97388-67-5

Upstream product

• 1318767-42-8 N-methoxy-N,5-dimethylhex-5-enamide 
• 1589-82-8 phenylmagnesium bromide 
• 3128-06-1 5-ketohexanoic acid 
• 3740-59-8 3,4-dihydro-6-methyl-2H-pyran-2-one 
• 6921-34-2 benzylmagnesium chloride 
• 97388-65-3 [4-Iodo-1-methyl-1-(toluene-4-sulfonyl)-butyl]-methylene-amine 
• 97388-64-2 [4-Chloro-1-methyl-1-(toluene-4-sulfonyl)-butyl]-methylene-amine 
• 97388-66-4 2,6-diisocyano-2,6-ditosyl-1-phenylheptane 
• 116931-72-7 1,5-bis(1-methyl-1H-imidazol-2-yl)-6-phenyl-5-(trimethylsilyloxy)hexan-1-one 

Relevant academic research and scientific papers

Oxidative Cleavage of Alkenes by O2with a Non-Heme Manganese Catalyst

The oxidative cleavage of C═C double bonds with molecular oxygen to produce carbonyl compounds is an important transformation in chemical and pharmaceutical synthesis. In nature, enzymes containing the first-row transition metals, particularly heme and non-heme iron-dependent enzymes, readily activate O2 and oxidatively cleave C═C bonds with exquisite precision under ambient conditions. The reaction remains challenging for synthetic chemists, however. There are only a small number of known synthetic metal catalysts that allow for the oxidative cleavage of alkenes at an atmospheric pressure of O2, with very few known to catalyze the cleavage of nonactivated alkenes. In this work, we describe a light-driven, Mn-catalyzed protocol for the selective oxidation of alkenes to carbonyls under 1 atm of O2. For the first time, aromatic as well as various nonactivated aliphatic alkenes could be oxidized to afford ketones and aldehydes under clean, mild conditions with a first row, biorelevant metal catalyst. Moreover, the protocol shows a very good functional group tolerance. Mechanistic investigation suggests that Mn-oxo species, including an asymmetric, mixed-valent bis(μ-oxo)-Mn(III,IV) complex, are involved in the oxidation, and the solvent methanol participates in O2 activation that leads to the formation of the oxo species.

Metal Coordination Controlled and Bifunctional H-Bonded Catalysis in Stereoselective Intramolecular Aldol Cyclizations toward Carbocyclic Tertiary β-Ketols

The principle of bifunctional catalysis is shown in the highly regio- and stereoselective intramolecular aldolization of 2-methyl-1,3-cyclopentanedione, C2-substituted with a methyl ethyl ketone group, to provide [3.2.1]-bicyclooctanol diones in the presence of catalytic amounts of either LiBr and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), or 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD). Mechanistic investigations corroborated by DFT calculations show that LiBr engages in a bifunctional coordination of two carbonyl moieties and leads to the preorganization of the reactive enolate intermediate for a base-mediated intramolecular aldol cyclization. On the other hand, TBD catalysis of the triketone substrate proceeds through a bifunctional H-bonded mechanism to give the same aldol product as the major diastereomer. The LiBr and TBD-catalyzed highly stereocontrolled intramolecular aldol cyclizations can be extended to other di- and triketones to give carbocyclic and carbobicyclic products as single diastereomers.

Organocatalytic asymmetric reaction cascade to substituted cyclohexylamines

We report a new strategy for organocatalytic cascade reactions. Accordingly, enamine catalysis, iminium catalysis, and Bronsted acid catalysis can work in concert in a highly enantioselective organocatalytic cascade sequence toward chiral cis-3-substituted cyclohexylamines. We found that an achiral amine in combination with a catalytic amount of a chiral Bronsted acid can accomplish an aldol addition-dehydration-conjugate reduction-reductive amination to provide potential intermediates of pharmaceutically active compounds in good yields and excellent enantioselectivities. Copyright

Synthesis and Application of Imidazole Derivatives: Preparation of Various Diketones from 1,n-Bis(1-methyl-1H-imidazol-2-yl)alkane-1,n-diones

Reaction of 1,n-bis(1-methyl-1H-imidazol-2-yl)alkane-1,n-dione (8) with an excess of Grignard reagent was examined.In the cases of n = 4 and 5, precursors (14) for synthesis of various asymmtric 1,4- and 1,5-diketones (12: R1 R2), respectively, were obtained in good yields by treating 8 with an excess of methylmagnesium iodide in ether followed by trimethylsilylation.In the case of n >/= 8, the two carbonyl groups of 8 were both attacked by the Grignard reagent, and the products (11: R1=R2=CH3) were convertible to symmetrical diketones (12: R1=R2=CH3) in good yields.In cases of n = 6 and 7, the mode of the Grignard reaction was transitional between the two types.Keywords - 2-acyl-1H-imidazole; 1,n-bis(1-methyl-1H-imidazol-2-yl)-1,n-alkanedione; diketone synthesis; asymmetric diketone; symmetric diketone; Grignard reaction; dihydrojasmone; cis-jasmone; muscone; 2-(1-hydroxy-1-alkyl)-1-methyl-1H-imidazole

ON THE SYNTHESIS OF 1,n-DIKETONES USING MONO-SUBSTITUTED DERIVATIVES OF TOSYLMETHYL ISOCYANIDE

A new method is described for the synthesis of symmetrical and unsymmetrical diketones.Particularly good results are obtained in the synthesis of 1,6- and 1,5-diketones.Procedures are reported for 1,2-diketones.The moderate results obtained for 1,4-diketones and the lack of success for 1,3-diketones are discussed.