Methoxycarbonylsulfamoyl Chloride1

[36914-92-8]  · C2H4ClNO4S  · Methoxycarbonylsulfamoyl Chloride  · (MW 173.59)

(precursor for the Burgess reagent;1 regent for heterocyclic cycloaddition6)

Physical Data: mp 70-74 °C.

Solubility: sol benzene, cyclohexane, THF, MeCN.

Form Supplied in: white crystalline solid.

Preparative Method: readily prepared in high yield from the reaction of Chlorosulfonyl Isocyanate and anhydrous methanol.1

Handling, Storage, and Precautions: is moisture sensitive and should be stored in a dark bottle, protected from light. Violent decomposition has been observed when the product is stored in a clear-glass container or when advertently exposed to sunlight.

Formation of the Inner Salt of the Burgess Reagent.

The reaction of anhydrous Triethylamine with methoxycarbonylsulfamoyl chloride (1) in benzene produces the inner salt of (Methoxycarbonylsulfamoyl)triethylammonium Hydroxide (the Burgess reagent) (eq 1).1 The Burgess reagent has been used in the formation of urethanes from primary alcohols; the urethanes are converted to primary amines upon hydrolysis.1,2 The Burgess reagent has commonly been used in stereospecific cis elimination of secondary and tertiary alcohols to provide alkenes,2,3 and in the synthesis of vinyltributyltin compounds.4

Cycloaddition Reactions.

Deprotonation of reagent (1) with Sodium Hydride provides the salt form of reagent (1), which undergoes cycloaddition with various alkenes. Decomposition of the salt form at 30 °C in THF yields the solvent complex of methyl N-sulfonylurethane, whereas reaction of the salt with acetonitrile, or other nitrile compounds, provides substituted 1,3,4,5-oxathiazines (eq 2). Both species are prone to cycloaddition reactions with alkenes (eq 2); however, the advantage of the latter species is the possibility of using higher reaction temperatures, thus enabling the formation of cycloadducts from otherwise unreactive alkenes.5,6 The stereospecificity of the cycloaddition reaction has been investigated with a model substrate, trans-styrene-b-d, in both THF and acetonitrile. In both cases, cycloadducts (4) and (5) are formed in a ratio of 1:3 in 72% overall yield;5 therefore, both [2 + 2] and [2 + 4] cycloadducts are formed with complete stereospecificity.

Intermediates (2) and (3) react with ynamines to form heterocycles (eq 3).7 As with the cycloaddition reactions with alkenes, the nature of the product is dependent on whether species (2) or (3) is allowed to react with the ynamine.

Metal-assisted cycloadditions with intermediate (2) have been reported (eq 4).8 These reactions are dominated by the metal functioning as an electron-donor center.

1. Burgess, E. M.; Penton, H. R., Jr.; Taylor, E. A.; Williams, W. M. OS 1977, 56, 40.
2. Duncan, J. A.; Hendricks, R. T.; Kwong, K. S. JACS 1990, 112, 8433.
3. Burgess, E. M.; Penton, H. R., Jr.; Taylor, E. A. JOC 1973, 38, 26.
4. Ratier, M.; Khatmi, D. SC 1989, 19, 285.
5. Burgess, E. M.; Williams, W. M. JACS 1972, 94, 4386.
6. Burgess, E. M.; Williams, W. M. JOC 1973, 38, 1249.
7. Kloek, J. A.; Leschinsky, K. L. JOC 1980, 45, 721.
8. Cutler, A.; Ehntholt, D.; Giering, W. P.; Lennon, P.; Raghu, S.; Rosan, A.; Rosenblum, M.; Tancrede, J.; Wells, D. JACS 1976, 98, 3495.

J. Joyce Siregar & Shahriar Mobashery

Wayne State University, Detroit, MI, USA

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