Mechanistic Studies on the Base-Promoted Conversion of Alkoxy-Substituted, Ring-Fused gem-Dihalocyclopropanes into Furans: Evidence for a Process Involving Electrocyclic Ring Closure of a Carbonyl Ylide Intermediate

Phillip P. Sharp; Jiri Mikusek; Junming Ho; Elizabeth H. Krenske; Martin G. Banwell; Michelle L. Coote; Jas S. Ward; Anthony C. Willis

doi:10.1021/acs.joc.8b01766

Mechanistic Studies on the Base-Promoted Conversion of Alkoxy-Substituted, Ring-Fused gem-Dihalocyclopropanes into Furans: Evidence for a Process Involving Electrocyclic Ring Closure of a Carbonyl Ylide Intermediate

Phillip P. Sharp, Jiri Mikusek, Junming Ho, Elizabeth H. Krenske, Martin G. Banwell, Michelle L. Coote, Jas S. Ward, Anthony C. Willis

Research output: Contribution to journal › Article › peer-review

7 Citations (Scopus)

Abstract

The mechanism associated with the base-promoted conversion of alkoxy-substituted and ring-fused gem-dihalocyclopropanes such as 40 into annulated furans has been explored. Treatment of compound 40 with potassium tert-butoxide affords a mixture of furans 23/27 and 41, an outcome that suggests the intermediacy of the slowly interconverting carbonyl ylides 42 and 43 that undergo rapid [1,5]-electrocyclizations and subsequent dehydrohalogenation to afford the observed products. This proposal is supported by ab initio MO and DFT calculations that also suggest a vinylcarbene insertion pathway is less likely to be operative.

Original language	English
Pages (from-to)	13678-13690
Number of pages	13
Journal	Journal of Organic Chemistry
Volume	83
Issue number	22
DOIs	https://doi.org/10.1021/acs.joc.8b01766
Publication status	Published - 16 Nov 2018
Externally published	Yes

Keywords

Lipids
Chromatography
Chemical reactions
Organic compounds
Nuclear magnetic resonance spectroscopy

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Sharp, P. P., Mikusek, J., Ho, J., Krenske, E. H., Banwell, M. G., Coote, M. L., Ward, J. S., & Willis, A. C. (2018). Mechanistic Studies on the Base-Promoted Conversion of Alkoxy-Substituted, Ring-Fused gem-Dihalocyclopropanes into Furans: Evidence for a Process Involving Electrocyclic Ring Closure of a Carbonyl Ylide Intermediate. Journal of Organic Chemistry, 83(22), 13678-13690. https://doi.org/10.1021/acs.joc.8b01766

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title = "Mechanistic Studies on the Base-Promoted Conversion of Alkoxy-Substituted, Ring-Fused gem-Dihalocyclopropanes into Furans: Evidence for a Process Involving Electrocyclic Ring Closure of a Carbonyl Ylide Intermediate",

abstract = "The mechanism associated with the base-promoted conversion of alkoxy-substituted and ring-fused gem-dihalocyclopropanes such as 40 into annulated furans has been explored. Treatment of compound 40 with potassium tert-butoxide affords a mixture of furans 23/27 and 41, an outcome that suggests the intermediacy of the slowly interconverting carbonyl ylides 42 and 43 that undergo rapid [1,5]-electrocyclizations and subsequent dehydrohalogenation to afford the observed products. This proposal is supported by ab initio MO and DFT calculations that also suggest a vinylcarbene insertion pathway is less likely to be operative.",

keywords = "Lipids, Chromatography, Chemical reactions, Organic compounds, Nuclear magnetic resonance spectroscopy",

author = "Sharp, {Phillip P.} and Jiri Mikusek and Junming Ho and Krenske, {Elizabeth H.} and Banwell, {Martin G.} and Coote, {Michelle L.} and Ward, {Jas S.} and Willis, {Anthony C.}",

year = "2018",

month = nov,

day = "16",

doi = "10.1021/acs.joc.8b01766",

language = "English",

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Sharp, PP, Mikusek, J, Ho, J, Krenske, EH, Banwell, MG, Coote, ML, Ward, JS & Willis, AC 2018, 'Mechanistic Studies on the Base-Promoted Conversion of Alkoxy-Substituted, Ring-Fused gem-Dihalocyclopropanes into Furans: Evidence for a Process Involving Electrocyclic Ring Closure of a Carbonyl Ylide Intermediate', Journal of Organic Chemistry, vol. 83, no. 22, pp. 13678-13690. https://doi.org/10.1021/acs.joc.8b01766

Mechanistic Studies on the Base-Promoted Conversion of Alkoxy-Substituted, Ring-Fused gem-Dihalocyclopropanes into Furans: Evidence for a Process Involving Electrocyclic Ring Closure of a Carbonyl Ylide Intermediate. / Sharp, Phillip P.; Mikusek, Jiri; Ho, Junming et al.
In: Journal of Organic Chemistry, Vol. 83, No. 22, 16.11.2018, p. 13678-13690.

Research output: Contribution to journal › Article › peer-review

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T1 - Mechanistic Studies on the Base-Promoted Conversion of Alkoxy-Substituted, Ring-Fused gem-Dihalocyclopropanes into Furans

T2 - Evidence for a Process Involving Electrocyclic Ring Closure of a Carbonyl Ylide Intermediate

AU - Sharp, Phillip P.

AU - Mikusek, Jiri

AU - Ho, Junming

AU - Krenske, Elizabeth H.

AU - Banwell, Martin G.

AU - Coote, Michelle L.

AU - Ward, Jas S.

AU - Willis, Anthony C.

PY - 2018/11/16

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N2 - The mechanism associated with the base-promoted conversion of alkoxy-substituted and ring-fused gem-dihalocyclopropanes such as 40 into annulated furans has been explored. Treatment of compound 40 with potassium tert-butoxide affords a mixture of furans 23/27 and 41, an outcome that suggests the intermediacy of the slowly interconverting carbonyl ylides 42 and 43 that undergo rapid [1,5]-electrocyclizations and subsequent dehydrohalogenation to afford the observed products. This proposal is supported by ab initio MO and DFT calculations that also suggest a vinylcarbene insertion pathway is less likely to be operative.

AB - The mechanism associated with the base-promoted conversion of alkoxy-substituted and ring-fused gem-dihalocyclopropanes such as 40 into annulated furans has been explored. Treatment of compound 40 with potassium tert-butoxide affords a mixture of furans 23/27 and 41, an outcome that suggests the intermediacy of the slowly interconverting carbonyl ylides 42 and 43 that undergo rapid [1,5]-electrocyclizations and subsequent dehydrohalogenation to afford the observed products. This proposal is supported by ab initio MO and DFT calculations that also suggest a vinylcarbene insertion pathway is less likely to be operative.

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KW - Nuclear magnetic resonance spectroscopy

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Sharp PP, Mikusek J, Ho J, Krenske EH, Banwell MG, Coote ML et al. Mechanistic Studies on the Base-Promoted Conversion of Alkoxy-Substituted, Ring-Fused gem-Dihalocyclopropanes into Furans: Evidence for a Process Involving Electrocyclic Ring Closure of a Carbonyl Ylide Intermediate. Journal of Organic Chemistry. 2018 Nov 16;83(22):13678-13690. doi: 10.1021/acs.joc.8b01766

Mechanistic Studies on the Base-Promoted Conversion of Alkoxy-Substituted, Ring-Fused gem-Dihalocyclopropanes into Furans: Evidence for a Process Involving Electrocyclic Ring Closure of a Carbonyl Ylide Intermediate

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