1,3,2-Dioxathiolane 2-oxides synthesis

Trithioles and 1,3,2-dioxathiolanes. 1,2,3-Trithiolanes are prepared by reaction of alkenes with elemental sulfur . The synthesis of 1,3,2-dioxathiolane -oxides (cyclic sulfites) and 1,3,2-dioxathiolane S, -dioxides (cyclic sulfates) is discussed in comprehensive reviews <1997AHC(68)89, 2000T7051>. The most widely used method for the preparation of 1,3,2-dioxathiolane A-oxides 557 is the reaction of the corresponding 1,2-diols 556 with thionyl chloride in the presence of pyridine or triethylamine (Scheme 251). More reactive 1,3,2-dioxathiolane S,A-dioxides 558 are usually obtained by oxidation of sulfites 557 with sodium periodate, which is mediated by ruthenium tetroxide generated in situ from a catalytic amount of ruthenium trichloride <1997AHC89, 2000T7051, CHEC-III(6.05.10.3)183>. 

The second chapter in this volume, 1,3,2-Dioxathiolane Oxides Epoxide Equivalents and Versatile Synthons, is authored by Dr. B. B. Lohray and Dr. V. Bhushan of the Reddy Research Foundation, Hyderabad, India. These compounds are cyclic sulfates and, over the past seven or eight years they have become important intermediates in organic synthesis. 

Ethylene, /3-(dimethylamino)-nitro-in pyrrole synthesis, 4, 334 Ethylene, dithienyl-in photochromic processes, 1, 387 Ethylene, furyl-2-nitro-dipole moments, 4, 555 Ethylene, l-(3-indolyl)-2-(pyridyl)-photocyclization, 4, 285 Ethylene, l-(2-methyl-3-indolyl)-l,2-diphenyl-synthesis, 4, 232 Ethylene, (phenylthio)-photocyclization thiophenes from, 4, 880 Ethylene carbonate C NMR, 6, 754 microwave spectroscopy, 6, 751 photochemical chlorination, 6, 769 synthesis, 6, 780 Ethylene oxide as pharmaceutical, 1, 157 thiophene synthesis from, 4, 899 Ethylene sulfate — see 2,2-dioxide under 1,3,2-Dioxathiolane... 

A review of cyclic sulfites and sulfates in organic synthesis includes many examples of 1,3,2-dioxathiolane 5-oxides and 5,5-dioxides <0OT7O51>. Reaction of cyclic sulfates such as... 

The various possibilities for the first two types of syntheses are listed schematically in Table 4, and the possibilities for synthesis from other heterocycles are listed in Table 5. In each case the method is discussed in more detail in the following sections Tables 4 and 5 indicate the section(s) in which a particular reaction is described. In the case of sulfur-containing heterocycles, 5-oxides and 5,5-dioxides are treated alongside the basic parent structures, since for 1,3,2-dioxathiolane, 1,2,3-oxadithiolane, and 1,2,5-oxadithiolane the unoxidized rings are unknown. 

Attempted thermal epimerization of the diastereomeric 1,3,2-dioxathiolane A-oxides 11 failed even when these compounds were refluxed in o-dichlorobenzene, which indicated a kinetic control of the diastereomeric ratio in the course of their synthesis <2003HAC587>. 

The syntheses and reactions of 1,3,2-dioxathiolane. Y-oxides and 1,3,2-dioxathiolane. Y,.Y-dioxides have been discussed in comprehensive reviews <1997AHC89, 2000T7051>. In publications on organic synthesis these compounds are usually named cyclic sulfites and cyclic sulfates, respectively (Sections 6.05.5 and 6.05.6 Tables 1-7). 

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