Selenium reaction with base

Simple derivatives of the parent compound in this group, exo,endo- and o ,o -2,6-dimethyl-l-phosphabicyclo[2.2.1]-heptane 211 and 212, have been synthesized by the cyclization of 2-methyl-4-(2-propenyl)phospholane in the presence of base <2002ZFA580>. The structures were determined via spectroscopic means as well as X-ray crystallography and further confirmed by reactions with selenium, sulfur, (CH3)2SeO, CH3I, and HS03F. 

The known dibromide 464 was converted in good yield to the dinitrile 465 by reaction with buffered potassium or sodium cyanide. Reaction of 2,5-dimethoxycarbonyl-3,4-dicyanomethylthiophene 465 with thionyl chloride and selenium oxychloride gave thieno[3,4-f]thiophene 466 and selenolo[3,4-f]thiophene 467, respectively (Scheme 57) <2002JOC2453>. In the case of thionyl chloride as the sulfur transfer reagent, an intermediate sulfoxide 468 must be involved, which then suffers a spontaneous base-catalyzed Pummerer reaction to give 466 in high yield. 

The isomerization of allyl ethers to 1-propenyl ethers, which is usually performed with potassium tert-butoxide in dimethyl sulfoxide, can also be carried out under milder conditions using tris(triphen-ylphosphine)rhodium chloride,208 and by an ene reaction with diethyl azodicarboxylate,209,210 which affords a vinyl ether adduct. Removal of an O-allyl group may be achieved by oxidation with selenium dioxide in acetic acid,211 and by treatment with N-bromosuccinimide, followed by an aqueous base.201,212... 

Cyclopropanations are known for several other carbanionic intermediates of the general type (7), in which the substituent G is ultimately lost as an anionic leaving group in the last step of the ring-forming pathway (see Scheme 3 above). The substituent G is most often a functional group based upon sulfur, selenium or nitrogen. Halide-substituted derivatives probably react via the a-elimination pathway in most cases (see Section 4.6.3.1), but in some reactions with electron deficient alkenes as substrates, the normal order of steps may be altered (e.g. Table 10, ref. 162). 

Another example of the resin-capture-release technique which should see widespread applications in the future is the selenium-mediated functionalization of organic compounds. Polymer-supported selenium-derived reagents [34] are very versatile because a rich chemistry around the carbon-selenium bond has been established in solution and the difficulties arising from the odor and the toxicity of low-molecular weight selenium compounds can be avoided. Thus, reagent 26 (X = Cl) was first prepared by Michels, Kato and Heitz [35] and was employed in reactions with carbonyl compounds. This treatment yielded polymer-bound a-seleno intermediates, which were set free back into solution as enones from hydrogen peroxide induced elimination. Recently, new selenium-based functionalized polymers 26 (X = Br)-28 were developed, which have been utilized in syntheses according to Scheme 11 (refer also to Scheme 3) [36],... 

Tellurium tetrachloride in combination with a strong amine base effected the mild dehydrosulfurization of thioamides to nitriles. Treatment of the thioamides (60) with tellurium tetrachloride and triethylamine in chloroform at room temperature formed nitriles (61) in excellent yield. Using selenium tetrachloride, a similar reaction also occurred in a little lower yield and accompanied by the formation of the 1,2,4-thiadiazole (63). In a plausible mechanism, some of the 1 1 adduct (61) undergoes a further addition reaction with another thioamide molecule prior to the degradation reaction to nitrile, leading to the formation of the 1,2,4-... 

Estimation of selenium by gas chromatography is based almost exclusively on measurement of the amount of piazselenol formed in the reaction of selenium(IV) with an appropriate reagent in acidic media. Piazselenols are easily extracted with organic solvents (most frequently toluene) in which they can be subsequently determined by... 

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