50795-93-2

Upstream product

• 3792-53-8 2-methyl-5-(prop-1-en-2-yl)cyclohexanone 
• 5524-05-0 (-)-dihydrocarvone 
• 75276-18-5 (2S,5S)-5-(1-Hydroperoxy-1-methoxy-ethyl)-2-methyl-cyclohexanone 
• 148154-91-0 4-acetyl-1,2-epoxy-1-methylcyclohexane 
• 6610-21-5 6-methylcyclohex-2-en-1-one 
• 54793-88-3 (1R)-2-oxo-bornanoic acid-⁽⁸⁾-chloride 
• 10334-07-3 (1R)-trans-Isoketopinic acid 
• 150760-93-3 2-methyl-5-(3-methyl-<1.2.4>trioxolan-3-yl)-cyclohexanone 
• 71785-79-0 2-Methyl-5-(α-ethoxyvinyl)-cyclohexanon 
• 623-11-0 1-methyl-4-nitrosobenzene 

Downstream Products

• 102448-04-4 5-[1-(2,4-dinitro-phenylhydrazono)-ethyl]-2-methyl-cyclohexanone-(2,4-dinitro-phenylhydrazone) 
• 1266614-98-5 C₁₉H₃₄Si₂ 

Relevant academic research and scientific papers

Ozonolysis in solvent/water mixtures: Direct conversion of alkenes to aldehydes and ketones

(Chemical Equation Presented) Ozonolysis of alkenes in the presence of solubilized water results in the direct formation of aldehydes and/or ketones, avoiding the need to isolate or decompose ozonides.

Complementary catalytic strategies to access α-chiral aldehydes

The present article summarizes the development of two novel and complementary catalytic methods to access α-chiral aldehydes. A C1-symmetric chiral (P,N) ligand with a structure derived from the ubiquitous binepine scaffold has been specifically designed for the Pd-catalyzed α arylation of aldehydes to access indane derivatives with a well-defined quaternary stereocenter in high yields and excellent enantioselectivities. In addition, a dinuclear palladium hydride catalyst has been synthesized for the isomerization of terminal and trisubstituted epoxides into aldehydes and ketones respectively. Combined experimental and theoretical investigations pointed to an unprecedented 'epoxide-opening/hydride-transfer' sequence. The mechanism also features two distinct enantio-determining steps in the kinetic resolution of racemic epoxides. Schweizerische Chemische Gesellschaft.

Pyridine is an organocatalyst for the reductive ozonolysis of alkenes

Whereas the cleavage of alkenes by ozone typically generates peroxide intermediates that must be decomposed in an accompanying step, ozonolysis in the presence of pyridine directly generates ketones or aldehydes through a process that neither consumes pyridine nor generates any detectable peroxides. The reaction is hypothesized to involve nucleophile-promoted fragmentation of carbonyl oxides via formation of zwitterionic peroxyacetals.

'Reductive ozonolysis' via a new fragmentation of carbonyl oxides

This account describes the development of methodologies for 'reductive' ozonolysis, the direct ozonolytic conversion of alkenes into carbonyl groups without the intermediacy of 1,2,4-trioxolanes (ozonides). Ozonolysis of alkenes in the presence of DMSO produces a mixture of aldehyde and ozonide. The combination of DMSO and Et3N results in improved yields of carbonyls but still leaves unacceptable levels of residual ozonides; similar results are obtained using secondary or tertiary amines in the absence of DMSO. The influence of amines is believed to result from conversion to the corresponding N-oxides; ozonolysis in the presence of amine N-oxides efficiently suppresses ozonide formation, generating high yields of aldehydes. The reactions with amine oxides are hypothesized to involve an unprecedented trapping of carbonyl oxides to generate a zwitterionic adduct, which fragments to produce the desired carbonyl group, an amine, and 1O2.

Magnesium/Methanol: An Effective Reducing Agent for Peroxides

Magnesium in methanol is an effective reagent for the chemoselective reduction of peroxides, including ozonides. Mg/MeOH is significantly more reactive than Me2S or PPh3 and somewhat more reactive than Zn/HOAc.

The mechanistic study and synthetic applications of the base treatment in the ozonolytic reactions

The E1cb mechanism is the overwhelming process in the reaction of bases and ozonides. As a quenching agent in the ozonolysis of a variety of alkenes, the reactions involving triethylamine often gave better yields and proceeded faster than those involving methyl sulfide. On the other hand, in the presence of 4 A molecular sieves, the secondary amines reacted with mono- and 1,1-di-substituted ozonides to afford the reductive amination products in high yields. The formation of ammonium formate in the reaction mixture also supported the E1cb mechanism in the reaction of ozonide and amine.

A convenient and efficient workup of ozonolysis reactions using triethylamine

Comparisons were made between triethylamine and methyl sulfide for their use as a quenching agent in the ozonolysis of a variety of alkenes. The reactions involving triethylamine often gave better yields and proceeded faster than those of involving methyl sulfide. The role of triethylamine played as base instead of reducing agent in the reaction.

CRIEGEE REARRANGEMENT OF α-ALKOXY HYDROPEROXIDES. A SYNTHESIS OF ESTERS AND LACTONES THAT COMPLEMENTS THE BAEYER-VILLIGER OXIDATION OF KETONES

α-Alkoxy hydroperoxides undergo Criegee rearrangement upon treatment with (CH3CO)2O to provide esters or lactones.

Copper 'ate' complexes of α-ethoxyvinyl-lithium: Reagents for coupling and 1,4 addition of a masked acyl anion

Stoicheiometric and mixed organocuprate reagents have been prepared from α-ethoxyvinyl-lithium and undergo ready conjugate addition and coupling reactions.