Sulfinic acid amides alcohols

Sulfinic acid amides are obtained in the reaction of sulfinic acids with amines in the presence of DCC." In the reaction of sulfuric acid with alcohols, thioalcohols and amines in the presence of DCC, the respective sulfates, thiosulfates and amides are obtained." The reaction of H3PO4 with DCC, followed by alcohol affords (R0)2P(0)H." ... 

Substrates usefully employed in Mannich reactions are, in general, XH compounds having nucleophilic properties, with X being equal to C, N, or other heteroatoms (Fig. 4). In particular, CH compounds are suitably activated saturated and unsaturated derivatives, and NH substrates may be amines, amides, hetcrocyclcs, etc. Out of OH sub-stratcs, alcohols are mainly able to give stable Mannich products. Sulfur- and phosphorus-containing substrates are XH derivatives having the H atom bonded to the hetcroatom in the lower oxidation state, i.e., thiols, sulfinic acids, and, respectively, phosphine and phosphorous acid derivatives. As and Se compounds have also been successfully used. All these substrates are listed in more detail in Sec. D of this chapter. 

Arylation of a wide range of NH/OH/SH substrates by oxidative cross-coupling with boronic acids in the presence of catalytic cupric acetate and either triethyl-amine or pyridine at room temperature in air. The reaction works for amides, amines, anilines, azides, hydantoins, hydrazines, imides, imines, nitroso, pyrazi-nones, pyridones, purines, pyrimidines, sulfonamides, sulfinates, sulfoximines, ureas, alcohols, phenols, and thiols. It is also the mildest method for NIO-vinylation. The boronic acids can be replaced with siloxanes or starmanes. The mild condition of this reaction is an advantage over Buchwald-Hartwig s Pd-catalyzed cross-coupling. The Chan-Lam C-X bond cross-coupling reaction is complementary to Suzuki-Miyaura s C-C bond cross-coupling reaction. 

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... 

---