Stereospecificity thermal elimination reactions

In some cases, eliminations occur in non-ionizing solvents and without the addition of any base. In these cases the reactant itself has an internal base and a cyclic transition state leads to elimination. The symbolism for the reactions is Ei, standing for elimination, intramolecular. Only heat is required to induce the reaction, and hence these reactions are called thermal eliminations (the term pyrolysis is also sometimes used). Thioesters, xanthates, selenoxides, and N-oxides are common in these reactions. The Cope elimination involves the formation of an N-oxide and subsequent elimination via the pathway shown in Eq. 10.91, and the Chugaev elimination involves xanthate esters [ROC(S)SR]. The Chugaev elimination was shown to follow a syn elimination pathway based on the stereospecific nature of the reaction (Eqs. 10.92 and 10.93). 

Thermal )6-elimination reactions of acetates, benzoates, xanthates, sulfoxides, selenoxides, and N-oxides are also group transfer reactions. All these elimination reactions are yn-stereospecific and proceed through a cyclic six membered—or five membered—ring transition state of 6e process by intramolecular transfer of hydrogen atom, where all the participating orbitals have suprafacial interactions. These reactions are fundamentally retro-group transfer reactions. 

It has been generally assumed that thermal decomposition of thiirane oxides proceeds stereospecifically to the corresponding olefins by elimination of sulfur monoxide, possibly through a concerted nonlinear chelatropic reaction with retention of configuration of the liberated olefin. 

The selenosulfonates (26) comprise another class of selenenyl pseudohalides. They are stable, crystalline compounds available from the reaction of selenenyl halides with sulftnate salts (Scheme 10) or more conveniently from the oxidation of either sulfonohydrazides (ArS02NHNH2) or sulftnic acids (ArS02H) with benzeneseleninic acid (27) (equations 21 and 22). Selenosulfonates add to alkenes via an electrophilic mechanism catalyzed by boron trifluoride etherate, or via a radical mechanism initiated thermally or photolytically. The two reaction modes produce complementary regioselectivity, but only the electrophilic processes are stereospecific (anti). Similar radical additions to acetylenes and allenes have been reported, with the regio- and stereochemistry as shown in Scheme 11. When these selenosulfonation reactions are used in conjunction with subsequent selenoxide eliminations or [2,3] sigmatropic rearrangements, they provide access to a variety of unsaturated sulfone products. 

The Chugaev reaction of S methyl xanthates is a synthetically useful p5u olysiss process. The corresponding electron impact induced elimination is a prominent feature of xanthate mass spectra, (45). > The electron impact induced cleavage is at least partially cfs-stereospecific as the thermal reaction is... 

Cyclic exponents of the same elimination type are of particular interest. Thus, numerous cyclopentanones photolytically decarbonylate to give 1,4-dienes (p. 876 ff. in Ref. 108)). With thujone (194) this [l,2,(3)4]-elimination of carbon monoxide proceeds quantitatively to give 195 109). With silver nitrate the norcaradiene 196 yields 197 (95%)110) apparently regioselectively, and the [l,2,(3)4]-elimination of methanethiol from 198 to give 199 was realized thermally (16%), acid-catalyzed (59%), and photochemiciiily (ca. 5%)105). For the acid-catalyzed reaction (acetic acid, 100 °C) a non-stereospecific process has been proved 105). 

Lipases are subclass of esterases, capable of hydrol3 ing esters, fats and lipids in aqueous media, hence they are described as hydrolases belonging to class EC 3.1.1.3. Lipases are one of the most versatile enzymes because they can catalyze many different reactions such as esterification, interesterification, hydrolysis, alcoholysis, peroxidation, aminolysis, and epox-idation. " " Most lipases have similarities in their amino acid sequence including within the catalytic region, His-X-Y-Gly-Z-Ser-W-Gly or Y-Gly-His-Ser-W-Gly where W, X, Y and Z refer to unspecified amino acid residues. These enzymes are stereospecific towards ester bonds thereby eliminating any undesirable by-products of the reaction. Lipase has been used extensively as a biocatalyst in industry because of its high thermal stability, versatile pH range and it can be used repeatedly if immobilized e.g. Novozyme 435). ... 

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