FRINK Linked Data Fragments server

Matches in SemOpenAlex for { <https://semopenalex.org/work/W2952079040> ?p ?o ?g. }

• W2952079040 endingPage "1466" @default.
• W2952079040 startingPage "1459" @default.
• W2952079040 abstract "The oxadi-π-methane rearrangement (ODPM) is considered to represent the normal photochemical behavior of β,γ-unsaturated ketones in the triplet excited π,π* state. However, the usual photoreactivity reported for the majority of β,γ-unsaturated aldehydes is decarbonylation. There are only two published reports of β,γ-unsaturated aldehydes that undergo the ODPM rearrangement. We now report efficient ODPM rearrangement in the triplet-sensitized irradiation of twelve cyclic and acyclic β,γ-unsaturated aldehydes, namely, 2,2-dimethyl-4,4-diphenyl-3-butenal (6), 1-methyl-3-phenyl-2-cyclohexene-1-carbaldehyde (7), 1-methyl-3-phenyl-2-cyclopentene-1-carbaldehyde (14a), 1-methyl-3-phenyl-2-cycloheptene-1-carbaldehyde (14b), 2,2-dimethyl-4-phenyl-3-butenal (18), 2-(3,4-dihydro-2-naphthyl)-2-methylpropanal (23), 3-(9-fluorenylidene)-2,2-dimethylpropanal (24), 5-cyclopentylidene-2,2-dimethyl-3-pentenal (27), 2,2,6-trimethyl-3,5-heptadienal (28), 2,2,4,4-tetraphenyl-3-butenal (35), 2-methyl-4,4-diphenyl-2-vinyl-3-butenal (36), and 4-methyl-2,2-diphenyl-3-pentenal (47). All of them afford the corresponding cyclopropyl aldehydes in 8−96% yield. Our results show that the ODPM rearrangement of aldehydes should be considered a normal photoreactivity of this type of compound. In one case (7), the formation of the corresponding 1,3-formyl migrated product was also observed. Aldehydes 35 and 47 undergo, in addition to the ODPM rearrangement, decarbonylation to the alkenes 37 and 51, respectively. The ODPM reaction takes place when the triplet energy from the sensitizer is efficiently transferred to the alkene moiety generating a T1 (3π,π*) excited state and, furthermore, when the biradical intermediates are stabilized by phenyl or vinyl substitution. Thus, 2,2,4-trimethyl-3-pentenal (46), in which these two requirements are not met, undergoes decarbonylation exclusively. Some structural factors that influence the efficiency of other di-π-methane processes, such as the di-π-methane (DPM) and azadi-π-methane (ADPM) rearrangements, are also operative in the ODPM rearrangement of aldehydes. Thus, diphenyl substitution on the central carbon of the β,γ-unsaturated aldehyde, as in 47, also promotes the ODPM rearrangement. In cases in which the competition between the ODPM and the DPM processes can occur, the selectivity observed depends on the relative stabilities of the 1,4-bridged biradical intermediates. Thus, aldehyde 36 yields the ODPM product exclusively, while 2-(2,2-diphenylvinyl)-2-methyl-4,4-diphenyl-3-butenal (43) affords the DPM product 44 only." @default.
• W2952079040 created "2019-06-27" @default.
• W2952079040 creator A5007664572 @default.
• W2952079040 creator A5009440380 @default.
• W2952079040 creator A5022369402 @default.
• W2952079040 creator A5024866992 @default.
• W2952079040 creator A5038897959 @default.
• W2952079040 creator A5043199638 @default.
• W2952079040 date "1996-01-01" @default.
• W2952079040 modified "2023-10-03" @default.
• W2952079040 title "Unexpected Oxadi-π-methane Rearrangement of β,γ-Unsaturated Aldehydes" @default.
• W2952079040 cites W1408744503 @default.
• W2952079040 cites W1520028072 @default.
• W2952079040 cites W1976789507 @default.
• W2952079040 cites W1982803072 @default.
• W2952079040 cites W1985598774 @default.
• W2952079040 cites W2005665177 @default.
• W2952079040 cites W2005814146 @default.
• W2952079040 cites W2007648934 @default.
• W2952079040 cites W2017246497 @default.
• W2952079040 cites W2018707756 @default.
• W2952079040 cites W2023549773 @default.
• W2952079040 cites W2029814530 @default.
• W2952079040 cites W2034167576 @default.
• W2952079040 cites W2040767318 @default.
• W2952079040 cites W2046163164 @default.
• W2952079040 cites W2063851647 @default.
• W2952079040 cites W2066059889 @default.
• W2952079040 cites W2074238905 @default.
• W2952079040 cites W2075222363 @default.
• W2952079040 cites W2077114129 @default.
• W2952079040 cites W2084735760 @default.
• W2952079040 cites W2085497612 @default.
• W2952079040 cites W2085802152 @default.
• W2952079040 cites W2091509224 @default.
• W2952079040 cites W2092671871 @default.
• W2952079040 cites W2093639873 @default.
• W2952079040 cites W2134832758 @default.
• W2952079040 cites W2327002760 @default.
• W2952079040 cites W2331192817 @default.
• W2952079040 cites W25328920 @default.
• W2952079040 cites W2951272745 @default.
• W2952079040 cites W2952410128 @default.
• W2952079040 cites W3004604991 @default.
• W2952079040 cites W3005168962 @default.
• W2952079040 doi "https://doi.org/10.1021/jo951032l" @default.
• W2952079040 hasPublicationYear "1996" @default.
• W2952079040 type Work @default.
• W2952079040 sameAs 2952079040 @default.
• W2952079040 citedByCount "24" @default.
• W2952079040 countsByYear W29520790402012 @default.
• W2952079040 countsByYear W29520790402015 @default.
• W2952079040 countsByYear W29520790402016 @default.
• W2952079040 countsByYear W29520790402017 @default.
• W2952079040 crossrefType "journal-article" @default.
• W2952079040 hasAuthorship W2952079040A5007664572 @default.
• W2952079040 hasAuthorship W2952079040A5009440380 @default.
• W2952079040 hasAuthorship W2952079040A5022369402 @default.
• W2952079040 hasAuthorship W2952079040A5024866992 @default.
• W2952079040 hasAuthorship W2952079040A5038897959 @default.
• W2952079040 hasAuthorship W2952079040A5043199638 @default.
• W2952079040 hasConcept C132190689 @default.
• W2952079040 hasConcept C155647269 @default.
• W2952079040 hasConcept C161790260 @default.
• W2952079040 hasConcept C178790620 @default.
• W2952079040 hasConcept C185592680 @default.
• W2952079040 hasConcept C2776011334 @default.
• W2952079040 hasConcept C2777811443 @default.
• W2952079040 hasConcept C2779472506 @default.
• W2952079040 hasConcept C2779484182 @default.
• W2952079040 hasConcept C2780378348 @default.
• W2952079040 hasConcept C75473681 @default.
• W2952079040 hasConcept C96350342 @default.
• W2952079040 hasConceptScore W2952079040C132190689 @default.
• W2952079040 hasConceptScore W2952079040C155647269 @default.
• W2952079040 hasConceptScore W2952079040C161790260 @default.
• W2952079040 hasConceptScore W2952079040C178790620 @default.
• W2952079040 hasConceptScore W2952079040C185592680 @default.
• W2952079040 hasConceptScore W2952079040C2776011334 @default.
• W2952079040 hasConceptScore W2952079040C2777811443 @default.
• W2952079040 hasConceptScore W2952079040C2779472506 @default.
• W2952079040 hasConceptScore W2952079040C2779484182 @default.
• W2952079040 hasConceptScore W2952079040C2780378348 @default.
• W2952079040 hasConceptScore W2952079040C75473681 @default.
• W2952079040 hasConceptScore W2952079040C96350342 @default.
• W2952079040 hasIssue "4" @default.
• W2952079040 hasLocation W29520790401 @default.
• W2952079040 hasOpenAccess W2952079040 @default.
• W2952079040 hasPrimaryLocation W29520790401 @default.
• W2952079040 hasRelatedWork W1967490306 @default.
• W2952079040 hasRelatedWork W1974889032 @default.
• W2952079040 hasRelatedWork W1990800502 @default.
• W2952079040 hasRelatedWork W2014849232 @default.
• W2952079040 hasRelatedWork W2038811353 @default.
• W2952079040 hasRelatedWork W2054443014 @default.
• W2952079040 hasRelatedWork W2104171918 @default.
• W2952079040 hasRelatedWork W2617387345 @default.
• W2952079040 hasRelatedWork W2952079040 @default.

• next