Thietes reactivity

Conversion of 3-chlorothietane 1,1-dioxide to the 3-(N,N-dimethylaraino) derivative followed by reduction, quaternization, and Hofmann elimination affords a convenient route to the highly reactive thiete (thiacyclobutenel... 

As highly reactive heterocycles, the thietes are well suited for the formation of metal complexes. Takahashi and Dittmer both individually and in collaboration have been involved with the interaction of thietes and iron or cobalt carbonyls. During the thermally or photochemically induced complexation process, ring opening takes place so that the resultant thioacrolein is the actual ligand in the organometallic compound (Scheme i7)/ 3-203,204... 

Since the publication of CHEC-II(1996), there have been no new reports on the reactivity of fully conjugated monocyclic thietanes and thietes. 

The reactivity of the benzo analogue of compound 41, that is, 2//-naphtho[l,2-4]thiete 47, has also been studied. Cycloaddition reactions with dienophiles or heterodienophiles performed in boiling toluene yielded naphtho-condensed sulfur heterocycles (Scheme 5) <1998JHC1505>. 

The cycloaddition of sulfenes with enamines provides a good synthetic route to thiete 1, 1-dioxides (174) (see Chapter 7, p. 115) (Scheme 69).8 Thiete-1, 1-dioxides like (174) react with alkylamines by conjugate addition to yield the corresponding amino derivatives (175), and by heating in the presence of a reactive alkene, e.g. norborene (176), they form the [2+4] cycloadducts, e.g. (177) (Scheme 69). 

A hydrazidoyl hatide (reviews [1437, 1753]) reacts with some C—C double bonds in the presence of TEA or a phase transfer catalyst [3086]. The reactive double bond of thiete sulphone (84.6) adds on diazoalkanes under mild conditions to form the fused pyrazole (84.7) but diazomethane gives mostly isomer (84.8) [2174]. Addition of diazomethanes to the unsubstituted CH sCH group of a 1,4-quinone occurs under mild conditions to give versatile intermediates [2693, 2700]. The chemistry of heterocyclic quinones has been reviewed [2947, 3650]. 

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