53783-57-6

Upstream product

• 18365-42-9 α-chloro-cinnamaldehyde 
• 507-40-4 tert-butylhypochlorite 
• 4407-36-7 (2E)-3-phenyl-2-propen-1-ol 
• 3234-51-3 1,1-dibromo-2-phenylcyclopropane 
• 1719-19-3 2-Methyl-4-phenyl-3-butyn-2-ol 
• 104-54-1 3-Phenylpropenol 
• 67-56-1 methanol 
• 1483-82-5 phenylethynyl chloride 

Downstream Products

• 53834-50-7 (Z)-1,2-dichloro-3-phenyl-2-propene 
• 673-32-5 1-Phenylprop-1-yne 
• 2327-99-3 1-phenylpropadiene 
• 13099-50-8 2-methyl-1-phenyl-1-propene, β,β-dimethylstyrene 
• 691006-92-5 C₁₁H₁₃Cl 
• 1616877-91-8 (E)-N-(5-(2-chloro-3-phenylallyl)quinolin-8-yl)pivalamide 

Relevant academic research and scientific papers

Hf-MOF catalyzed Meerwein?Ponndorf?Verley (MPV) reduction reaction: Insight into reaction mechanism

Hf-MOF-808 exhibits excellent activity and specific selectivity on the hydrogenation of carbonyl compounds via a hydrogen transfer strategy. Its superior activity than other Hf-MOFs is attributed to its poor crystallinity, defects and large specific surface area, thereby containing more Lewis acid-base sites which promote this reaction. Density functional theory (DFT) computations are performed to explore the catalytic mechanism. The results indicate that alcohol and ketone fill the defects of Hf-MOF to form a six-membered ring transition state (TS) complex, in which Hf as the center of Lewis stearic acid coordinates with the oxygen of the substrate molecule, thus effectively promoting hydrogen transfer process. Other reactive groups, such as –NO2, C = C, -CN, of inadequate hardness or large steric hindrance are difficult to coordinate with Hf, thus weakening their catalytic effect, which explains the specific selectivity Hf-MOF-808 for reducing the carbonyl group.

Visible Light-Enabled sp3-C?H Functionalization with Chloro- and Bromoalkynes: Chemoselective Route to Vinylchlorides or Alkynes

An unprecedented direct atom-economic chemo- and regioselective hydroalkylation of chloroalkynes and an sp3-C?H alkynylation of bromoalkynes was achieved. The reaction partners are unfunctionalized ethers, alcohols, amides, and even non-activated hydrocarbons. We found that a household fluorescent bulb was able to excite a diaryl ketone, which then selectively abstracts a H-atom from an sp3-C?H bond. The product of a formal alkyne insertion into the sp3-C?H bond was obtained with chloroalkynes, providing valuable vinyl chlorides. The photo-organocatalytic hydrogen atom transfer strategy gives rise to a broad range of diversely functionalized olefins. When bromoalkynes are applied in the presence of a base, a chemoselectivity switch to an alkynylation is observed. This reaction can even be performed for the alkynylation of unactivated sp3-C?H bonds, in this case with a preference of the more substituted carbon. Accompanying quantum chemical calculations indicate a vinyl radical intermediate with pronounced linear coordination of the carbon radical center, thus enabling the formation of both diastereoisomers after H-atom abstraction, suggesting that the (Z)-diastereoisomer is preferred, which supports the experimentally observed (E/Z)-distribution.

Convenient in situ generation of various dichlorinating agents from oxone and chloride: Diastereoselective dichlorination of allylic and homoallylic alcohol derivatives

A safe and convenient protocol was developed for in situ generation of various dichlorinating agents (cf. Cl2, NCl3, Et 4NCl3, ArICl2) from oxone and chloride. The synthetic utility of this protocol was demonstrated by diastereoselective dichlorination of a series of allylic and homoallylic alcohol derivatives with excellent yields and diastereoselectivity. The Royal Society of Chemistry 2013.

Meerwein-Ponndorf-Verley alkynylation of aldehydes: Essential modification of aluminium alkoxides for rate acceleration and asymmetric synthesis

A novel carbonyl alkynylation has been accomplished based on utilization of the Meerwein-Ponndorf-Verley (MPV) reaction system. The success of the MPV alkynylation crucially depends on the discovery of the remarkable ligand acceleration effect of 2,2′-biphenol. For example, the alkynylation of chloral (2c) with the aluminium alkoxide 6 (R = Ph), prepared in situ from Me3Al, 2,2′-biphenol and 2-methyl-4-phenyl-3-butyn-2-ol (1a) as an alkynyl source, proceeded smoothly in CH2Cl2 at room temperature to give the desired propargyl alcohol 3ca in almost quantitative yield after 5 h stirring. The characteristic feature of this new transformation involving no metal alkynides can be visualized by the fact that the alkynyl group bearing keto carbonyl was transferred successfully to aldehyde carbonyl without any side reactions on keto carbonyl. Although the use of (S)-1,1′-bi-2-naphthol and its simple analogues was found to be unsuitable for inducing asymmetry in this reaction, design of new chiral biphenols bearing a certain flexibility of the biphenyl axis led to satisfactory results in terms of enantioselectivity as well as reactivity.

Reduction of α-Chlorocarbonyl Compounds by the Tributyltin Hydride-Phosphine Oxide Combined System. Chemoselective Reduction of the Carbonyl Group

α-Chlorocarbonyl compounds undergo selective reduction at the carbonyl group with tributyltin hydride-phosphine oxide combined systems to yield chlorohydrins.