Stereocontrolled syntheses of functionalized cis- and trans-siladecalins
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.
- Publication Date:
- 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 Volume: 141; Journal Issue: 44; Journal ID: ISSN 0002-7863
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE
Citation Formats
Stereocontrolled syntheses of functionalized cis- and trans-siladecalins. United States: N. p., 2019.
Web. doi:10.1021/jacs.9b09902.
Stereocontrolled syntheses of functionalized cis- and trans-siladecalins. United States. doi:10.1021/jacs.9b09902.
Thu .
"Stereocontrolled syntheses of functionalized cis- and trans-siladecalins". United States. doi:10.1021/jacs.9b09902. https://www.osti.gov/servlets/purl/1570378.
@article{osti_1570378,
title = {Stereocontrolled syntheses of functionalized cis- and trans-siladecalins},
author = {None, None},
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 = 44,
volume = 141,
place = {United States},
year = {2019},
month = {10}
}
Web of Science
Works referencing / citing this record:
Reductive halocyclosilazane polymerization
journal, January 2020
- Folster, Carlton P.; Nguyen, Phi N.; Klausen, Rebekka S.
- Dalton Transactions