Abstract
α-Hydroxyalk-2-enylphosphonates undergo Claisen orthoester rearrangement on heating with orthoesters, and their arylsulphenates undergo [2,3]-sigmatropic rearrangement to give 3-arylsulphinylalk-1-enylphosphonates. The addition of allyloxide anion to the central carbon of the allene Me2CCCHP(O)(OEt)2 is followed by rapid Claisen rearrangement of the resulting allylic carbanion to give the two possible β-ketoalkylphosphonates. Allenic phosphonates of the general formula R1R2CCH[CH2]nCR3CCHP(O)(OEt)2 have been prepared: when R1= R2= H, R3= Me, and n= 2, Cope rearrangement occurs to give isomeric dienes; when R1,R2,R3= Me and n= 0, [1,5] hydride shift gives a triene which then cyclises to a cyclohexadiene; when R1= Me, R2= H, R3= H or Me, and n= 0, the diene component can be used in Diels–Alder reactions.
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