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

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journal contribution
posted on 1996-07-26, 00:00 authored by Rolf Gleiter, Frank Ohlbach
Reaction of a twofold excess of n-butyllithium with 1,6-bis(tert-butylsulfonyl)tetracyclo[,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[,3.02,10.03,9.09,11]hexadecane (8) yields a 1:1 mixture of 15-n-butyltetracyclo[,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.