5204-91-1Relevant articles and documents
Sunlight-induced C–C bond formation reaction: Radical addition of alcohols/ethers/acetals to olefins
Hayakawa, Mamiko,Shirota, Hisashi,Hirayama, Souta,Yamada, Ryuusei,Aoyama, Tadashi,Ouchi, Akihiko
, (2021/04/09)
A sunlight-induced C–C bond formation reactions upon the addition of alcohols/ethers/acetals to olefins proceeded efficiently using di-tert-butyl peroxide (DTBP). The reactions proceeded faster than many of the previously reported sunlight and many conventional lamp photolyses, typically in 3–4 h under irradiation with sunlight, in excellent yield using olefins bearing two electron withdrawing groups (EWGs) (product yield > 95 %) and in good to fair yield with olefins bearing one EWG. The yields observed for some products were ~20 % higher than those obtained using a conventional Xe lamp as the light source, which was confirmed to be due to a light intensity effect. Gram-scale experiments showed similar yields to those observed in their corresponding small-scale experiments.
Benzyl radicals from toluene by photosensitization with naphthalene-1,4- dicarbonitrile - Benzylation and hydroxymethylation of unsaturated compounds
Mella, Mariella,Fagnoni, Maurizio,Albini, Angelo
, p. 2137 - 2142 (2007/10/03)
In aprotic media, photoinduced electron transfer from toluene to 1,4- naphthalenedicarbonitrile (DCN) is followed by in-cage proton transfer and radical coupling. However, in the presence of a protic co-solvent, the radical ions diffuse out of the cage and deprotonation of the toluene radical cation takes place from the free solvated species. With (BuOH, this results in reductive benzylation of DCN through coupling of benzyl radicals with DCN-·. With MeOH, secondary hydrogen abstraction by PhCH2- yields hydroxymethyl radicals, which couple with DCN-·. Both benzyl and hydroxymethyl radicals are efficiently trapped by electrophilic alkenes. Thus, in the presence of dimethyl maleate, DCN-photosensitized benzylation - or hydroxy-methylation - of the substrate occurs through direct activation of the C-H bond. The same reaction has been accomplished with acrylonitrile, albeit with a lower yield.