Formation of Seven-Membered Rings by Ring-Closing Metathesis of Vinyl Bromides
Formation of Seven-Membered Rings by Ring-Closing Metathesis of Vinyl Bromides
A Grubbs II catalyst mediated ring-closing metathesis (RCM) of monobrominated dienes is reported to proceed in moderate to good yields (40 80%) where the linking chain contains five atoms, leading to carbocyclic and heterocyclic seven-membered bromoolefins. Notably, RCM to form five-, six-, or eight-membered bromoolefins was unsuccessful, with the exception of one example where RCM afforded diethyl 3-bromocyclohex-3-ene-1,1-dicarboxylate. In this case, a bromomethyl-substituted cyclohexene was obtained as a byproduct. The utility of selected bromoolefin RCM products was demonstrated through their participation in Suzuki Miyaura reactions. Vinylic halide exchange (Br → Cl) was noted as a side reaction under RCM conditions.
carbocycles, Grubbs catalyst, heterocycles, ring-closing metathesis, vinylic bromides
1453-1457
Ajavakom, Vachiraporn
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Pandokrak, Potchanee
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Salim, Sofia S.
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Moustafa, Gamal
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Bellingham, Richard K.
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Hill-Cousins, Joseph T.
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Ajavakom, Anawat
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Brown, Richard C.D.
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6 May 2022
Ajavakom, Vachiraporn
f993a9cd-e859-41c0-995b-a40f1bf19a7c
Pandokrak, Potchanee
83904219-68f5-49b5-a024-fd4cfb86e036
Salim, Sofia S.
d5de5263-b418-469b-b3f5-bdd05ee48387
Moustafa, Gamal
1a452cdc-4856-4243-9864-b391fb115f07
Bellingham, Richard K.
ffa421f3-f2fb-4de9-b3f1-bba3f18b8976
Hill-Cousins, Joseph T.
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Ajavakom, Anawat
5bfbc657-18ac-4cfd-8e6c-3969f2a51e0e
Brown, Richard C.D.
21ce697a-7c3a-480e-919f-429a3d8550f5
Ajavakom, Vachiraporn, Pandokrak, Potchanee, Salim, Sofia S., Moustafa, Gamal, Bellingham, Richard K., Hill-Cousins, Joseph T., Ajavakom, Anawat and Brown, Richard C.D.
(2022)
Formation of Seven-Membered Rings by Ring-Closing Metathesis of Vinyl Bromides.
Synlett, 33 (14), .
(doi:10.1055/a-1845-4195).
Abstract
A Grubbs II catalyst mediated ring-closing metathesis (RCM) of monobrominated dienes is reported to proceed in moderate to good yields (40 80%) where the linking chain contains five atoms, leading to carbocyclic and heterocyclic seven-membered bromoolefins. Notably, RCM to form five-, six-, or eight-membered bromoolefins was unsuccessful, with the exception of one example where RCM afforded diethyl 3-bromocyclohex-3-ene-1,1-dicarboxylate. In this case, a bromomethyl-substituted cyclohexene was obtained as a byproduct. The utility of selected bromoolefin RCM products was demonstrated through their participation in Suzuki Miyaura reactions. Vinylic halide exchange (Br → Cl) was noted as a side reaction under RCM conditions.
Text
a-1845-4195
- Accepted Manuscript
More information
Accepted/In Press date: 6 May 2022
e-pub ahead of print date: 6 May 2022
Published date: 6 May 2022
Additional Information:
Funding Information:
The authors acknowledge EPSRC and GlaxoSmithKline for a CASE award (S.S.S.), the Royal Society for a University Research Fellowship (R.C.D.B.), and the European Regional Development Fund (ERDF) for funding the AI-Chem project through the INTERREG IVa program 4061. This work was also supported by the Center of Excellence for Innovation in Chemistry (PERCH-CIC). EngineeingandPhysical SciencesReseachCouncilGlaxoSmihtKlineRoyal SoietyEuopeanRegional DevelopmentFundCenterofExcellenceforInnovatoninChemisy
Publisher Copyright:
© 2022 Georg Thieme Verlag. All rights reserved.
Keywords:
carbocycles, Grubbs catalyst, heterocycles, ring-closing metathesis, vinylic bromides
Identifiers
Local EPrints ID: 457323
URI: http://eprints.soton.ac.uk/id/eprint/457323
ISSN: 0936-5214
PURE UUID: c872ee26-8672-4b5f-ba10-1600c8c2e55b
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Date deposited: 01 Jun 2022 16:38
Last modified: 17 Mar 2024 07:18
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Contributors
Author:
Vachiraporn Ajavakom
Author:
Potchanee Pandokrak
Author:
Sofia S. Salim
Author:
Richard K. Bellingham
Author:
Joseph T. Hill-Cousins
Author:
Anawat Ajavakom
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