45941-96-6

Upstream product

• 593-71-5 Chloroiodomethane 
• 122-01-0 4-chloro-benzoyl chloride 
• 2788-86-5 4-Chlorostyrene oxide 
• 75-05-8 acetonitrile 
• 29540-84-9 4-chlorophenyl trifluoromethanesulfonate 
• 107-18-6 allyl alcohol 
• 1712-70-5 1-chloro-4-(1-methylethenyl)-benzene 
• 106-39-8 bromochlorobenzene 
• 107-19-7 propargyl alcohol 
• 50-00-0 formaldehyd 
• 89619-10-3 1-(1-bromovinyl)-4-chlorobenzene 

Downstream Products

• 89618-94-0 2-(4-chlorophenyl)prop-2-en-1-yl 4-toluenesulfonate 
• 89619-19-2 2-(4-chlorophenyl)-1-(2,2,2-trifluoroethoxy)prop-2-ene 
• 26717-54-4 β-(4-chlorophenyl)-γ-butyrolactone 
• 89220-51-9 α-bromomethyl-4-chlorostyrene 
• 127876-32-8 <2-(4-chlorophenyl)prop-2-enyl>amine 
• 1447974-53-9 tert-butyl (2-(4-chlorophenyl)allyl)carbamate 
• 89359-16-0 (S)-β-(4-chlorophenyl)-γ-butyrolactone 

Relevant academic research and scientific papers

Palladium-catalyzed allylic C-H oxidation under simple operation and mild conditions

We discovered an effective and simple system (Pd/BQ/air/r.t.) for making allylic alcohols through Pd-catalyzed allylic C-H bond functionalization. This approach exhibits advantages due to its simple operation, mild conditions, and environmentally benign features. By modifying reaction conditions, it can be suitable for preparing unsaturated aldehydes, allylic esters, ethers, and amines.

Copper-Catalyzed Enantiotopic-Group-Selective Allylation of gem-Diborylalkanes

We report a copper-catalyzed enatiotopic-group-selective allylation of gem-diborylalkanes with allyl bromides. The combination of copper(I) bromide and H8-BINOL derived phosphoramidite ligand proved to be the most effective catalytic system to provide various enantioenriched homoallylic boronate esters, containing a boron-substituted stereogenic center that is solely derived from gem-diborylalkanes, in good yields with high enantiomeric ratios under mild conditions. Experimental and theoretical studies have been conducted to elucidate the reaction mechanism, revealing how the enatiotopic-group-selective transmetalation of gem-diborylalkanes with chiral copper complex occurs to generate chiral α-borylalkyl-copper species for the first time. Additional synthetic applications to the synthesis of various chiral building blocks are also included.

Synthesis of Six-Membered Spiro Azacyclic Oxindole Derivatives via a One-Pot Process of Umpolung Allylation/Aza-Prins Cyclization

An unprecedented synthetic approach involving umpolung allylation/aza-Prins cyclization of N-2,2,2-trifluoroethylisatin ketimines is described. The reactions proceed smoothly with allyl bromide in the presence of 1,8-diazabicyclo[5.4.0]undec-7-ene, H2O, and trimethylsilyl bromide; this one-pot protocol allows access to six-membered spiro azacyclic oxindole derivatives in good to excellent yields. Notably, while the general aza-Prins cyclization involves amines and aldehydes, the present synthetic strategy represents the first aza-Prins cyclization that utilizes the umpolung property of N-2,2,2-trifluoroethylisatin ketimines.

Asymmetric Reductive and Alkynylative Heck Bicyclization of Enynes to Access Conformationally Restricted Aza[3.1.0]bicycles

Conformationally restricted azabicycles are becoming increasingly important in medicinal research. Asymmetric Heck bicyclization of enynes proceeds to give medicinally useful aza[3.1.0] and aza[4.1.0] bicycles with excellent enantioselectivity. The key organopalladium species after bicyclization can be trapped by silanes and terminal alkynes.

Enantioselective Synthesis of 4-Allyl Tetrahydroquinolines via Copper(I) Hydride-Catalyzed Hydroallylation of 1,2-Dihydroquinolines

CuCl/(R,R)-Ph-BPE-catalyzed asymmetric hydroallylation of 1,2-dihydroquinolines, prepared from readily available quinolines, was developed. The optically active tetrahydroquinolines (THQs) bearing an allylic functionality at position 4 were obtained in good yields and excellent enantioselectivity. The introduced allylic groups are amenable to diverse transformations, thus offering chances to rapidly expand the THQ libraries.

Palladium-Catalyzed Regioselective Aerobic Allylic C?H Oxygenation: Direct Synthesis of α,β-Unsaturated Aldehydes and Allylic Alcohols

A protocol for the synthesis of α,β-unsaturated aldehydes and allylic alcohols from simple allylic hydrocarbons with water via palladium-catalyzed functionalization of allylic C?H bonds was described. Molecular oxygen is utilized as the sole oxidant in this oxygenation of terminal alkenes. This protocol features good functional group compatibility, broad substrate scope, and high atom- and step-economy. Moreover, the synthetic utility of this method can be highlighted by its application to the synthesis of ibuprofen, which is a highly potent analgesic. (Figure presented.).

Traversing Steric Limitations by Cooperative Lewis Base/Palladium Catalysis: An Enantioselective Synthesis of α-Branched Esters Using 2-Substituted Allyl Electrophiles

Cooperative catalysis enables the direct enantioselective α-allylation of linear prochiral esters with 2-substituted allyl electrophiles. Critical to the successful development of the method was the recognition that metal-centered reactivity and the sourc

Enantioselective bromocyclization of allylic amides catalyzed by BINAP derivatives

A highly enantioselective bromocyclization of allylic amides with N-bromosuccinimide (NBS) was developed with DTBM-BINAP as a catalyst, affording chiral oxazolines with a tetrasubstituted carbon center in high yield with up to 99% ee. By utilizing the bro

N-BuLi/LiCH2CN-mediated one-carbon homologation of aryl epoxides into conjugated allyl alcohols

A series of styrene oxides in the presence of a 1:1 mixture of n-butyllithium (n-BuLi) and lithioacetonitrile (LiCH2CN) in THF are converted into one-carbon homologated allyl alcohols in an unusual regioselective manner.

Solvent-dependent enantiodivergence in the chlorocyclization of unsaturated carbamates

A remarkable solvent-controlled enantiodivergence is seen in the hydroquinidine 1,4-phthalazinediyl diether ((DHQD)2PHAL)-catalyzed chlorocyclization of unsaturated carbamates. Eyring plot analyses of this previously unreported reaction are used to probe and compare the R- and S-selective pathways. In the CHCl3/hexanes solvent system, the pro-R process shows a surprising increase in selectivity with increasing temperature. These studies point to a strongly solvent-dependent entropy-enthalpy balance between the pro-R and pro-S pathways. Two solvents, two enantiomers: Enantiodivergent hydroquinidine 1,4-phthalazinediyl diether ((DHQD) 2PHAL)-catalyzed chlorocyclization of unsaturated carbamates, controlled solely by the choice of solvent, yields oxazolidinones in high enantioselectivity (see scheme; DCDMH=1,3-dichloro-5,5-dimethyl hydantoin). The origin of the observed enantiodivergence is traced back to a solvent-selected entropy-enthalpy balance between pro-R and pro-S pathways that dictates the course of the reaction. Copyright