Stereocontrolled syntheses of functionalized cis- and trans-siladecalins

doi:10.1021/jacs.9b09902

This content will become publicly available on October 10, 2020

Title: Stereocontrolled syntheses of functionalized cis- and trans-siladecalins

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Abstract

Here, we study the synthesis of both diastereomers of an all-silicon analog of decalin, the ubiquitous bicyclic structural motif. The synthesis provides materials functionalized with either Si–Ph or Si–H groups, versatile entry points for further chemical diversification. The synthesis of silicon-stereogenic silanes is significantly less precedented than the synthesis of asymmetric carbon centers and strategies for control of relative stereochemistry in oligosilanes are hardly described. This report provides insights of potential generality, such as the epimerization of the cis-isomer to the thermodynamically downhill trans-isomer via a hypothesized pentavalent intermediate. Decalin is a classic example in the conformational analysis of organic ring systems and the carbocyclic diastereomers have highly divergent conformational profiles. Like the carbocycle, we observe different conformational properties in cis- and trans-siladecalins with consequences for NMR spectroscopy, optical properties, and vibrational spectroscopy. Our research showcases the utility of targeted synthesis for preparing complex and functionalized polycyclic silanes.

Authors:

Marro, Eric A. ^[1]; Folster, Carlton P. ^[1]; Press, Eric M. ^[1]; Im, Hoyeon ^[1]; Ferguson, John T. ^[1]; Siegler, Maxime A. ^[1]; Klausen, Rebekka S. ^[1]

Johns Hopkins Univ., Baltimore, MD (United States)

Publication Date:: 2019-10-10

Research Org.:: Johns Hopkins Univ., Baltimore, MD (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division

OSTI Identifier:: 1570378

Grant/Contract Number:: SC0013906

Resource Type:: Accepted Manuscript

Journal Name:: Journal of the American Chemical Society

Additional Journal Information:: Journal Name: Journal of the American Chemical Society; Journal ID: ISSN 0002-7863

Publisher:: American Chemical Society (ACS)

Country of Publication:: United States

Language:: English

Subject:: 36 MATERIALS SCIENCE

Citation Formats


                    Marro, Eric A., Folster, Carlton P., Press, Eric M., Im, Hoyeon, Ferguson, John T., Siegler, Maxime A., and Klausen, Rebekka S. Stereocontrolled syntheses of functionalized cis- and trans-siladecalins.  United States: N. p., 2019. 
        Web.  doi:10.1021/jacs.9b09902.

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                    Marro, Eric A., Folster, Carlton P., Press, Eric M., Im, Hoyeon, Ferguson, John T., Siegler, Maxime A., & Klausen, Rebekka S. Stereocontrolled syntheses of functionalized cis- and trans-siladecalins.  United States.  doi:10.1021/jacs.9b09902.

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                    Marro, Eric A., Folster, Carlton P., Press, Eric M., Im, Hoyeon, Ferguson, John T., Siegler, Maxime A., and Klausen, Rebekka S. Thu .  
        "Stereocontrolled syntheses of functionalized cis- and trans-siladecalins".  United States.  doi:10.1021/jacs.9b09902.

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@article{osti_1570378,

  title        = {Stereocontrolled syntheses of functionalized cis- and trans-siladecalins},

  author       = {Marro, Eric A. and Folster, Carlton P. and Press, Eric M. and Im, Hoyeon and Ferguson, John T. and Siegler, Maxime A. and Klausen, Rebekka S.},

  abstractNote = {Here, we study the synthesis of both diastereomers of an all-silicon analog of decalin, the ubiquitous bicyclic structural motif. The synthesis provides materials functionalized with either Si–Ph or Si–H groups, versatile entry points for further chemical diversification. The synthesis of silicon-stereogenic silanes is significantly less precedented than the synthesis of asymmetric carbon centers and strategies for control of relative stereochemistry in oligosilanes are hardly described. This report provides insights of potential generality, such as the epimerization of the cis-isomer to the thermodynamically downhill trans-isomer via a hypothesized pentavalent intermediate. Decalin is a classic example in the conformational analysis of organic ring systems and the carbocyclic diastereomers have highly divergent conformational profiles. Like the carbocycle, we observe different conformational properties in cis- and trans-siladecalins with consequences for NMR spectroscopy, optical properties, and vibrational spectroscopy. Our research showcases the utility of targeted synthesis for preparing complex and functionalized polycyclic silanes.},

  doi          = {10.1021/jacs.9b09902},

  journal      = {Journal of the American Chemical Society},

  number       = ,

  volume       = ,

  place        = {United States},

  year         = {2019},

  month        = {10}

}

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