Intramolecular Pericyclic Re-hydroboration via Six-membered Transition State: Synthesis of Fused Borolo[3,2-b]siloles
The result's identifiers
Result code in IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388980%3A_____%2F24%3A00600593" target="_blank" >RIV/61388980:_____/24:00600593 - isvavai.cz</a>
Result on the web
<a href="https://hdl.handle.net/11104/0360094" target="_blank" >https://hdl.handle.net/11104/0360094</a>
DOI - Digital Object Identifier
<a href="http://dx.doi.org/10.1002/chem.202402585" target="_blank" >10.1002/chem.202402585</a>
Alternative languages
Result language
angličtina
Original language name
Intramolecular Pericyclic Re-hydroboration via Six-membered Transition State: Synthesis of Fused Borolo[3,2-b]siloles
Original language description
We experimentally demonstrate a new type of the intramolecular reaction between non-activated alkyne units and the dialkylboryl group (9-BBN), which was previously only hypothesized and studied on a calculational level. The reaction described here can formally be classified as a 1,2-hydroboration reaction, but, in contrast to the classical mechanism via a cyclic four-membered transition state, the reaction proceeds by a pericyclic mechanism involving a six-membered transition state. In practice, the reaction allows the synthesis of a new class of the borolenes fused with silole or dihydrosilole units. Thus, the heating (125°C) of 2,3-dihydrosiloles or 2,3-dihydrosilolo[2,3-b]silole bearing 9-BBN and propargyl or dimethylpropargyl groups in positions 4 and 5, respectively, affords, in high to moderate yields, di- and tricyclic compounds containing a borolo[3,2-b]silole unit. In all cases, the reactions are accompanied by an unprecedented dehydroboration of the 9-BBN fragment, leading, in the final products, to a cyclooct-4-enyl group on the boron atom. The effects of the substituents on the rate and the selectivity of the reaction are discussed. The structures of all the new compounds have been determined from HRMS together with multinuclear 1D and 2D NMR spectroscopy, the results of which are in excellent agreement with DFT calculated chemical shifts.
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
10402 - Inorganic and nuclear chemistry
Result continuities
Project
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Continuities
I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace
Others
Publication year
2024
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů
Data specific for result type
Name of the periodical
Chemistry - A European Journal
ISSN
0947-6539
e-ISSN
1521-3765
Volume of the periodical
30
Issue of the periodical within the volume
70
Country of publishing house
DE - GERMANY
Number of pages
8
Pages from-to
e202402585
UT code for WoS article
001363336900001
EID of the result in the Scopus database
2-s2.0-85210393602