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Oxidation of Aryl‐ and Diarylcyclopropanes in a Pentasil Zeolite: Ring Opening with Deprotonation or Net Hydrogen Migration
Author(s) -
Herbertz Torsten,
Lakkaraju Prasad Sreeramachandra,
Blume Florian,
Blume Matthias,
Roth Heinz Dieter
Publication year - 2000
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/(sici)1099-0690(200002)2000:3<467::aid-ejoc467>3.0.co;2-b
Subject(s) - isotopomers , chemistry , deprotonation , zeolite , aryl , ring (chemistry) , catalysis , redox , photochemistry , medicinal chemistry , inorganic chemistry , organic chemistry , molecule , ion , alkyl
Incorporation of trans ‐1,2‐diphenylcyclopropane ( 1 ) and its 3,3‐D 2 ‐isotopomer into the channels of a redox‐active pentasil zeolite (Na‐ZSM‐5) resulted in the formation of exo , exo ‐1,3‐diphenylallyl radical ( 2 •) and its 2‐D 1 isotopomer, respectively. This conversion requires oxidation, ring opening, and deprotonation, in an unspecified sequence. The allyl radical 2 • is also formed upon incorporation of trans ‐1,3‐diphenylpropene ( 3 ). A comparison with the solution photochemistry, in the presence or absence of added base, shows the conversion of 1 into 2 • to be a zeolite‐specific reaction. Incorporation of arylcyclopropanes 9 (R = H, OCH 3 ) into ZSM‐5 generated trans ‐propenylbenzene radical cations 10 • + (R = H, OCH 3 ); the 2,2‐D 2 isotopomer of 9 (R = OCH 3 ) gave rise to three different isotopomers of 10 • + (R = OCH 3 ).