58541-14-3

Upstream product

• 4452-32-8 diethylcyclohexenylphosphate 
• 13170-43-9 (trimethylsilyl)methylmagnesium chloride 
• 822-87-7 2-Chlorocyclohexanone 
• 108-94-1 cyclohexanone 
• 17883-02-2 (ethoxydimethylsilyl)(trimethylsilyl)methane 
• 6651-36-1 1-(Trimethylsilyloxy)cyclohexene 
• 58541-08-5 Phenyl-carbamic acid 1-trimethylsilanylmethyl-cyclohexyl ester 

Downstream Products

• 135312-72-0 1-(2-bromo-1-ethoxypropyl)-2-methylenecyclohexane 
• 121077-75-6 2-Methylene-cyclohexanecarboxylic acid 4-chloro-phenyl ester 
• 100636-52-0 2,2,2-Trichloro-1-(2-methyl-cyclohex-1-enyl)-ethanone 
• 100636-53-1 2,2,2-Trichloro-1-(2-methylene-cyclohexyl)-ethanone 
• 517867-54-8 (1'R,2S,3R)-2-(2'-methylenecyclohexyl)-5-oxotetrahydrofuran-3-carbaldehyde 
• 135312-77-5 1-methylene-2-((E,Z)-1-propenyl)cyclohexane 
• 78426-32-1 2-(hydroxymethyl)-1-methylenecyclohexane 

Relevant academic research and scientific papers

ONE-POT SYNTHESIS OF ALLYLSILANES FROM α-CHLOROCARBONYL COMPOUNDS

The successive treatment of different α-chlorocarbonyl compounds with trimethylsilylmethylmagnesium chloride and lithium powder leads to allylsilanes in a regioselective manner.

Enantioselective Synthesis of α-Allyl Amino Esters via Hydrogen-Bond-Donor Catalysis

We report a chiral-squaramide-catalyzed enantio- and diastereoselective synthesis of α-allyl amino esters. The optimized protocol provides access to N-carbamoyl-protected amino esters via nucleophilic allylation of readily accessible α-chloro glycinates. A variety of useful α-allyl amino esters were prepared, including crotylated products bearing vicinal stereocenters that are inaccessible through enolate alkylation, with high enantioselectivity (up to 97% ee) and diastereoselectivity (>10:1). The reactions display first-order kinetic dependence on both the α-chloro glycinate and the nucleophile, consistent with rate-limiting C-C bond formation. Computational analysis of the uncatalyzed reaction predicts an energetically inaccessible iminium intermediate, and a lower energy concerted SN2 mechanism.

α-Lithioalkoxysilanes: Applications to alkene synthesis

α-Lithioalkoxysilanes [RO(Me2)Si]CH(Li)(X), where R=Me or Et and X=H or SiMe3, react with carbonyl compounds in hydrocarbon solution to produce alkenes in moderate to high yield via Peterson-type reactions. For X=SiMe3, the corresponding vinylsilanes are isolated directly following work-up. The reaction is regiospecific and shows fair stereoselectivity. When the carbonyl substrates are cyclic ketones in six- or seven-membered rings, the products are exocyclic alkenes. For X=H, the initial product is a β-hydroxysilane, which is then efficiently converted to the corresponding terminal alkene by heating with sodium acetate in acetic acid. Both types of α-lithioalkoxysilane reagents are amenable to reaction with enolizable carbonyl compounds.

NICKEL-CATALYZED CROSS-COUPLING OF SILYL ENOL ETHERS WITH GRIGNARD REAGENTS. REGIO- AND STEREOCONTROLLED SYNTHESIS OF OLEFINS

The substitution of the siloxy group in silyl enol ethers with Grignard reagents to form olefins is accomplished by use of nickel acetylacetonate or phosphine-nickel complexes as catalysts, the stereo- and regiochemistry of coupled olefins depending upon the nature of the catalyst and reaction conditions employed.