74272-01-8

Upstream product

• 89-82-7 pulegone 
• 762-72-1 allyl-trimethyl-silane 
• 1371536-96-7 (2R,5R)-5-methyl-2-(2-methylpent-4-en-2-yl)cyclohexanol 
• 106-95-6 allyl bromide 

Downstream Products

• 1371536-94-5 (1S,2S,5R)-5-methyl-2-(2-methylpent-4-en-2-yl)cyclohexanol 
• 1371536-95-6 (1S,2R,5R)-5-methyl-2-(2-methylpent-4-en-2-yl)cyclohexanol 
• 1481650-84-3 (2S,3R,6S)-2-allyl-3-methyl-6-(2-methylpent-4-en-2-yl)cyclohexanone 
• 1371536-70-7 (2R,5R,E)-2-(6-azido-2-methylhex-4-en-2-yl)-5-methylcyclohexanone 
• 880168-93-4 (1'S,4'R)-3-methyl-3-(4'-methyl-2'-oxo-cyclohexyl)-butyraldehyde 
• 1371536-66-1 (2S,5R,E)-2-(6-azido-2-methylhex-4-en-2-yl)-5-methylcyclohexanone 
• 112295-35-9 (2S,5R)-2-(1',1',4'-trimethyl-3'-pentenyl)-5-methylcyclohexanone 
• 880168-95-6 (2S,5R)-2-(trans-1',1'-dimethyl-3'-pentenyl)-5-methylcyclohexanone 
• 880168-94-5 (2S,5R)-2-(cis-1',1'-dimethyl-3'-pentenyl)-5-methylcyclohexanone 

Relevant academic research and scientific papers

Synthetic study of presilphiperfolan-8-ol: Construction of the tricyclo[5.3.1.04,11]undecane framework utilizing intramolecular aldol condensation and mcmurry coupling

The tricyclo[5.3.1.04,11]undecane framework of presilphiperfolan- 8-ol, tricyclic sesquiterpene alcohol was constructed by intramolecular aldol condensation and the McMurry coupling from two types of diketone compounds, which were obtained from (+)-pulegone through a five-step process. This synthetic route does not require the use of any protective groups.

Stereocontrol in a combined allylic azide rearrangement and intramolecular schmidt reaction

Pre-equilibration of an interconverting set of isomeric allylic azides is coupled with an intramolecular Schmidt reaction to afford substituted lactams stereoselectively. The effect of substitution and a preliminary mechanistic study are reported. The syn

Syn- and anti-selective prins cyclizations of δ,ε-unsaturated ketones to 1,3-halohydrins with Lewis acids

Ten acyclic and monocyclic δ,ε-unsaturated ketones, with and without methyl substituents on the double bond, underwent halide-terminated Prins (halo-Prins) cyclizations under anhydrous conditions in the presence of Lewis acids. TiCl4, TiBr4, BCl3, and BBr 3 promoted syn-selective cyclizations to sterically congested chloro- and bromohydrins, while SnCl4, SnBr4, InCl3, ZrCl4, and several other Lewis acids effected highly anti-selective reactions to furnish the corresponding trans halohydrins. The stronger Lewis acids (TiX4 and BX3) favor the syn process that involves axial delivery of a halide ligand. Competition experiments showed that substitution at the δ carbon (methallyl enones) led to increased rates (40-50-fold), while substitution at the ε position (cis and trans crotyl enones) retarded the rate and eroded the selectivity of the cyclizations. The trends in syn vs anti selectivity, reactivity, and effects of different Lewis acidic metal halides are rationalized by competitive reaction pathways proceeding through syn carbocation-halide ion pairs and a higher order transition state that leads to inversion of configuration and formation of trans halohydrins, along with cyclic olefins arising from proton elimination.

Importance of Structure of α,β-Ethylenic Ketones during Their Reductive Coupling Promoted by the TiCl4-Mg Reagent

In most cases, the reductive coupling of α,β-ethylenic ketones by the TiCl4-Mg reagent leads to 1,3,5-trienes and bisallylic pinacols.Some α,β-enones of s-cis configuration, such as (+)-pulegone, show a particular reactivity: formation of dihydro ketones in the presence of tert-butyl alcohol and reductive alkylation with allylic halides or benzyl bromide.Results are accordance with a polymeric structure for the native low-valent titanium species, and in the case of some s-cis-enones, they can be explained by the intervention of a oxametallacyclopentene.