Sulfides carbonyl compound synthesis from

The Aggarwal group has used chiral sulfide 7, derived from camphorsulfonyl chloride, in asymmetric epoxidation [4]. Firstly, they prefonned the salt 8 from either the bromide or the alcohol, and then formed the ylide in the presence of a range of carbonyl compounds. This process proved effective for the synthesis of aryl-aryl, aryl-heteroaryl, aryl-alkyl, and aryl-vinyl epoxides (Table 1.2, Entries 1-5). 

Annulation /raw-3,4-Disubstituted tetrahydrothiophenes are obtained from conjugated carbonyl compounds and chloromethyl trimethylsilylmethyl sulfide in a reaction mediated by CsF. When the conjugated carbonyl component bears a chiral auxiliary, the process is amenable to synthesis of enantiopure derivatives. 

Dilithium tetrachlorocuprate is recommended as an additive for cross coupling of Grignard compounds with tosylates even allylic and benzylic acetates give good yields . a-Methylene-ketones, -carboxylic acids and -lactones have been prepared via sulfides and sulfoxides. A convenient and general synthesis of acetylene derivatives from boranes via the reaction of iodine with lithium 1-alkynyltriorganoborates has been published ar-Nitrostyrenes can be easily obtained by a Wittig synthesis with formaldehyde in an aqueous medium . A new synthesis of unsym. ketones by reaction of dialkyldiloroboranes with lithium aldimines has recently been published . Metallo aldimines have also served for the synthesis of a variety of other compound classes such as a-hydroxyketones, a-keto acids, nitriles, and for the asym. synthesis of a-amino acids . Polycondensations of malononitriles with benzylic chlorides have been carried out quantitatively under mild conditions in dimethyl sulfoxide with triethylamine as acid acceptor . Carbonyl compounds can react with dibromoacetonitrile to yield a-bromo esters with additional carbon atom . ... 

A polymeric sulfur ylid reagent containing dimethylsulfonium methylide was synthesized by Tanimoto et al. (1967) from a copolymer of p-vinylphenylmethyl thioether, styrene, and DVB, according to Scheme 12-17. The reagent was used for the synthesis of epoxides from the carbonyl compounds. It was claimed that, in addition to simplifying the procedure for isolation of the products, the polymeric reagent is nonodorous and convenient to handle, compared to the noxious, volatile, low-molecular-weight sulfides used in classical syntheses. 

On the pages which follow, general methods are illustrated for the synthesis of a wide variety of classes of organic compounds including acyl isocyanates (from amides and oxalyl chloride p. 16), epoxides (from reductive coupling of aromatic aldehydes by hexamethylphosphorous triamide p. 31), a-fluoro acids (from 1-alkenes p. 37), 0-lactams (from olefins and chlorosulfonyl isocyanate p. 51), 1 y3,5-triketones (from dianions of 1,3-diketones and esters p. 57), sulfinate esters (from disulfides, alcohols, and lead tetraacetate p. 62), carboxylic acids (from carbonylation of alcohols or olefins via carbonium-ion intermediates p. 72), sulfoxides (from sulfides and sodium periodate p. 78), carbazoles... 

Numerous unusual organosulfiir transition metal compounds have been obtained by reactions of various metal carbonyls and cyclopentadienyl-metal carbonyls with certain mercaptans, sulfides, disulfides, and dithietenes (1,2). Other types of organosulfiir transition metal compounds have been obtained from metal sulfides and certain acetylene derivatives (3). This paper discusses a new and entirely different synthesis of new types of organosulfur derivatives of metal carbonyls with metal-sulfiir bonds. These new compounds have been obtained by thermal or photochemical decarbonylation of compounds of general formula CH S CH ) U(CO)yHC H )y (n = 1,2 or 3 M = Fe [x 2, y = 1], or Mn [x = 5, y = OJ) without metal-sulfur bonds. These sulfur-containing transition metal alkyl derivatives, none of which has been previously reported, may in turn be obtained from metal carbonyl anions and the chloroalkyl methyl sulfides CH S(CHpnCl. 

To overcome this limitation, the vinyl sulfide and selenide were used as the substrates instead of mono- and 1,2-disubstituted olefins [129]. With these substrates, the ene products are formed with almost complete enantioselectivity. The carbonyl-ene adducts have been applied to the synthesis of natural compounds such as (R)-(—)-ipsdienol, an insect aggregation pheromone [130] (Scheme 14.49). For trisubstituted olefin substrates, a more Lewis acidic catalyst prepared from 6,6 -Br2BINOL gave better results [128b, c]. 

This section covers the removal of COS, CS2, and light mercaptans from gas streams by amine solutions. These are the principal organic sulfur compounds normally encountered in fuel and synthesis gases. The removal of organic sulfur compounds from liquid hydrocarbons is discussed in the next section. The presence of the above components (and many other reactive species) in a gas to be treated raises two questions (1) How much, if any, of the material will be removed during the treating operation and (2) will the impurities cause deterioration of the amine solution The question of solution deterioration by reaction with various gas impurities is discussed in detail in Chapter 3 this discussion is concerned primarily with removal of carbonyl sulfide, carbon disulfide, and mercaptans from the gas by amine solutions. 

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