94227-04-0

Upstream product

• 96-34-4 methyl chloroacetate 
• 768-03-6 Phenyl vinyl ketone 
• 2190-48-9 3-chloro-3-methyl-1-butene 
• 503-60-6 3,3-dimethyl-allyl chloride 
• 30316-02-0 6-bromo-2-methyl-hex-2-ene 
• 98-88-4 benzoyl chloride 
• 861216-48-0 tert-butyl 2-methylbut-3-en-2-yl carbonate 
• 29526-96-3 1-phenylcyclopropan-1-ol 
• 591208-90-1 6-methyl-1-phenyl-5-penten-1-ol 
• 98-86-2 acetophenone 
• 2270-59-9 1-bromo-4-methylpent-3-ene 
• 13466-32-5 acetophenone dimethylhydrazone 
• 1393823-80-7 2-benzhydryl-3-(5-methylhex-4''-en-1''-yl)-3-phenyl-1,2-oxaziridine 
• 1393823-59-0 2-cyclohexyl-3-(5-methylhex-4'-en-1'-yl)-3-phenyl-1,2-oxaziridine 

Downstream Products

• 1393749-81-9 4-hydroxy-6-methyl-1-phenylhept-5-en-1-one 
• 5350-71-0 dibenzhydryl-amine 
• 1026079-41-3 2-(5-methyl-4-hexenyl)-2-phenyl-oxirane 
• 591208-90-1 6-methyl-1-phenyl-5-penten-1-ol 

Relevant academic research and scientific papers

Nickel-Catalyzed Ring-Opening Allylation of Cyclopropanols via Homoenolate

We report herein a nickel-catalyzed ring-opening allylation of cyclopropanols with allylic carbonates that occurs under mild and neutral conditions. The reaction displays linear selectivity for both linear and branched acyclic allylic carbonates and is also applicable to cyclic allylic carbonates, affording a variety of δ,?-unsaturated ketones in moderate to good yields. Mechanistic experiments are in accord with a catalytic cycle involving decarboxylative oxidative addition of allylic carbonate to Ni(0), alkoxide exchange with cyclopropanol, cyclopropoxide-to-homoenolate conversion on Ni(II), and C-C reductive elimination.

Visible-Light-Promoted Oxidative [4 + 2] Cycloadditions of Aryl Silyl Enol Ethers

Visible-light-promoted oxidative [4 + 2] cycloadditions of μ,3-unsaturated silyl enol ethers have been developed to efficiently and diastereoselectively construct polycyclic skeletons under mild conditions. The diastereoselectivities were dependent on the stereoconfiguration of silyl enol ether, substitutions on the link, as well as electric properties of substitutions on aryl rings. The intermediates could be trapped by TEMPO, oxygen or methanol. Mechanistic studies indicated the reaction was initiated by one-electron oxidation of the silyl enol ether.

Cis-2,6-Bis-(methanolate)-piperidine oxovanadium(V) complexes as catalysts for oxidative alkenol cyclization by tert-butyl hydroperoxide

cis-2,6-Bis-(methanolate)-piperidine oxovanadium(V) complexes are Lewis acids able to catalyze oxidative cyclization of alkenols by tert-butyl hydroperoxide (TBHP). Terminal dimethyl-substituted (prenyl-type) 4-pentenols bearing an alkyl or a phenyl group in position 1 afford under such conditions 2,5-cis-derivatives of 2-(tetrahydrofuran-2-yl)-2-propanol as major and tetrahydropyran-3-ols as minor products (four examples). Oxidizing 1-phenyl-6-methylhept-5-en-1-ol yields a 75/25-mixture of the derived 2-(tetrahydropyran-2-yl)-2-propanol and an oxepan-3-ol, whereas 2-propenols give epoxides in up to 94% yield. Epoxidizing geraniol by TBHP in the presence of a vanadium catalyst prepared from (2S,6R)-2-diphenylmethanol-6- hydroxymethylpiperidine occurs enantioselectively. Highfield shifts of vanadium-51 resonances upon adding alkyl hydroperoxides to solutions of cis-2,6-bis-(methanolate)-piperidine vanadium(V) complexes point to vanadium(V) tert-butyl peroxy complex formation as key step for activating peroxides.

Copper-catalyzed oxaziridine-mediated oxidation of C-H bonds

The highly regio- and chemoselective oxidation of activated C-H bonds has been observed via copper-catalyzed reactions of oxaziridines. The oxidation proceeded with a variety of substrates, primarily comprising allylic and benzylic examples, as well as one example of an otherwise unactivated tertiary C-H bond. The mechanism of the reaction is proposed to involve single-electron transfer to the oxaziridines to generate a copper-bound radical anion, followed by hydrogen atom abstraction and collapse to products, with regeneration of the catalyst by a final single-electron transfer event. The involvement of allylic radical intermediates was supported by a radical-trapping experiment with TEMPO.

Preparation and Reactivities of (η3-1- and 2-Trimethylsiloxyallyl)Fe(CO2)NO Complexes. Intermediates Functioning as Equivalents of β- and α-Acyl Carbocations and Acyl Carbanions

(η3-1- and 2-Trimethylsiloxyallyl)Fe(CO)2NO complexes were prepared by the reaction of the corresponding siloxyallylic halides with Bu4N.These complexes reacted with both of carbon nucleophiles and carbon electrophiles preferentially at the less hindered sites of the allylic ligands.In these reactions, (η3-1-trimethylsiloxyallyl)Fe(CO)2NO complexes served as synthetically equivalent synthons for both of β-acyl carbocations and β-acyl carbanions and (η3-2-trimethylsiloxyallyl)Fe(CO)2NO complexes as both of α-acyl carbocations and α-acyl carbanions.The stereochemical courses of the reactions are described.