Synthesis of a biofuel target through conventional organic chemistry

Page, Jordan P.; Robinson, Joshua W.; Albrecht, Karl O.; Cosimbescu, Lelia

doi:10.1016/j.tetlet.2018.02.073

Title: Synthesis of a biofuel target through conventional organic chemistry

Abstract

Here in this work, the biofuel target compound 2-ethyl-5,5-dimethylcyclopenta-1,3-diene (1) and its exo isomers (9a and 9b), were successfully synthesized via two different pathways from the common intermediate 4,4-dimethylcyclopent-2-ene-1-one (2). The first pathway produced the endocyclic product as a pure isomer via a triflate intermediate obtained from ketone 2 in 60% yield, followed by copper-catalyzed coupling with ethyl magnesium bromide in 63% yield. The second pathway employed a Grignard reaction with ketone 2, which generated an alcohol that was immediately subjected to mild acid-catalyzed elimination to yield primarily a mixture of exo isomers 9a and 9b in 46% yield. The preparation method developed by this work allowed for the production of a sufficient quantity of these targets to evaluate their fuel properties, which will be reported in a separate study.

Authors:

Page, Jordan P. ^[1]; Robinson, Joshua W. ^[1]; Albrecht, Karl O. ^[1]; Cosimbescu, Lelia ^[1]

Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Energy and Environment Directorate

Publication Date:: 2018-02-28

Research Org.:: Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

Sponsoring Org.:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Sustainable Transportation Office. Bioenergy Technologies Office; USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V)

OSTI Identifier:: 1423329

Report Number(s):: PNNL-S-129880
Journal ID: ISSN 0040-4039; PII: S0040403918302739

Grant/Contract Number:: AC0576RL01830

Resource Type:: Accepted Manuscript

Journal Name:: Tetrahedron Letters

Additional Journal Information:: Journal Volume: 2018; Related Information: © 2018 Elsevier Ltd. All rights reserved.; Journal ID: ISSN 0040-4039

Publisher:: Elsevier

Country of Publication:: United States

Language:: English

Subject:: 09 BIOMASS FUELS; Divergent synthesis; Grignard cross-coupling; Alkenes; Biofuels; Cyclopentadiene

Citation Formats


                    Page, Jordan P., Robinson, Joshua W., Albrecht, Karl O., and Cosimbescu, Lelia. Synthesis of a biofuel target through conventional organic chemistry.  United States: N. p., 2018. 
Web.  doi:10.1016/j.tetlet.2018.02.073.

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                    Page, Jordan P., Robinson, Joshua W., Albrecht, Karl O., & Cosimbescu, Lelia. Synthesis of a biofuel target through conventional organic chemistry.  United States.  https://doi.org/10.1016/j.tetlet.2018.02.073

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                    Page, Jordan P., Robinson, Joshua W., Albrecht, Karl O., and Cosimbescu, Lelia. Wed .  
"Synthesis of a biofuel target through conventional organic chemistry".  United States.  https://doi.org/10.1016/j.tetlet.2018.02.073.  https://www.osti.gov/servlets/purl/1423329.

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@article{osti_1423329,

  title        = {Synthesis of a biofuel target through conventional organic chemistry},

  author       = {Page, Jordan P. and Robinson, Joshua W. and Albrecht, Karl O. and Cosimbescu, Lelia},

  abstractNote = {Here in this work, the biofuel target compound 2-ethyl-5,5-dimethylcyclopenta-1,3-diene (1) and its exo isomers (9a and 9b), were successfully synthesized via two different pathways from the common intermediate 4,4-dimethylcyclopent-2-ene-1-one (2). The first pathway produced the endocyclic product as a pure isomer via a triflate intermediate obtained from ketone 2 in 60% yield, followed by copper-catalyzed coupling with ethyl magnesium bromide in 63% yield. The second pathway employed a Grignard reaction with ketone 2, which generated an alcohol that was immediately subjected to mild acid-catalyzed elimination to yield primarily a mixture of exo isomers 9a and 9b in 46% yield. The preparation method developed by this work allowed for the production of a sufficient quantity of these targets to evaluate their fuel properties, which will be reported in a separate study.},

  doi          = {10.1016/j.tetlet.2018.02.073},

  journal      = {Tetrahedron Letters},

  number       = ,

  volume       = 2018,

  place        = {United States},

  year         = {2018},

  month        = {2}

}

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Figures / Tables:

Scheme 1: Approach to the desired 2-ethyl-5,5-dimethylcyclopenta-1,3-diene (1), an identified biofuel target

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Synthesis of a biofuel target through conventional organic chemistry

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