Thioaldehydes, from

Further examples of the photolytic generation of thioaldehydes from phenacyl sulfides include the synthesis of 3,6-dihydro-27/-thiopyrans bearing a variety of functions at C-2 of which some are potent acyl-CoA-cholesterol acyl-transferase inhibitors (Equation 135) <1996BMC1493>. 

Only a few intramolecular thioaldehyde [4 + 2] cycloadditions have been executed to date. Vedejs et al. have looked at systems such as that shown in equation (88).Their photochemical method is useful in effecting intramolecular reactions but stereoselectivity in the process was only moderate. Baldwin and Lopez have described the single intramolecular cycloaddition shown in equation (89) which involves a new thermal method for generating thioaldehydes from alkyl thiosulfinates. ... 

Generation of thioaldehydes from a-mercaptonitriles Gas-phase dehydrocyanation in vacuo... 

Nonchelation control also results from the trifluoroborane-mediated addition of the following silylketcne acetal to 2-thioaldehydes. The diastereomeric ratios of the adducts surpasses 98 2... 

Selenoaldehydes 104, like thioaldehydes, have also been generated in situ from acetals and then directly trapped with dienes, thus offering a useful one-pot procedure for preparing cyclic seleno-compounds [103,104], The construction of a carbon-selenium double bond was achieved by reacting acetal derivatives with dimethylaluminum selenide (Equation 2.30). Cycloadditions of seleno aldehydes occur even at 0 °C. In these reactions, however, the carbon-selenium bond formed by the nucleophilic attack of the electronegative selenium atom in 105 to the aluminum-coordinated acetal carbon, may require a high reaction temperature [103], The cycloaddition with cyclopentadiene preferentially gave the kinetically favorable endo isomer. 

The addition of H2S to an aldehyde or ketone can result in a variety of products. The most usual product is the trithiane (8). ° ot-Hydroxy thiols (5) can be prepared from polychloro and polyfluoro aldehydes and ketones.Apparently, compounds 5 are stable only when prepared from these compounds, and not even for all of them. Thioketones (6) can be prepared from certain ketones, such as diaryl ketones, by treatment with H2S and an acid catalyst, usually HCl. They are often unstable and tend to trimerize (to 8) or to react with air. Thioaldehydes are even less stable and simple ones apparently have never been isolated, though t-BuCHS has been... 

The reaction of thioaldehydes, generated from phosphonium ylides and sulphur with secondary amines such as dimethylamine, leads to thioamides. If the thioaldehydes possess a a-hydrogen atom enamines are produced (equation 103)326. 

Concomitant C-Si cleavage by tetra-n-butylammonium fluoride and extrusion of a phenylthiolate anion from ot-trialkylsilyldisulphides provides a route to reactive thioaldehydes [44],... 

It is very well known that polymers of high commercial value are obtained from formaldehyde by addition polymerization of its carbon-oxygen double bond. Not so well known is the addition polymerization capability of the carbon-sulfur double bond, probably because none of the polymers so obtained has yet become commercially acceptable. However, the polymerization chemistry of the carbon-sulfur double bond has been the subject of a number of studies and these have defined the preparation and properties of polythioformaldehyde, polythio-acetone, polymers from a small number of higher thioketones, and polymers from fluorine analogs of thioaldehydes and thioketones. The monomers have great reactivity beyond polymerization, and their general chemistry has been discussed in earlier reviews (/, 2). 

Thioaldehyde oxides are reported to be one of the lachrymatory agents in onions and are speculated to dimerize via an initial [4+2] cycloaddition to a five-membered ring that rearranges to a 1,2-dithietane dioxide. The latter has also been isolated from extracts of onions (80JA2490) and is reported to be the only characterized derivative of a 1,2-dithietane (Scheme 121). 

When a,/3-unsaturated esters are the target molecules, the use of a thioaldehyde or thioketone is advisable for the easy elimination of H2S from the intermediate thiol adduct. This strategy has been applied to thiolactams 94a and to thionolactones 94b, opening a route to vinylogous carbamates 95a143 and carbonates 95b144(equation 57). 

Silathietanes can be readily prepared from the appropriate bis(chloromethyl)silane and KSH or by intramolecular hydrosilation in the presence of Wilkinson s catalyst (Scheme 97) (81JOM(204)13). Electron impact and photoionization mass spectrometry support the loss of silathione ions (R2Si=S) (R = Me, Et) indicating a transannular interaction, though decomposition by the loss of silenes and thioaldehyde also readily occurs (81JOM(214)145). 

Thiocarbonyl compounds can be generated thermally in the gas-phase from a variety of precursors. Bock et al. [77JCS(CC)287 82CB492] have shown that pyrolysis of 1,2,4-trithiolane derivatives (81) is especially advantageous for this purpose. The fragmentation reactions were monitored by PE spectroscopy. By this method thioaldehydes including thioformaldehyde and thioketones that polymerize readily were obtained. 1,2,4-Trithiolane 4-oxide (82) yields a mixture of thioformaldehyde and thioformaldehyde oxide. 

Similarly, the thioaldehyde complexes 66a,b were formed via addition of thiols to the vinylidene complex 64 and elimination of ethene. The vinylidene complex 64 reacted with benzyl mercaptan to yield the isolable intermediate 65. On heating 65 lost ethene in a first-order reaction to give 66b.188 The complexes 66a-d could also be prepared from the benzyne-(hydrido) complex 67 and thiols RCH2SH (Scheme 18).188... 

The thioaldehyde complexes 81a,b were formed from the thiolato complexes 80a,b on treatment with PMe3 (Scheme 21). The thiolato compounds were obtained from 79 and MeCH2SH or PhCH2SH. Although the complexes 81a,b were stable even in refluxing benzene for several hours, they... 

Another route to thioaldehyde and thioketone complexes uses the tungstate [W(CO)5SH] as the precursor. When [W(CO)5SH] was treated with ketones in the presence of trifluoroacetic acid, thioketone complexes [W(CO)5 S = C(R1)R2 ] were formed. Analogously, thiobenzaldehyde complexes were obtained from [W(CO)sSH]- and benzaldehydes bearing electron-releasing para substituents. Benzaldehyde, benzaldehydes with electron-withdrawing substituents, and aliphatic aldehydes did not react. Presumably, the binuclear dianion [p,-S W(CO)5 2]2 is an intermediate in the reaction, as on acidification of a mixture of [ju,-S W(CO)5 2]2 and p-N, A -dimethylaminobenzaldehyde the thioaldehyde complex [W(CO)5 S = C(C6H4NMe2-p)H ] is formed.143... 

The reactions of dinuclear thioaldehyde and -ketone complexes with PR3 take a different course. When the dimeric complexes 112 are treated with PMe3 a Ti-S bond in 112 is cleaved and the monomeric complexes 113 are reversibly formed (see Scheme 26), 69 The reaction of 112 with benzene-thiol led to a Ti-C cleavage and formation of 1,3-propanedithiolato-(phenylthiolato) complex.69 The reaction of binuclear p-191 rf-thioketone molybdenum complexes related to 115 (M = Mo, E = S, R = Aryl) with P(OEt)3 also gave mononuclear complexes [Mo(CO)2(Et) i72-S = C(Aryl)2 (i75-C5H5)] by a rather complicated reaction sequence. When other phosphites were employed additionally binuclear complexes derived from addition of the phosphite to one molybdenum atom were isolated.225... 

The C = C bond of several alkynes inserted into the Zr-C bond of the rj2-thioaldehyde zirconocene complexes 81 (see Scheme 21) to form the five-membered thiazirconacycles 144. The imine metallacycle obtained from 81 and butyronitrile tautomerized under the reaction conditions to cleanly give the enamine metallacycle 145 (Scheme 38).70... 

However, the reaction of the binuclear rj2-thioaldehyde titanocene complexes 112 (see Scheme 26) with valeronitrile, benzonitrile, and methyl thiocyanate proceeded in a similar fashion (Scheme 39).69 Related metalla-cyclic compounds were also obtained from the reactions of 112 with benzo-phenone (Scheme 39), various imines, phenyl isothiocyanate, or dicyclohexyl carbodiimide via insertion of the C = 0 and C = N bond, respectively, into the Ti-C bond.69,70... 

Thioaldehydes Thioaldehydes can be generated from a-silyl disulfides (1) by treatment with CsF in THF at 25° or with Bu4NF in THF at 0°. The thioaldehyde is identified by cycloaddition to cyclopentadiene. 

Substituted penam (I, Fig. 9) has been reported to be obtained by coupling of thioaldehyde with azomethine ylide which was derived from the (3-lactam based oxazolidinone [262]. 

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