Diol monosulfonates

Rearrangement of diol monosulfonates can also be done using Lewis acids. These conditions lead to inversion of configuration at the migration terminus, as would be implied by a concerted mechanism.66... 

A comparison has been made" of various monoterpenoid rearrangements cataiysed by either zirconium phosphates or by zirconium organo-substituted phosphonates, and acid-catalysed rearrangements of a-trans- and /3-cis-3,4-epoxycaranes have been described." It has been observed" that on exposure to Li (OBu )3AlH, perhydro-naphthalene-l,4-diol monosulfonate ester (269) rearranges to the 11-oxatricyclo-[5.3.1.0.2,6]undecane derivative (270) (see Scheme 88). 

Opening at C-3 of glycidol sulfonates generates a 1,2-diol monosulfonate array which is ideally situated for closure under mildly alkaline conditions to a new epoxide group, as shown in eq 10 and also, below, in eq 18. Either the intermediate monosulfonate or the new epoxide present an activated electrophilic site for further synthetic transformations. 

The great utility of fragmentations, especially those of 1,3-diol monosulfonates, for the construction of functionalized, medium-sized cycloalkenes was developed by Wharton, by applying previous results. In recognition of his important contributions to the chemistry of heterolytic fragmentations of cyclic 1,3-diol derivatives, this reaction type has been referred to in a recent review as the Wharton fragmentation . ... 

Wharton fragmentation Base-induced formation of medium-sized cyclic alkenes from 1,3-diol monosulfonates. 480... 

Wijnberg, J. B. P. A., De Groot, A. Induced ionization in 1,4-diol monosulfonate esters and its application in the synthesis of natural... 

Use as a Base. Both 1,2- and 1,3-diol monosulfonate esters react with LiAHTj functioning initially as a base and subsequently in a reducing capacity (eqs 21 and 22). ... 

A fourth approach to the oxatricyclo-[5.3.1.0 ]-undecane ring system of furanether B (18.8) was published recently by de Groot et al. 159) who relied upon a stereoselective base-induced rearrangement reaction of 1,4-diol monosulfonate esters to establish the bridged ether core of 18.8 (26.103 26.105, Scheme 35). The starting material of the synthesis was the known ketone 26.99 which was converted to the required methanesulfonate 26.103 by standard procedures. 

Monocyclic ethylenealcohols from bicyclic diol monosulfonates Fragmentation-type reductive ring opening... 

Fragmentation-type ring opening of cyclic diol monosulfonates... 

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