103584-54-9

Upstream product

• 590-67-0 1-Methylcyclohexanol 
• 140-88-5 ethyl acrylate 
• 931-96-4 1-methyl-3-cyclohexene-1-carboxaldehyde 

Downstream Products

• 98413-34-4 ethyl 4-(1-methylcyclohexyl)-2-oxobutyrate 
• 98413-81-1 2-((R)-5-Carboxymethyl-4-oxo-2,3,4,5-tetrahydro-benzo[b][1,4]thiazepin-3-ylamino)-4-(1-methyl-cyclohexyl)-butyric acid ethyl ester; hydrochloride 
• 98413-58-2 2-((R)-5-tert-Butoxycarbonylmethyl-4-oxo-2,3,4,5-tetrahydro-benzo[b][1,4]thiazepin-3-ylamino)-4-(1-methyl-cyclohexyl)-butyric acid ethyl ester 

Relevant academic research and scientific papers

Oxalates as Activating Groups for Alcohols in Visible Light Photoredox Catalysis: Formation of Quaternary Centers by Redox-Neutral Fragment Coupling

Alkyl oxalates are new bench-stable alcohol-activating groups for radical generation under visible light photoredox conditions. Using these precursors, the first net redox-neutral coupling of tertiary and secondary alcohols with electron-deficient alkenes is achieved.

Radical dehydroxylative alkylation of tertiary alcohols by Ti catalysis

Deoxygenative radical C?C bond-forming reactions of alcohols are a long-standing challenge in synthetic chemistry, and the current methods rely on multistep procedures. Herein, we report a direct dehydroxylative radical alkylation reaction of tertiary alcohols. This new protocol shows the feasibility of generating tertiary carbon radicals from alcohols and offers an approach for the facile and precise construction of all-carbon quaternary centers. The reaction proceeds with a broad substrate scope of alcohols and activated alkenes. It can tolerate a wide range of electrophilic coupling partners, including allylic carboxylates, aryl and vinyl electrophiles, and primary alkyl chlorides/bromides, making the method complementary to the cross-coupling procedures. The method is highly selective for the alkylation of tertiary alcohols, leaving secondary/primary alcohols (benzyl alcohols included) and phenols intact. The synthetic utility of the method is highlighted by its 10-g-scale reaction and the late-stage modification of complex molecules. A combination of experiments and density functional theory calculations establishes a plausible mechanism implicating a tertiary carbon radical generated via Ti-catalyzed homolysis of the C?OH bond.