Sulfenates tris

Tris(fluorosulfuroyl)fluoromethane (329) reacted with bis(diethylamido)benzyl phosphite to yield an intermediate (330) which extruded a molecule of SO2 to give as final product the bis(fluorosulfonyl) compound (331). The kinetics and mechanism of the reaction of fluorinated tricoordinate phosphorus compounds (332) and aryl 2,2,2-trifluoroethyl sulfenates (333) have been reviewed. ... 

You shouldn t at this stage try to leam ail the names for every type of organosulfur compound—what matters is the structures. Here the names are ail very similar and easily confused so. just for reference, here are the structures of a sulfonate ester (such as a tosylate or mesylate), a sulfinate ester, and a sulfenate ester. 

Tris(organoamino)boranes have been utilized to prepare, in reasonable yields,4,5 mono- and dihalo(organoamino)boranes which are often difficult to obtain by direct amination of the boron trihalides. Carboxylic acids, 1,3-diketones, ketones, and /3-ketoesters have been converted into carboxamides, enamino-ketones, enamines, and j -enamino-amides, respectively, by reaction with an appropriate tris(organoamino)borane under very mild conditions.6 Sulfenamides (R2NSC6H5) have also been prepared in high yield from selected tris(organoamino)boranes and sulfenic esters under relatively mild conditions.7... 

Sulfenes when generated in the presence of tricarbonyl partners give rise to 1,3,4-dioxathiane S,S-dioxides <82AP(315)57>. Typically, the treatment of propane-2-sulfonyl chloride (305) with tri-ethylamine in the presence of 1,2,3-indanetrione (307) gives initially the )S-sultone (308) that arises by cycloaddition of the intermediate sulfene (306). Thereafter, attack by chloride ion on (308) furnishes the jS-chlorosulfonate (309). At the same time, further cycloaddition occurs with excess of (307) to generate the doubly spirocyclic 1,3,4-dioxathiane dioxide (310) (Scheme 46). 

The sulfenes (149), generated in situ from the corresponding alkanesulfonyl chloride and tri-ethylamine, add to the nitrones (148) to yield the 1,3-cycloadducts (150), which then rearrange to the final products (152), 1,2,5-benzoxathiazepines, via the intermediates (151) as shown in Scheme 23 (69JOC3097>, A mechanism has been proposed on the basis of 0-labeling studies. 

Equimolar amounts of benzyloxycarbonyl-L-phenylalanine, ethyl glycinate, mercuric chloride, di-o-nitrophenyl disulfide, triphenylphosphine, and 2 moles tri-ethylamine in methylene chloride mixed 3 hrs. at room temp. ethyl benzyl-oxycarbonyl-L-phenylalanylglycinate. Y 89%. Also related condensation of sulfen-amides and cupric carboxylates s. T. Mukaiyama et al.. Am. Soc. 90, 4490 (1968). 

This 23-sigmatropic shift has been of substantial utility since Evans and Hof mann realized that allyl alcohols can be obtained by intercepting the sulfenate with thiophilic agents. One possible way of preparing optically active allylic sulfoxides, which started to racemize even at 0 C was the isomerization of the corresponding vinylic sulfoxide followed by the sulfenate rearrangement in the presence of tri-methyl [diosphite (Scheme 51). ... 

The cycloaddition reactions are subdivided into di-, tri- and oligomerization reactions, [2-1-1]-, [2-1-2]-, [3-1-2]- and [4- -2] cycloaddition reactions and other cycloaddition reactions. The insertion reactions into single bonds are also discussed. The cyclodimerization or cyclotrimerization reactions are special examples of the [2-1-2] and the [2-I-2-I-2] cycloaddition reactions, respectively. The cumulenes vary in their tendency to undergo these reactions. The highly reactive species, such as sulfines, sulfenes, thioketenes, carbon suboxide and some ketenes, are not stable in their monomeric form. Other cumulenes have an intermediate reactivity, i.e. they can be obtained in the monomeric state at room temperature and only heat or added catalysts cause di- or trimerization reactions. In this group, with decreasing order of reactivity, are allenes, phosphorus cumulenes, isocyanates, carbodiimides and isothiocyanates. 

Kinetic and deuteration experiments demonstrated that the hydrolysis of (tri-methylsilyl) methylsulfonyl chloride 14 in water (0.01 MKCl) involves the sulfenes 15 and 16 " (Equation 13). 

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