940286-90-8

Upstream product

• 108-86-1 bromobenzene 
• 922-65-6 divinylcarbinol 
• 104-53-0 3-phenyl-propionaldehyde 
• 37630-43-6 (Z)-1-(methylsulfonyl)-2-phenylethene 
• 1779-49-3 Methyltriphenylphosphonium bromide 
• 100-52-7 benzaldehyde 
• 62510-08-1 (E)-1,5-diphenyl-1-penten-3-one 
• 2550-26-7 4-Phenyl-2-butanone 
• 100-42-5 styrene 
• 7436-90-0 2,2-dibromostyrene 
• 588-72-7 [(E)-2-bromoethenyl]benzene 

Downstream Products

• 1044744-63-9 (E)-4-(1,5-diphenylpent-1-en-3-yl)-2-methylphenol 
• 123200-69-1 (E)-pent-1-ene-1,3,5-triyltribenzene 
• 1246896-00-3 (S,E)-1,5-diphenylpent-1-en-3-ol 

Relevant academic research and scientific papers

Electrochemical Nozaki-Hiyama-Kishi Coupling: Scope, Applications, and Mechanism

One of the most oft-employed methods for C-C bond formation involving the coupling of vinyl-halides with aldehydes catalyzed by Ni and Cr (Nozaki-Hiyama-Kishi, NHK) has been rendered more practical using an electroreductive manifold. Although early studies pointed to the feasibility of such a process, those precedents were never applied by others due to cumbersome setups and limited scope. Here we show that a carefully optimized electroreductive procedure can enable a more sustainable approach to NHK, even in an asymmetric fashion on highly complex medicinally relevant systems. The e-NHK can even enable non-canonical substrate classes, such as redox-active esters, to participate with low loadings of Cr when conventional chemical techniques fail. A combination of detailed kinetics, cyclic voltammetry, and in situ UV-vis spectroelectrochemistry of these processes illuminates the subtle features of this mechanistically intricate process.

Br?nsted Acid Enabled Nickel-Catalyzed Hydroalkenylation of Aldehydes with Styrene and its Derivatives

A Br?nsted acid enabled nickel-catalyzed hydroalkenylation of aldehydes and styrene derivatives has been developed. The Br?nsted acid acts as a proton shuttle to transfer a proton from the alkene to the aldehyde, thereby leading to an economical and byproduct-free coupling. A series of synthetically useful allylic alcohols were obtained through one-step reactions from readily available styrene derivatives and aliphatic aldehydes in up to 88 % yield and with high linear selectivity.

Kinetic Resolution of Racemic Allylic Alcohols by Catalytic Asymmetric Substitution of the OH Group with Monosubstituted Hydrazines

A new strategy has been established for the kinetic resolution of racemic allylic alcohols through a palladium/sulfonyl-hydrazide-catalyzed asymmetric OH-substitution under mild conditions. In the presence of 1 mol % [Pd(allyl)Cl]2, 4 mol % (S)-SegPhos, and 10 mol % 2,5-dichlorobenzenesulfonyl hydrazide, a range of racemic allylic alcohols were smoothly resolved with selectivity factors of more than 400 through an asymmetric allylic alkylation of monosubstituted hydrazines under air at room temperature. Importantly, this kinetic resolution process provided various allylic alcohols and allylic hydrazine derivatives with high enantiopurity.

Convergent synthesis of conjugated 1,2-disubstituted E-allylic alcohols from two aldehydes and methylenetriphenylphosphorane

β-Lithiooxyphosphonium ylides, made in situ from an aldehyde and methylenetriphenylphosphorane, react with a second aldehyde to form E-allylic alcohols. α-Branching and α,β-unsaturation in the second aldehyde, together with the lack of further substitution on the phosphorane carbon play important roles in selectivity. A range of these aldehydes, in addition to aromatic aldehydes as the second aldehyde also provided synthetically useful access to E-allylic alcohols.

Titanocene(II)-promoted stereoselective alkenylation utilizing (Z)-alkenyl sulfones

(Chemical Equation Presented) The stereoselective alkenylation of unsaturated compounds by means of a (Z)-alkenyl sulfone-titanocene-(II) system is described. Treatment of alkynes and (Z)-alkenyl methyl sulfones with the titanocene(II) reagent Cp2Ti[P(OEt)3]2 produced conjugated dienes. This alkenylation system is also applicable to polar C=O bonds; the simple mixing of carbonyl compounds, (Z)-alkenyl methyl sulfones, and the titanocene-(II) reagent formed allylic alcohols. The advantages of alkenylation are that it requires no prepreparation of the alkenylmetal reagent and that it proceeds with complete stereoselectivity.

Development of an anomalous heck reaction: Skeletal rearrangement of divinyl and enyne carbinols

(Chemical Equation Presented) A general set of conditions that achieves the union of aryl halides and divinyl or enyne carbinols to afford tri- or tetrasubstituted olefins in good yields (up to 83%) is described. The mechanism by which this proceeds is believed to involve the intermediacy of a cyclopropanol, followed by a novel skeletal reorganization. The ability to suppress β-hydride elimination of organopalladium intermediates appears to be critical to the success of these processes.