Intermolecular C-H Activation at the Allylic/Benzylic and Homoallylic/Homobenzylic Positions of Cyclic Hydrocarbons by a Stable Divalent Silicon Species.
Chemistry
; 27(2): 724-734, 2021 Jan 07.
Article
em En
| MEDLINE
| ID: mdl-32931054
ABSTRACT
Direct activation of inert C(sp3 )-H bonds by main group element species is yet a formidable challenge. Herein, the dehydrogenation of cyclohexene and 1,2,3,4-tetrahydronaphthalene through the allylic/benzylic and homoallylic/homobenzylic C-H bond activation by cyclic (alkyl)(amino)silylene 1 in neat conditions is reported to yield the corresponding aromatic compounds. As for the reaction of cyclohexene, allylsilane 3 and 7-silanorbornene 4 were also observed, which could be interpreted as a direct dehydrogenative silylation reaction of monoalkenes at the allylic positions. Experimental and computational studies suggest that the dehydrogenation of cyclohexene at the homoallylic position was accomplished by a combination of silylene 1 and radical intermediates such as hydrosilyl radical INT1 or cyclohexenyl radical H, which are generated in the initial step of the reaction.
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MEDLINE
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En
Ano de publicação:
2021
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Article