Serini reaction

Three possible mechanisms for the Serini reaction were originally suggested. These proceed via (a) a A -enol acetate, (b) a A -epoxide, or (c) a cyclic orthoester ... 

Rubin and Blossey standardized the experimental conditions for the Serini reaction, using freshly activated zinc in refluxing xylene for 20-24 hr with vigorous stirring yields of68-100 % could then be obtained. They noted, however, that the presence of a 16a- or -methyl group markedly decreased the yield, and that a primary-secondary glycol monoacetate failed to react. 

Serini reaction, 167 Simmons-Smith reaction, 107 Sodium acetylide, 138 Sodium bismuthate, 147, 149 Sodium bistrimethylsilylamide, 90 Sodium chloroacetylide, 68 Solvolytic cleavage of cyclic ethers, 267 3- (5 -Spiro-2, 2 -dimethyloxazolidi nyl) -cholestane, 360... 

Serini reaction. This reaction consists in refluxing a aic-diol monoacetate of type (1) or (3) with zinc dust in toluene and results in elimination of acetic acid with formation of a 20-ketone (2,4) inverted at C, . Discussion of mechanism." ... 

Serini reaction. Zinc-promoted rearrangement of 17-hydroxy-20-acetoxysterol derivatives into C-20 ketones. The reaction is applicable to other cyclic, as well as open-chain alcohols. 

Salcomine, 360 Salicylaldehyde, 96, 217, 457 Sandmeyer reaction, 87 o-Santalene, 291 Schiff bases, 66, 249 Selenium dioxide, 93, 360-362 Selenium dioxide-Hydrogen peroxide, 362 Semicarbazide, 98 Semicarbazones, 65 Sensitizers, 285-286 L-Serine, 143 Serini reaction, 459, 460 Silica gels, 453 Silver acetate, 233, 362-363 Silver benzoate, 103 Silver carbonate, 363 Silver chlorate, 363-364 Silver cyanate, 224 Silver fluoride, 364-365 Silver fluoroborate, 365-366 Silver nitrate, 224, 240, 363, 366-368, 369, 371... 

Serini reaction [1, 1282, after citation of ref. 42], The activation of 1100 g. of granular 30-mesh zinc with 4.4 liters of coned, sulfuric acid containing 2 ml. of 90% nitric acid and its use in the Serini reaction is described by Rubin and Brown.423 The Serini reaction is actually a general synthetic method. Thus Ghera et al.iib... 

Benzoates and/r-nitrobenzoate esters can be used as well as acetates, higher yields being obtained with the former. Yields are in the range 50-95%. Replacement of metallic zinc by anhydrous zinc acetate gives similar results. Ghera discusses the mechanism and stereochemistry of the Serini reaction. He suggests that the catalyst functions as a complexing Lewis acid. 

Serini reaction (1, 1282 2, 459-460). Ghera10 has published the full paper on the synthesis of ketones by zinc-catalyzed rearrangement of secondary esters of trisubstitutcd 1,2-glycols ... 

Ketones from glycol monoesters Serini reaction... 

Other references related to the Serini reaction are cited in literature 5. 

The mechanism of the Serini reaction has been studied further by Ghera, and the pathway shown in Scheme 59 proposed for this general reaction of 1,2-trisubstituted r/c-glycol monoesters. A related process is seen in the formation of olefins by zinc-induced fragmentation of 1,3-diol monoesters a... 

In 1921 Passerini reported the synthesis of the a-acyloxycaiboxamides (6a-e) according to the scheme below. The formation of a-acyloxycarboxamides by a three-component reaction of carboxylic acids (3), carbonyl compounds (4) and isocyanides (5) is the proper Passerini reaction. The reactions described in Sections 4.6.2.2-4.6.2.4 are closely related to the I serini reaction we call them reactions of the Passerini type. - ... 

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