113365-36-9

Upstream product

• 145279-03-4 1-(tert-butylthio)-2-methyl-1-(trimethylsilyloxy)prop-1-ene 
• 105-07-7 4-cyanobenzaldehyde 
• 77078-44-5 Trimethyl-(2-methyl-1-methylsulfanyl-propenyloxy)-silane 
• 104-88-1 4-chlorobenzaldehyde 
• 359792-06-6 1-(tert-Butyldimethylsiloxy)-1-phenylselanyl-2-methyl-1-propene 
• 619-65-8 4-cyanobenzoic Acid 
• 556-56-9 allyl iodid 
• 17314-40-8 3-Methyl-2-butenyl-trimethylstannane 

Downstream Products

• 105-07-7 4-cyanobenzaldehyde 
• 619-65-8 4-cyanobenzoic Acid 

Relevant academic research and scientific papers

EFFICIENT FORMATION OF PINACOLS FROM ALDEHYDES OR KETONES MEDIATED BY SAMARIUM DIIODIDE

Samarium diiodide is an excellent reagent for aldehyde or ketone coupling.With aromatic aldehydes, reactions are very fast with a complete selectivity versus substituents such as cyano, carbonyl or nitro groups.

Notable sulfur atom effects on the regio- and stereoselective formation of oxetanes in Paterno-Buchi photocycloaddition of aromatic aldehydes with silyl O,S-ketene acetals

Paterno-Buchi photocycloaddition of silyl O,S-ketene acetals (SKA) 1 and aromatic aldehydes 2 was investigated in detail. The photoreaction of aldehydes 2a-d with β,β-dimethyl-O,S-SKA 1a-e has been found to give, regio- (ca. 70/30 to 90/10) and stereoselectively (ca. 70/30 to 90/10), trans-3-siloxyoxetanes 3 independent upon the aldehyde, the substituents SR1 and SIR3, and reaction medium (solvent and salts). The triplet 2- oxatetramethylene 1,4-diradical T-1,4-DR is reasonably proposed as a common intermediate. The regioselectivity is rationalized by (1) the relative stability of 1,4-diradicals and (2) the relative nucleophilicity of sp2- carbons in O,S-SKA. The trans-selectivity is explained by the sulfur atom effects in O,S-SKA 1, which control the approach direction of the electrophilic oxygen of triplet nπ* aldehydes to the nucleophilic alkene. The fast ISC process of the triplet 1-alkylthio-1-siloxy-2-oxatetramethylene 1,4-diradical T-1,4-DR in competition with the bond rotation has been proposed. The substrate-dependent formation of 3fb from E- or Z-1f supports the hypothesis. The S-directed regio- and diastereoselectivity are found for the first time in the present study.

Reductive coupling of aromatic aldehydes promoted by an aqueous TiCl 3/tBuOOH system in alcoholic cosolvents

The tert-butoxyl radical, generated by the aqueous TiIII/TBHP system, abstracts an H atom from alcoholic cosolvents (EtOH, iPrOH), leading to α-hydroxyalkyl radicals that reduce aromatic aldehydes to the corresponding 1,2-diols. The reactivities observed are explained by resonance stabilization of the α-hydroxybenzyl radicals formed in the electron-transfer (ET) process. Good Hammett-type correlations are obtained. Wiley-VCH Verlag GmbH & Co. KGaA, 2007.

Ultrasonic Effects on Electroorganic Processes. Electroreduction of Benzaldehydes on Ultrasound-vibrating Electrodes

Ultrasound-vibrators (stepped horns) themselves were used as cathodes for electroreduction of benzaldehydes.Current efficiency for the reduction and selectivity for the corresponding hydrodimeric products (HD) were increased with increase in ultrasound-oscilating power.

Photocatalytic pinacol C-C coupling and jet fuel precursor production on ZnIn2S4nanosheets

Visible light-driven C-C bond formation has attracted increasing attention recently, thanks to the advance in molecular photosensitizers and organometallic catalysts. Nevertheless, these homogeneous methodologies typically necessitate the utilization of noble metal-based (e.g., Ir, Ru, etc.) photosensitizers. In contrast, solid-state semiconductors represent an attractive alternative but remain less explored for C-C bond-forming reactions driven by visible-light irradiation. Herein, we report that photocatalytic pinacol C-C coupling of benzaldehyde to hydrobenzoin can be achieved on two-dimensional ZnIn2S4 nanosheets upon visible-light irradiation in the presence of a sacrificial electron donor (e.g., triethylamine). We further demonstrate that it is feasible to take advantage of both excited electrons and holes in irradiated ZnIn2S4 for C-C coupling reactions in the absence of any sacrificial reagent if benzyl alcohol is utilized as the starting substrate, maximizing the energy efficiency of photocatalysis and circumventing any byproducts. In this case, industrially important benzoin and deoxybenzoin are formed as the final products. More importantly, by judiciously tuning the photocatalytic conditions, we are able to produce either benzoin or deoxybenzoin with unprecedented high selectivity. The critical species during the photocatalytic process were systematically investigated with various scavengers. Finally, such a heterogeneous photocatalytic pinacol C-C coupling strategy was applied to produce a jet fuel precursor (e.g., hydrofuroin) from biomass-derived furanics (e.g., furfural and furfural alcohol), highlighting the promise of our approach in practical applications.

Visible Light Induced Reduction and Pinacol Coupling of Aldehydes and Ketones Catalyzed by Core/Shell Quantum Dots

We present an efficient and versatile visible light-driven methodology to transform aryl aldehydes and ketones chemoselectively either to alcohols or to pinacol products with CdSe/CdS core/shell quantum dots as photocatalysts. Thiophenols were used as proton and hydrogen atom donors and as hole traps for the excited quantum dots (QDs) in these reactions. The two products can be switched from one to the other simply by changing the amount of thiophenol in the reaction system. The core/shell QD catalysts are highly efficient with a turn over number (TON) larger than 4 × 104 and 4 × 105 for the reduction to alcohol and pinacol formation, respectively, and are very stable so that they can be recycled for at least 10 times in the reactions without significant loss of catalytic activity. The additional advantages of this method include good functional group tolerance, mild reaction conditions, the allowance of selectively reducing aldehydes in the presence of ketones, and easiness for large scale reactions. Reaction mechanisms were studied by quenching experiments and a radical capture experiment, and the reasons for the switchover of the reaction pathways upon the change of reaction conditions are provided.

Application of coumarin dyes for organic photoredox catalysis

Here we report the application of readily prepared and available coumarin dyes for photoredox catalysis, which are able to mimic powerful reductant [Ir(iii)] complexes. Coumarin derivatives 9 and 10 were employed as photoreductants in pinacol coupling and in other reactions, in the presence of Et3N as a sacrificial reducing agent. As the electronic, photophysical, and steric properties of coumarins could be varied, a wide applicability to several classes of photoredox reactions is predicted.

Chemoselective Transformation of Diarylethanones to Arylmethanoic Acids and Diarylmethanones and Mechanistic Insights

The chemoselective transformation of diarylethanones via either aerobic oxidative cleavage to give arylmethanoic acids or tandem aerobic oxidation/benzilic acid rearrangement/decarboxylation to give diarylmethanones has been developed. The transformation is controllable and applicable to a broad spectrum of substrates and affords the desired products in good to excellent yields. Mechanistic insights with control reactions, 1H NMR tracking, and single-crystal X-ray diffraction reveal a complex mechanistic network in which two common intermediates, α-ketohydroperoxide and diarylethanedione, and three plausible pathways are proposed and verified. These pathways are interlinked and can be switched reasonably by changing the reaction conditions. This method enables scalable synthesis and access to a number of valuable compounds, including vitamin B3, diphenic acid, and the nonsteroidal anti-inflammatory drug ketoprofen. The present protocol represents a step forward in exploiting complex mechanistic networks to control reaction pathways, achieving divergent syntheses from the same class of starting materials.

Transition-metal-free and chemoselective NaOtBu-O 2-mediated oxidative cleavage reactions of vic-1,2-diols to carboxylic acids and mechanistic insight into the reaction pathways

A method for efficient oxidative cleavage of vic-1,2-diols using a NaO tBu-O2 system resulted in the formation of carboxylic acids in high yields. The present protocol is an eco-friendly alternative to a conventional transition-metal-based method. This new strategy allows large-scale production with nonchromatographic purification while also suppressing competitive reaction pathway such as benzilic acid rearrangement.

METHOD OF PRODUCING DIOL, POLYDIOL, SECONDARY ALCOHOL OR DIKETONE COMPOUND

The invention is a process of using, as a reducing agent, a 12CaO·7Al2O3 electride containing electrons in a number of 1019 cm-3 or more and 2.3 × 1021 cm-3 or less in its cages to subject a carbonyl compound to reductive coupling in a solvent, thereby synthesizing a diol or polydiol. The invention is also a process of reducing a ketone compound in a solvent, thereby synthesizing a secondary alcohol or diketone compound. According to the process of the invention, it is possible to synthesize a diol or polydiol, or a secondary alcohol or diketone compound through simple operations in a short period without using an expensive and harmful metal hydride or metal salt nor limiting the atmosphere for the synthesis to an inert gas atmosphere as in conventional processes.