72237-38-8

Upstream product

• 72237-37-7 1-Phenyl-3,7-dimethyl-6-octen-1-ol 
• 100-52-7 benzaldehyde 
• 106-72-9 2,6-dimethyl-5-hepten-1-al 
• 106-23-0 3,7-dimethyl-oct-6-enal 
• 100-58-3 phenylmagnesium bromide 

Downstream Products

• 128951-99-5 (1,1-dimethylethyl)dimethyl<(1-phenyl-3,7-dimethyl-1(Z),6-octadienyl)oxy>silane 
• 139585-16-3 (1,1-dimethylethyl)dimethyl<(1-phenyl-3,7-dimethyl-1(E),6-octadienyl)oxy>silane 
• 84099-16-1 C₁₇H₂₅NO₃S 

Relevant academic research and scientific papers

Selective Synthesis of Z-Silyl Enol Ethers via Ni-Catalyzed Remote Functionalization of Ketones

We report a remote functionalization strategy, which allows the Z-selective synthesis of silyl enol ethers of (hetero)aromatic and aliphatic ketones via Ni-catalyzed chain walking from a distant olefin site. The positional selectivity is controlled by the directionality of the chain walk and is independent of thermodynamic preferences of the resulting silyl enol ether. Our mechanistic data indicate that a Ni(I) dimer is formed under these conditions, which serves as a catalyst resting state and, upon reaction with an alkyl bromide, is converted to [Ni(II)-H] as an active chain-walking/functionalization catalyst, ultimately generating a stabilized η3-bound Ni(II) enolate as the key selectivity-controlling intermediate.

N-Heterocyclic Carbene-Catalyzed Decarboxylative Alkylation of Aldehydes

We found that N-heterocyclic carbene catalysis promoted the unprecedented decarboxylative coupling of aryl aldehydes and tertiary or secondary alkyl carboxylic acid-derived redox-active esters to produce aryl alkyl ketones. The mild and transition-metal-free reaction conditions are attractive features of this method. The power of this protocol was demonstrated by the functionalization of pharmaceutical drugs and natural product. A reaction pathway involving single electron transfer from an enolate form of Breslow intermediate to a redox ester followed by recombination of the resultant radical pair to form a carbon-carbon bond is proposed.

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.

α-nitration of ketones via enol silyl ethers. Radical cations as reactive intermediates in thermal and photochemical processes

Highly colored (red) solutions of various enol silyl ethers and tetranitromethane (TNM) are readily bleached to afford good yields of α-nitro ketones in the dark at room temperature or below. Spectral analysis show the red colors to be associated with the intermolecular 1:1 electron donor-acceptor (EDA) complexes between the enol silyl ether and TNM. The formation of similar vividly colored EDA complexes with other electron acceptors (such as chloranil, tetracyanobenzene, tetracyanoquinodimethane, etc.) readily establish enol silyl ethers to be excellent electron donors. The deliberate irradiation of the diagnostic (red) charge-transfer absorption bands of the EDA complexes of enol silyl ethers and TNM at -40 °C affords directly the same α-nitro ketones, under conditions in which the thermal reaction is too slow to compete. A common pathway is discussed in which the electron transfer from the enol silyl ether (ESE) to TNM results in the radical ion triad [ESE?+, NO2?, C(NO2)3-]. A subsequent fast homolytic coupling of the cation radical of the enol silyl ether with NO2? leads to the α-nitro ketones. The use of time-resolved spectroscopy and the disparate behavior of theisomeric enol silyl ethers of α- and β-tetralones as well as of 2-methylcyclohexanone strongly support cation radicals (ESE?+) as the critical intermediate in thermal and photoinduced electron-transfer as described in Schemes 1 and 2, respectively.

Oxidative Cyclization of δ,ε- and ε,ζ-Unsaturated Enol Silyl Ethers and Unsaturated Siloxycyclopropanes

Oxidative cyclization of δ,ε- and ε,ζ-unsaturated enol silyl ethers 4a and 4b with cupric triflate and cuprous oxide or ceric ammonium nitrate and sodium bicarbonate in acetonitrile provides the tricyclic ketones 5a and 5b stereoselectively.These cyclizat

Oxidative Cyclization of δ,ε- and ε,ζ-Unsaturated Enol Silyl Ethers

Oxidative cyclization of δ,ε- and ε,ζ-unsaturated enol silyl ethers of aryl ketones with cupric triflate and cuprous oxide or ceric ammonium nitrate and sodium bicarbonate in acetonitrile provides tricyclic ketones stereoselectively.

Oxidation of Primary and Secondary Alcohols by the Catalysis of Palladium

Saturated and unsaturated alcohols are oxidized to the corresponding ketones in good or excellent yields by using an aryl halide (phenyl bromide or mesityl bromide) as an oxidant and palladium(0) or -(II) as a catalyst (0.6-3 mol percent relative to the alcohol) in the presence of a base (NaH or K2CO3).The similar oxidation of primary alcohols provides the corresponding aldehydes and/or esters.The aldehyde/ester selectivity is correlated to the steric and electronic features of substrates.The procedure is applied to the oxidation of 1-primary,ω-primary diols to lactones.