Methoxycarbonylsulfamoyl triethylammonium Hydroxide

Solubility sol benzene, toluene, THF, triglyme, acetonitrile. Form Supplied in colorless solid. 

Preparative Method although the Burgess reagent is commercially available, it can be easily sjmthesized in two steps the reaction of anhydrous methanol with Chlorosulfonyl Isocyanate followed by the addition of Triethylamine affords the 

Handling, Storage, and Precautions moisture sensitive the use of anhydrous solvent and atmosphere in reactions with this reagent is recommended. 

It was noted that when this reaction was applied to allylic alcohols, either elimination (see below) or an SnI rearrangement ensued. The fate of this reaction can be determined by the experimental conditions employed. Whereas the reaction in triglyme gave good yields of dienes (eq 3), thermal decomposition of the A -methoxycarbonylsulfamate intermediate at 80 °C as a solid provided 90% of the allylurethane product (eq 4). 

The requirement for a cis elimination chemistry was discussed earlier however, there are a few exceptional reaction outcomes reported in steroid chemistry. The results depicted in eqs 11 and 12 were unanticipated since the 1 la-hydroxyl and 9p-hydrogen (eq 11) are rra 5-diaxial, as are the 3a-hydroxyl and 4p-hydrogen in eq 12. These results are rationalized by an intramolecular 1,2-hydrogen transfer. For example, it was suggested for eq 11 that a C-11 cation is formed first, which subsequently undergoes an intramolecular hydrogen transfer from C-9 to C-11. The resultant C-9 carbocation was postulated to be quenched by the loss of a hydrogen from C-11 and the formation of the A -double bond.  

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Burgess reagent, (methoxycarbonylsulfamoyl)triethylammonium hydroxide, usually used for the dehydration of secondary or tertiary alcohols, was successfully employed in the formation of cyclic sulfamidates from the corresponding epoxides. It was further shown that the same reaction with aromatic epoxides resulted in the formation of seven-membered ring systems, for example, 57 (Figure 23) <2003SL1247>. 

Lamberth, C. Burgess reagent ([methoxycarbonylsulfamoyl]triethylammonium hydroxide, inner salt) dehydrations and more. J. Prakt. Chem./Chem.-Ztg. 2000, 342, 518-522. 

In some cases the method chosen for dehydration has a decisive effect on the outcome of the reaction. Thus, the adduct of 4,4-dimethylcyclohex-2-enone underwent dehydration with (methoxycarbonylsulfamoyl)triethylammonium hydroxide, inner salt (Burgess reagent) in refluxing benzene to give 5,5-dimethyl-2-[l-(phenylsulfanyl)cyclopropyl]cyclohexa-l,3-diene (5) in 93% yield. 

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