Functionalized Cyclopentenes via the Formal [4+1] Cycloaddition of Photogenerated Siloxycarbenes from Acyl Silanes

João R. Vale; Rafael F. Gomes; Carlos A.M. Afonso; Nuno R. Candeias

doi:10.1021/acs.joc.2c00591

Functionalized Cyclopentenes via the Formal [4+1] Cycloaddition of Photogenerated Siloxycarbenes from Acyl Silanes

João R. Vale, Rafael F. Gomes, Carlos A.M. Afonso, Nuno R. Candeias

Materials Science and Environmental Engineering

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Abstract

This work describes the first formal cycloaddition reaction of photogenerated nucleophilic carbenes derived from acylsilanes with electrophilic dienes. The resulting transient donor-Acceptor cyclopropane rearranges to its stable and highly functionalized cyclopentene isomer in an unprecedented metal-free process. The cyclopropanation-vinyl cyclopropane rearrangement sequence was corroborated by computational calculations. The cyclopropane formation corresponds to a higher energetic barrier, and the vinylcyclopropane-cyclopentene rearrangement proceeds through different mechanisms, although of comparable energies, depending on the stereochemistry of the cyclopropane.

Original language	English
Pages (from-to)	8910-8920
Number of pages	11
Journal	Journal of Organic Chemistry
Volume	87
Issue number	14
DOIs	https://doi.org/10.1021/acs.joc.2c00591
Publication status	Published - 23 Jul 2022
Publication type	A1 Journal article-refereed

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Publication forum level 2

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Organic Chemistry

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10.1021/acs.joc.2c00591

Functionalized cyclopentenes via formal
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title = "Functionalized Cyclopentenes via the Formal [4+1] Cycloaddition of Photogenerated Siloxycarbenes from Acyl Silanes",

abstract = "This work describes the first formal cycloaddition reaction of photogenerated nucleophilic carbenes derived from acylsilanes with electrophilic dienes. The resulting transient donor-Acceptor cyclopropane rearranges to its stable and highly functionalized cyclopentene isomer in an unprecedented metal-free process. The cyclopropanation-vinyl cyclopropane rearrangement sequence was corroborated by computational calculations. The cyclopropane formation corresponds to a higher energetic barrier, and the vinylcyclopropane-cyclopentene rearrangement proceeds through different mechanisms, although of comparable energies, depending on the stereochemistry of the cyclopropane.",

author = "Vale, {Jo{\~a}o R.} and Gomes, {Rafael F.} and Afonso, {Carlos A.M.} and Candeias, {Nuno R.}",

note = "Funding Information: The Academy of Finland is acknowledged for financial support to N.R.C. (decision nos. 326487 and 326486). Funda{\c c}{\~a}o para a Ci{\^e}ncia e Tecnologia (FCT) is acknowledged for financial support to J.R.V. (SFRH/BD/120119/2016) and N.R.C. under the Scientific Employment Stimulus (CEECINST/00026/2018). This work was supported through the projects UIDB/50006/2020, UIDP/50006/2020, UIDB/04138/2020, and UIDP/04138/2020 funded by FCT/MCTES through national funds. The CSC-IT Center for Science Ltd, Finland, is acknowledged for the allocation of computational resources. Publisher Copyright: {\textcopyright} 2022 American Chemical Society. All rights reserved.",

year = "2022",

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doi = "10.1021/acs.joc.2c00591",

language = "English",

volume = "87",

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journal = "Journal of Organic Chemistry",

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T1 - Functionalized Cyclopentenes via the Formal [4+1] Cycloaddition of Photogenerated Siloxycarbenes from Acyl Silanes

AU - Vale, João R.

AU - Gomes, Rafael F.

AU - Afonso, Carlos A.M.

AU - Candeias, Nuno R.

N1 - Funding Information: The Academy of Finland is acknowledged for financial support to N.R.C. (decision nos. 326487 and 326486). Fundação para a Ciência e Tecnologia (FCT) is acknowledged for financial support to J.R.V. (SFRH/BD/120119/2016) and N.R.C. under the Scientific Employment Stimulus (CEECINST/00026/2018). This work was supported through the projects UIDB/50006/2020, UIDP/50006/2020, UIDB/04138/2020, and UIDP/04138/2020 funded by FCT/MCTES through national funds. The CSC-IT Center for Science Ltd, Finland, is acknowledged for the allocation of computational resources. Publisher Copyright: © 2022 American Chemical Society. All rights reserved.

PY - 2022/7/23

Y1 - 2022/7/23

N2 - This work describes the first formal cycloaddition reaction of photogenerated nucleophilic carbenes derived from acylsilanes with electrophilic dienes. The resulting transient donor-Acceptor cyclopropane rearranges to its stable and highly functionalized cyclopentene isomer in an unprecedented metal-free process. The cyclopropanation-vinyl cyclopropane rearrangement sequence was corroborated by computational calculations. The cyclopropane formation corresponds to a higher energetic barrier, and the vinylcyclopropane-cyclopentene rearrangement proceeds through different mechanisms, although of comparable energies, depending on the stereochemistry of the cyclopropane.

AB - This work describes the first formal cycloaddition reaction of photogenerated nucleophilic carbenes derived from acylsilanes with electrophilic dienes. The resulting transient donor-Acceptor cyclopropane rearranges to its stable and highly functionalized cyclopentene isomer in an unprecedented metal-free process. The cyclopropanation-vinyl cyclopropane rearrangement sequence was corroborated by computational calculations. The cyclopropane formation corresponds to a higher energetic barrier, and the vinylcyclopropane-cyclopentene rearrangement proceeds through different mechanisms, although of comparable energies, depending on the stereochemistry of the cyclopropane.

U2 - 10.1021/acs.joc.2c00591

DO - 10.1021/acs.joc.2c00591

M3 - Article

AN - SCOPUS:85134514786

SN - 0022-3263

VL - 87

SP - 8910

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JO - Journal of Organic Chemistry

JF - Journal of Organic Chemistry

IS - 14

ER -

Functionalized Cyclopentenes via the Formal [4+1] Cycloaddition of Photogenerated Siloxycarbenes from Acyl Silanes

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