higher level of complexity (an additional ring and stereocenter(s)). In this study, we describe the application of chiral phosphepine catalysts to address this challenge, thereby providing access to useful scaffolds that are found in bioactive compounds, including diquinane and quinolin-2-one derivatives, with very good stereoselectivity. The products of the [3+2] annulation can be readily transformed into structures that are even more stereochemically rich. Mechanistic studies are consistent with β addition of the phosphepine to the allene being the turnover-limiting step of the catalytic cycle, followed by a concerted [3+2] cycloaddition to the pendant olefin. (Chemical Equation Presented)

AB - Substantial progress has been described in the development of asymmetric variants of the phosphine-catalyzed intermolecular [3+2] annulation of allenes with alkenes; however, there have not been corresponding advances for the intramolecular process, which can generate a higher level of complexity (an additional ring and stereocenter(s)). In this study, we describe the application of chiral phosphepine catalysts to address this challenge, thereby providing access to useful scaffolds that are found in bioactive compounds, including diquinane and quinolin-2-one derivatives, with very good stereoselectivity. The products of the [3+2] annulation can be readily transformed into structures that are even more stereochemically rich. Mechanistic studies are consistent with β addition of the phosphepine to the allene being the turnover-limiting step of the catalytic cycle, followed by a concerted [3+2] cycloaddition to the pendant olefin. (Chemical Equation Presented)

UR - http://www.scopus.com/inward/record.url?scp=84926644385&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84926644385&partnerID=8YFLogxK

U2 - 10.1021/jacs.5b01985

DO - 10.1021/jacs.5b01985

M3 - Article

C2 - 25815702

AN - SCOPUS:84926644385

VL - 137

SP - 4587

EP - 4591

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

SN - 0002-7863

IS - 13

ER -