76589-16-7Relevant articles and documents
Nucleophilic Alkoxylations of Unactivated Alkyl Olefins and α-Methyl Styrene by Photoredox Catalysis
Seyfert, Fabienne,Mitha, Mathis,Wagenknecht, Hans-Achim
supporting information, p. 773 - 776 (2021/01/12)
N,N-diisobutylaminophenyl-phenothiazine is a strongly reducing catalyst that allows – for the first time – the photoredox catalytic addition of alcohols to alkyl olefins as non-activated substrates to products with Markovnikov orientation. The irradiation at 365 nm does not require any additional reagent. Using α-methyl styrene as activated substrate we additionally show that this photoredox catalytic method tolerates other functional groups, including allyl, alkynyl, cyanide, and even acid-labile Boc groups within the substrate scope.
Photochemistry of Alkenes. 6. Direct Irradiation of 1,5-Hexadienes: and Sigmatropic Allyl Shifts
Manning, T. D. R.,Kropp, Paul J.
, p. 889 - 897 (2007/10/02)
The photochemical behavior of a series of alkyl-substituted 1,5-hexadienes has been studied.Competing allylcyclopropane formation and rearrangement to an isomeric 1,5-hexadiene via competing and sigmatropic allyl shifts, respectively, were observed.In one case a product (30 from 27) and in another a product (35 from 31) was obtained, but only in low yield.Extensive cis trans isomerization competed with the allyl shifts, and, in addition, other products were obtained which are characteristic of the photochemical behavior of isolated double bonds.At low conversion diene 10t underwent stereoselective rearrangement to 8t and 11t, whereas the cis isomer 10c afforded mixtures of the cis and trans isomers of 8 and 11.Attempts to induce the allyl migrations by sensitization with p-xylene or by irradiation at 254 nm afforded only cis trans isomerization.It is concluded that the allyl migrations occur via an excited state involving interaction between the double bonds and requiring a conformation in which the central C3-C4 bond is in a plane orthogonal to both double bonds, as proposed previously.In contrast with the acyclic dienes, 1,5-cyclooctadiene (50) afforded products 51-53 from competing , , and allyl shifts, respectively.The divergent behavior in this case apparently arises because appropriate interaction between the two double bonds can occur only in the boat conformation.
