Rearrangements of the Diels-Alder cycloadducts obtained from acetylenic sulfones and 1,3-diphenylisobenzofuran.
1,3-Diphenylisobenzofuran afforded Diels-Alder cycloadducts 4a,b with n-butyl- and phenyl-substituted acetylenic sulfones 3a,b, respectively. The products underwent various types of rearrangements under pyrolytic, acid-catalyzed, and photochemical conditions. In the presence of acid, or upon heating in xylenes, they afforded the ketones 5a,b. In addition, the dehydration product 7a was produced from the pyrolysis of 4a, and the unexpected transposed ketone 6b was generated under acid-catalyzed or pyrolytic conditions from 4b via a postulated epoxide intermediate. The photolysis of 4a afforded ketone 5a as the sole isolated product, whereas 5b afforded oxepin 8b and indenyl phenyl ketone 9b. The formation of the latter two products can be rationalized by a series of pericyclic reactions. These include an intramolecular [2+2] cycloaddition, followed by a 1,3-dipolar cycloreversion, for the transformation of 4b to 8b and a series of electrocyclic and [1,3]sigmatropic reactions to convert 8b into 9b.
Back
Thomas G
TG
Department of Chemistry, University of Calgary, Calgary, Alberta, Canada, T2N 1N4. tgback@ucalgary.ca
Parvez
Masood
M
Zhai
Huimin
H
D000114:Acetylene / Q000737:chemistry*; D001572:Benzofurans / Q000737:chemistry*; D002384:Catalysis; D003500:Cyclization; D007659:Ketones / Q000138:chemical synthesis* / Q000737:chemistry; D015394:Molecular Structure; D013237:Stereoisomerism; D013450:Sulfones / Q000737:chemistry*
D001572:Benzofurans; D007659:Ketones; D013450:Sulfones; C011238:1,3-diphenylisobenzofuran; D000114:Acetylene