67002-62-4

Upstream product

• 123-38-6 propionaldehyde 
• 503071-47-4 diisopropyl-phenethyloxy-silane 
• 100-42-5 styrene 
• 71-23-8 propan-1-ol 
• 74-85-1 ethene 
• 768-32-1 trimethylphenylsilane 
• 14289-65-7 2-(2-propenyloxy)ethylbenzene 
• 122-78-1 phenylacetaldehyde 
• 56576-81-9 phenyl-acetaldehyde dipropylacetal 

Relevant academic research and scientific papers

Oxidative 1,2-Difunctionalization of Ethylene via Gold-Catalyzed Oxyarylation

Under the conditions of oxidative gold catalysis, exposure of ethylene to aryl silanes and alcohols generates products of 1,2-oxyarylation. This provides a rare example of a process that allows catalytic differential 1,2-difunctionalization of this feedstock chemical.

Photocatalytic nucleophilic addition of alcohols to styrenes in Markovnikov and anti-Markovnikov orientation

The nucleophilic addition of methanol and other alcohols to 1,1-diphenylethylene (1) and styrene (6) into the Markovnikov- and anti-Markovnikov-type products was selectively achieved with 1-(N,N-dimethylamino)pyrene (Py) and 1,7-dicyanoperylene-3,4:9,10-tetracarboxylic acid bisimide (PDI) as photoredox catalysts. The regioselectivity was controlled by the photocatalyst. For the reductive mode towards the Markovnikov-type regioselectivity, Py was applied as photocatalyst and triethylamine as electron shuttle. This approach was also used for intramolecular additions. For the oxidative mode towards the anti-Markovnikov-type regioselectivety, PDI was applied together with Ph-SH as additive. Photocatalytic additions of a variety of alcohols gave the corresponding products in good to excellent yields. The proposed photocatalytic electron transfer mechanism was supported by detection of the PDI radical anion as key intermediate and by comparison of two intramolecular reactions with different electron density. Representative mesoflow reactor experiments allowed to significantly shorten the irradiation times and to use sunlight as "green"light source.

Tetra-hydroxy-calix[4]arene derivatives with two P(III) or P(V) units attached at the upper rim

5,17-Bis(diphenylphosphino)-25,26,27,28-tetra-hydroxy-calix[4]arene (2) and the corresponding bis-(phosphine oxide) (3) and bis-(phosphine sulfide) (4) have been synthesized. A single crystal X-ray diffraction study was carried out for bis(phosphine oxide) 3, which revealed a pinched cone conformation for the calixarene core. In the solid state, each calixarene is linked to two other calixarenes via hydrogen bonds involving the phosphoryl groups as well as two of the four hydroxyl groups, thereby generating a supramolecular polymeric structure. Selective formation of chelate complexes from diphosphine 2 failed, probably because of rapid trans annular rotation of the phenoxyl groups that prevents appropriate ligand preorganisation. Upon reaction with appropriate Ru-, Rh-, and Ir-complexes, ligand 2 readily formed dinuclear complexes. One of them, namely the complex [2·{RhCl(1,5-cyclooctadiene)}2] was assessed in the catalytic hydrogenation of linear and cyclic olefins.

Etherification of alkoxydialkylsilanes with carbonyl compounds

A novel method for preparing ethers from alkoxydialkylsilanes and carbonyl compounds through reductive etherification is described. The salient feature in this method is the utilization of internal hydrogen as the hydride source for reducing the oxonium intermediate generated by using the Cl(R)2SiBr[BiBr3/Cl(R)2SiH] catalytic system.