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Stereocontrolled Syntheses of Functionalized cis- and trans-Siladecalins

Journal Article · · Journal of the American Chemical Society
DOI:https://doi.org/10.1021/jacs.9b09902· OSTI ID:1570378
 [1];  [2];  [2];  [2];  [2];  [2];  [2]
  1. Johns Hopkins Univ., Baltimore, MD (United States); Johns Hopkins University
  2. Johns Hopkins Univ., Baltimore, MD (United States)
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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.

Research Organization:
Johns Hopkins Univ., Baltimore, MD (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
SC0013906
OSTI ID:
1570378
Journal Information:
Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 44 Vol. 141; ISSN 0002-7863
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

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Cited By (1)

Reductive halocyclosilazane polymerization journal January 2020

Figures / Tables (20)

Figure 1(p. 3)figure Figure 1
Scheme 1(p. 3)figure Scheme 1
Figure 2(p. 4)figure Figure 2
Figure 3(p. 4)figure Figure 3
Scheme 2(p. 5)figure Scheme 2
Table 1(p. 5)table Table 1
Table 2(p. 5)table Table 2
Figure 4(p. 6)figure Figure 4
Scheme 3(p. 6)figure Scheme 3
Table 3(p. 6)table Table 3
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Table 4(p. 8)table Table 4
Figure 9(p. 9)figure Figure 9
Table 5(p. 9)table Table 5
Figure 10(p. 10)figure Figure 10
Figure 11(p. 11)figure Figure 11
Figure 12(p. 11)figure Figure 12

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36 MATERIALS SCIENCE