Chalcogen cycloaddition

The chalcogene heterocycles have been used as stable precursors for sulfur-said selenium-cantaining hetero-l,3-dienes in cycloaddition reactions 3//-l,2,4-Thiaselenazoles are a convenient source of 4,4-bis(trifluoromethyl)-l-thia-3-aza-buta-1,3-dienes, and 3//-diselenazoles are a convenient source of 4,4-bis(trifluoromethyl)-l-selena-3-azabuta-l,3-dienes as well as bis(tnfluoro-methyl)-substrtuted nitrile ylides [137]... 

Cycloaddition reactions also have important applications for acyclic chalcogen-nitrogen species. Extensive studies have been carried out on the cycloaddition chemistry of [NSa]" which, unlike [NOa]", undergoes quantitative, cycloaddition reactions with unsaturated molecules such as alkenes, alkynes and nitriles (Section 5.3.2). ° The frontier orbital interactions involved in the cycloaddition of [NSa]" and alkynes are illustrated in Fig. 4.13. The HOMO ( Tn) and LUMO ( r ) of the sulfur-nitrogen species are of the correct symmetry to interact with the LUMO (tt ) and HOMO (tt) of a typical alkyne, respectively. Although both... 

Chalcogenation of a divalent germanium compound with styrene sulfide has been examined as an alternative route to the first free germanethione Tbt(Tip)Ge = S 165142 (Scheme 32) and later on allowed the synthesis of new base-stabilized germanethiones 187 and 188156 [Eq. (37)]. Phenyl isocyanate also may serve as a sulfur source leading to 165, which was evidenced by electronic spectroscopy and underwent a subsequent [2 + 2] cycloaddition with phenyl isocyanate157 (Scheme 36). 

Cationic polar cycloaddition, 16, 289 (19, xi) Cations, polycyclic aromatic nitrogen, 55,261 Chalcogen heterocyclic chemistry, some recent developments in, 71, 115 Chemistry... 

In view of the preference of the tetrasilabuta-1,3-diene 139 for the s-cis form, it seemed worthwhile to examine its behavior in [4 + 2] cycloadditions of the Diels-Alder type. Since 139, like many disilenes, should behave as an electron-rich diene, we attempted to react it with various electron-poor and also with some electron-rich olefins. No reaction was detected in any case. Only in the presence of water did 139 react with quinones to furnish the unsymmetrically substituted disilenes 36 and 37 (see Section III.A). The effective shielding of the double bonds by the bulky aryl groups and, above all, the 1, 4-separation of the terminal silicon atoms of about 5.40 A appear to be responsible for these failures. Thus, it was surprising that treatment of 139 with the heavier chalcogens afforded five-membered ring compounds in a formal [4 + 1] cycloaddition (see below). 

In analogy to the reactions of acyclic disilenes with the heavier chalcogens78,79 it can be assumed that an initial [2 + 1] cycloaddition of the respective chalcogen to one of the Si=Si double bonds of 139 takes place, followed by a rearrangement of the resultant three-membered ring to a less strained five-membered ring. 

Five-membered heterocycles with two vicinal chalcogen atoms in the ring system can be used as stable precursors for sulfur as well as for selenium-containing hetero-1,3-dienes in cycloaddition reactions. Consequently, 3//-1,2,4-thiaselenazoles have been used for the in situ formation of 4,4-bis(trifluoromethyl)-l-thia-3-azabuta-1,3-dienes, which exist at room temperature only as 4,4-bis(trifluoromethyl)-2//-l,3-thiazetes. This strategy was applied to the synthesis of the first stable selenophosphorane from bis(trifluoromethyl)-substituted 3//-diselenazol and 2-methoxy-1,3,2-dioxaphospholan [78AG(E)774] (Scheme 83). 

Half this review is concerned with aziridination, but other cycloadditions are generally excluded, being reviewed elsewhere in this series (Volume 4, Part 4 and Volume 5, Part 4). The second half of this review covers additions of nitrogen and a chalcogen or halogen, or a second nitrogen. No examples of addition of N + P were found this transformation can be achieved indirectly by opening aziridines with phosphorus nucleophiles. ... 

Terminal chalcogenido zirconium complexes (23) are conveniently synthesized by the reactions of dicarbonylzir-conocene with either N2O or the elemental chalcogens (S, Se, Te) see Chalcogens) in the presence of pyridine. The Zr=E bond in these complexes is highly reactive and leads to a variety of 1,2-addition and cycloaddition reactions (Scheme 8). ... 

Although the mechanism of formation of 11-13 cannot be proven experimentally, the following proposal seems to be reasonable. In analogy to the reaction of disilenes, the reaction sequence could be initiated by a [2+1] cycloaddition of a chalcogen atom to one of the Si=Si double bonds, followed by a rearrangement of these intermediates into the less strained five-membered rings ll-13.f ... 

Since genuine [4-1-2] cycloaddition products had previously not been prepared, it was surprising to find that the action of sulfur on 24 resulted in a formal [4-I-1] cycloaddition to furnish the first ftve-membered ring with an endocyclic silicon-silicon double bond 25. The heavier chalcogens selenium and tellurium did not react with 24. However, in the presence of small amounts of triethylphosphane smooth reactions with these elements did occur to furnish two further ftve-membered ring compounds 26, 27, each with an endocyclic silicon-silicon double bond (Eq. 8) [14]. 

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