Adamantylidenecarbene: Photochemical Generation, Trapping, and Theoretical Studies.

Autor: Roth AD; Department of Chemistry, Colby College, Waterville, Maine 04901, United States., Wamsley CE; Department of Chemistry, Colby College, Waterville, Maine 04901, United States., Haynes SM; Department of Chemistry, Colby College, Waterville, Maine 04901, United States., Thamattoor DM; Department of Chemistry, Colby College, Waterville, Maine 04901, United States.
Jazyk: angličtina
Zdroj: The Journal of organic chemistry [J Org Chem] 2023 Oct 20; Vol. 88 (20), pp. 14413-14422. Date of Electronic Publication: 2023 Sep 28.
DOI: 10.1021/acs.joc.3c01399
Abstrakt: Photolysis of 1-(2-adamantylidene)-1a,9b-dihydro-1 H -cyclopropa[ l ]phenanthrene in benzene (or benzene- d 6 ) at ambient temperature produces adamantylidenecarbene. The carbene undergoes dimerization to a cumulene and may also be trapped in a stereospecific fashion by cis - and trans -4-methyl-2-pentene. No products attributable to 4-homoadamantyne, resulting from ring expansion of the carbene, could be detected. Coupled cluster/density functional theory calculations place the singlet carbene ∼49 kcal/mol below the triplet and show that the former must overcome a barrier of ∼13.5 kcal/mol to rearrange into 4-homoadamantyne.
Databáze: MEDLINE
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