One-Pot Synthesis of 2,5-Dihydrosiloles and Their Silole-Annulated Analogs Starting from Alkynylsilanes with a Terminal Alkynyl Group
The result's identifiers
Result code in IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388963%3A_____%2F21%3A00541597" target="_blank" >RIV/61388963:_____/21:00541597 - isvavai.cz</a>
Alternative codes found
RIV/68378271:_____/21:00541597 RIV/61388980:_____/21:00541597
Result on the web
<a href="https://pubs.acs.org/doi/pdf/10.1021/acs.joc.0c02711" target="_blank" >https://pubs.acs.org/doi/pdf/10.1021/acs.joc.0c02711</a>
DOI - Digital Object Identifier
<a href="http://dx.doi.org/10.1021/acs.joc.0c02711" target="_blank" >10.1021/acs.joc.0c02711</a>
Alternative languages
Result language
angličtina
Original language name
One-Pot Synthesis of 2,5-Dihydrosiloles and Their Silole-Annulated Analogs Starting from Alkynylsilanes with a Terminal Alkynyl Group
Original language description
In contrast to the reaction of vinyl(alkynyl)silanes with 9-BBN-H, leading to the quantitative formation of 5-R-4-(9-BBN)-2,3-dihydro-1H-siloles, treatment of bis(alkynyl)silanes bearing one terminal alkynyl group with 2 equiv of 9-BBN-H followed by methanolysis afforded 5-R-4-(9-BBN)-2,5-dihydro-1H-siloles with yields of 85-90% (by NMR integration). The reaction proceeds via a double 1,2-hydroboration of the terminal triple bond with the formation of the geminal diborane followed by ring closure via intramolecular 1,1-carboboration of the remaining alkynyl fragment. Depending on the nature of the substituent R in position 5, the allylic BBN group locates in position 3 (R = Ph) or position 5 (R = SiHMe2, SiMe3) to give 2,3-or 2,5-dihydrosiloles, respectively. The protodeborylation of the allylic BBN group with MeOH of both 3,4-(9-BBN)2-2,3-dihydro- A nd 4,5-(9-BBN)2-2,5-dihydrosiloles results in the exclusive formation of 4-(9-BBN)-2,5-dihydrosiloles. In all cases, the formation of 10-12% of 2-R-2,4-(9-BBN)2-2,3-dihydrosilole minor isomers has been observed, which occurs from vicinal diboranes formed as side products by a second hydroboration of the terminal triple bond. Similarly, treatment of the tri- A nd tetraalkynes containing a terminal triple bond with 2 equiv of 9-BBN-H followed by treatment with methanol resulted in the high-yield formation of 1,2,6,6a-tetrahydro-1,6-disilapentalenes and 2,6,7,7a-tetrahydro-1,6,7-trisila-1H-cyclopenta[a]pentalenes, respectively.
Czech name
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Czech description
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Classification
Type
J<sub>imp</sub> - Article in a specialist periodical, which is included in the Web of Science database
CEP classification
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OECD FORD branch
10400 - Chemical sciences
Result continuities
Project
<a href="/en/project/GA17-22253S" target="_blank" >GA17-22253S: New family of helicenes based on fused silacyclopentadienes</a><br>
Continuities
I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace
Others
Publication year
2021
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů
Data specific for result type
Name of the periodical
Journal of Organic Chemistry
ISSN
0022-3263
e-ISSN
1520-6904
Volume of the periodical
86
Issue of the periodical within the volume
5
Country of publishing house
US - UNITED STATES
Number of pages
11
Pages from-to
3871-3881
UT code for WoS article
000626845000019
EID of the result in the Scopus database
2-s2.0-85101519409