• Yamada, N. et al.: Biosci. Biotechnol. Biochem., 56, 1943 (2011)
• Shima, S. et al.: FEBS Lett., 585, 353 (2011)
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Successive alkylation with different alkyl groups, followed by acid hydrolysis, leads to unsymmetrical ketones: Tetrahedron Lett., 4229 (1977). Similarly, dialkylation with ɑω-dihalides gives cyclobutanones: Synthesis, 325 (1980), or larger-ring ketones: Tetrahedron Lett., 22, 4193 (1981). Reaction of monoalkylated TosMIC with ɑω-dihalides is a useful route to 1,5- or 1,6-diketones: Rec. Trav. Chim., 104, 50 (1985):
• For a brief feature on uses of the reagent in synthesis, see: Synlett, 363 (2005).
• In contrast, aldehydes with K2CO3 in refluxing methanol lead to high yields of 5-substituted oxazoles: Tetrahedron Lett., 2369 (1972); with acid chlorides, the corresponding 4-tosyl oxazoles are obtained. For asymmetric induction in the oxazole synthesis by use of π-arylaldehyde-chromium tricarbonyl complexes, see: Tetrahedron: Asymmetry, 3, 287 (1992).
• Other applications in heterocyclic synthesis include the synthesis of:
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Imidazoles by reaction with imidoyl chlorides: Tetrahedron Lett., 2373 (1972). Thiazoles by reaction with CS2 under phase-transfer conditions: Synthesis, 501 (1977). 1,2,4-Triazoles by reaction with diazonium salts, and pyrroles by reaction with Michael acceptors: Tetrahedron Lett., 5337 (1972). Pyrroles are also formed by reaction with aldehydes followed by either ethyl cyanoacetate to give 3-cyanopyrroles: J. Org. Chem., 57, 2245 (1992), or nitromethane to give 3-nitropyrroles: Tetrahedron, 47, 4639 (1991); Synthesis, 871 (1996). The same products are also obtained by reaction of TosMIC with nitroalkenes, from Henry reaction of the aldehydes with nitromethane:
• In the presence of base (e.g. KO-t-Bu) in an aprotic solvent, e.g. DME, ketones are cyanated to give the homologous nitriles; see, e.g.: Org. Synth. Coll., 6, 41 (1988). Hindered ketones can be cyanated in DMSO: J. Org. Chem., 42, 3114 (1977). Aldehydes condense with TosMIC at -50o, followed by hydrolysis in refluxing methanol: Synth. Commun., 10, 399 (1980).
Toxic (T)