In Quest of a Prismene. Organolithium-Induced Desulfonylation on Strained Hydrocarbons

Reaction of a twofold excess of n-butyllithium with 1,6-bis(tert-butylsulfonyl)tetracyclo[4.2.0.05,7]octane (14) yields a mixture of 3- and 5-n-butyl-2-(tert-butylsulfonyl)bicyclo[2.2.2]octa-2,5-dienes 15 and 16, respectively, while the reaction with 2,3-bis(tert-butylsulfonyl)quadricyclane (11) lea...

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Bibliographic Details
Published inJournal of organic chemistry Vol. 61; no. 15; pp. 4929 - 4932
Main Authors Gleiter, Rolf, Ohlbach, Frank
Format Journal Article
LanguageEnglish
Published WASHINGTON American Chemical Society 26.07.1996
Amer Chemical Soc
Subjects
Chemistry
Chemistry, Organic
Physical Sciences
Science & Technology
PHOTOCHEMICAL BEHAVIOR
DOUBLY BRIDGED PRISMANES
1,5-DEHYDROQUADRICYCLANE
INTERMEDIATE
GENERATION
DIENOPHILE
CUBENE
DEWAR-BENZENES
1,7-DEHYDROQUADRICYCLANE
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Summary:Reaction of a twofold excess of n-butyllithium with 1,6-bis(tert-butylsulfonyl)tetracyclo[4.2.0.05,7]octane (14) yields a mixture of 3- and 5-n-butyl-2-(tert-butylsulfonyl)bicyclo[2.2.2]octa-2,5-dienes 15 and 16, respectively, while the reaction with 2,3-bis(tert-butylsulfonyl)quadricyclane (11) leads to 5-n-butyl-2-(tert-butylsulfonyl)bicyclo[2.2.1]hepta-2,6-diene (24), and the reaction with 2-(tert-butylsulfonyl)hexacyclo[9.5.0.01,3.02,10.03,9.09,11]hexadecane (8) yields a 1:1 mixture of 15-n-butyltetracyclo[7.5.2.0.02,8]hexadeca-2(8),15-diene (34) and 1-n-butyl-2,3:4,5-dipentanobenzene (35). Common to all three reactions is the elimination of tert-butylsulfinate and the addition of a butyllithium moiety. A radical mechanism is suggested rather than an elimination via a strained double bond incorporated in a strained cage system.
Bibliography:Abstract published in Advance ACS Abstracts, June 15, 1996.
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istex:E3603923145491DABF26D634A7071819A9B4D252
ISSN:0022-3263
1520-6904
DOI:10.1021/jo960327b