114158-17-7Relevant articles and documents
Development of pharmaceutical drugs, drug intermediates and ingredients by using direct organo-click reactions
Ramachary, Dhevalapally B.,Kishor, Mamillapalli,Reddy, Y. Vijayendar
supporting information; experimental part, p. 975 - 993 (2009/04/11)
Here we report on our studies of the use of combinations of amino acids, amines, K2CO3 or Cs2CO3 and CuSO4/Cu for catalysing green cascade reactions. We aimed to prepare the highly reactive and substituted olefin species 7 and 8, under very mild and environmentally friendly conditions, thus giving the hydrogenated products 10 and 12 through the action of Hantzsch ester (4) by self-catalysis through decreasing the HOMO-LUMO energy gaps between olefins 7/8 and Hantzsch ester (4) through biomimetic reductions. Highly useful compounds 10 to 14 were assembled from simple substrates such as aldehydes 1, ketones 2, CH acids 3, Hantzsch ester (4) and alkyl halides 5 by diversity-oriented green synthesis involving cascade olefination/hydrogenation (O/H), olefination/hydrogenation/alkylation (O/H/A) and hydrogenation/olefination/hydrogenation (H/O/H) reaction sequences in one-pot fashion with stereospecific organo- and organo-/metal-carbonate catalysis. Highly functionalized diverse compounds such as 10 to 14 are biologically active products and have found wide applications as pharmaceutical drugs, drug intermediates and drug ingredients. For the first time in organocatalysis, we report the O/H/A/TE reaction to furnish high yields of transesterification products 11 by simply mixing the reactants under proline/K2CO3 catalysis conditions. Additionally, a novel organocatalytic H/O/H reaction sequence for the synthesis of alkyl-substituted aromatics has been developed. Furthermore, for the first time we have developed organocatalysed cascade olefination/hydrogenation/hydrolysis (O/H/H) reactions to furnish highly useful materials such as 2-oxochroman-3-carboxylic acid (14kc) and 2-amino-4H-chromene-3-carbonitrile (14kj) in good yields. Experimentally simple and environmentally friendly organocatalytic two-carbon homologation through cascade O/H/H reactions of aldehydes 1, Meldrum's acid (3c), Hantzsch ester (4) and acetic acid/triethylamine in ethanol has been demonstrated. Additionally, we have developed a green synthesis of the highly substituted 1,2,3-triazole 17 from simple substrates through a two-step combination of olefination/hydrogenation/alkylation and Huisgen cycloaddition reaction sequences under stereospecific organocopper catalysis conditions. In this paper we have found strong support for our hypothesis that, "decreasing the HOMO-LUMO energy gap between olefins 7/8 and Hantzsch ester (4) will drive the biomimetic hydrogenation reaction by self-catalysis". This self-catalysis was further confirmed with many varieties of examples. Wiley-VCH Verlag GmbH & Co. KGaA, 2008.
Rhodium(II) Acetate Catalysed Reactions of 2-Diazo-1,3-indandione and 2-Diazo-1-indanone with Various Substrates
Rosenfeld, M. J.,Shankar, B. K. Ravi,Shechter, H.
, p. 2699 - 2705 (2007/10/02)
Decomposition of 2-diazo-1,3-indandione (3) by rhodium(II) acetate (1) in cyclohexane and in benzene results in overall carbon-hydrogen insertion to give 2-substituted 1,3-indandiones.Anisole, 1, and 3 yield 2-(4-methoxyphenyl)-1,3-indandione (74 percent); benzenes substituted by a single methyl or halogen groups yield the corresponding ortho- and para-substitution products.Spirocyclopropanes are obtained by rhodium(II)-catalyzed additions of 3 to olefins; electron-deficient olefins do not give adducts.Substituted 4H-indenofuran-4-ones and 2,3-disubstituted spiroindene>-1',3'-diones are formed from rhodium(II)-catalyzed reactions of 3 with acetylenes.Reactions of 1 and 3 with cyclohexane, olefins, acetylenes, and arenes involve selective electrophilic carbenic or ylidic processes. 2-Diazo-1-indanone (4) is converted by 1 to 2,2'-bis (48).Thiophenol reacts with 4 and 1 to yield 2-(phenylthio)-1-indanone (49).Cyclopropanations of cyclohexene and styrene by 4 as catalyzed by 1 result in spiroheptane-7,2'-indan>-1-one (50) and 2-phenylspiroinden>-1'(3'H)-one (51), respectively.
