Highly-functionalised difluorinated (hydroxymethyl)conduritol analogues via the Diels–Alder reactions of a difluorinated dienophile

Andrea Arany, Patrick J. Crowley, John Fawcett, Michael B. Hursthouse, Benson M. Kariuki, Mark E. Light, Andrew C. Moralee, Jonathan M. Percy, Vittoria Salafia
2004 Organic and biomolecular chemistry  
A difluorodienophile, synthesised using a Stille coupling reaction underwent tin()-catalysed cycloaddition with three furans to afford oxa[2.2.1]bicycloheptenes in good yield. Reduction of ester and carbamate carbonyl groups and diol protection as the acetonide set the stage for palladium-catalysed hydrostannylation in two cases. Treatment of the stannanes with methyllithium triggered ring-opening to afford highly-functionalised difluorinated cyclohexenols which could be deprotected to afford
more » ... protected to afford (hydroxymethyl)conduritol analogues. Scheme 1 i) ZnI 2 , furan, hydroquinone, 80 ЊC, 85 h; (ii) TBAFؒ3H 2 O, 45 ЊC, 2 h. T h i s j o u r n a l i s © T h e R o y a l S o c i e t y o f C h e m i s t r y 2 0 0 4 O r g . B i o m o l . C h e m . , 2 0 0 4 , 2, 4 5 5 -4 6 5 Scheme 4 i, LiAlH 4 , THF, reflux, 3 h; ii acetone, CuSO 4 , TsOHؒH 2 O, rt, 12 h. 457 O r g . B i o m o l . C h e m . , 2 0 0 4 , 2, 4 5 5 -4 6 5
doi:10.1039/b314314g pmid:14770223 fatcat:qnpmrpex6be6nnrp6owvpj75ju