20850-05-9

Upstream product

• 20432-35-3 3-(4-dimethylamino-phenyl)-propenal 
• 1552-97-2 ethyl (E)-3-(4-(dimethylamino)phenyl)acrylate 
• 100-10-7 4-dimethylamino-benzaldehyde 
• 6203-18-5 p-dimethylaminocinnamaldehyde 
• 1552-97-2 3-[4-(dimethylamino)phenyl]-2-propenoic acid ethyl ester 
• 63511-96-6 methyl 3-(p-dimethylaminophenyl)-2-propenoate 

Downstream Products

• 20432-35-3 3-(4-dimethylamino-phenyl)-propenal 
• 1041954-90-8 (E)-4-(3-chloroprop-1-enyl)-N,N-dimethylbenzenamine 
• 6203-18-5 p-dimethylaminocinnamaldehyde 
• 5339-02-6 (E)-N,N-dimethyl-4-(non-1-en-1-yl)aniline 
• 2077-50-1 (E)-N,N-dimethyl-4-(prop-1-en-1-yl)aniline 
• 1451369-20-2 (R)-2-((E)-3-(4-(N,N-dimethylamino)phenyl)prop-2-en-1-yl)cyclohexanone 

Relevant academic research and scientific papers

Hydroxyl Radicals via Collision-Induced Dissociation of Trimethylammonium Benzyl Alcohols

The hydroxyl radical is a well known reactive oxygen species important for interstellar, atmospheric, and combustion chemistry in addition to multiple biochemical processes. Although there are many methods to generate the hydroxyl radical, most of these are inorganic based, with only a few originating from organic precursor molecules. Reported herein is the observation that trimethylammonium benzyl alcohols and their corresponding deuterated isotopologues act as a good source of hydroxyl and deuteroxyl radicals in the gas-phase under collision-induced dissociation (CID) conditions. Attempts to replicate this chemistry in the condensed phase are described.

Palladium-Catalyzed Allyl-Allyl Reductive Coupling of Allylamines or Allylic Alcohols with H2as Sole Reductant

Catalytic carbon-carbon bond formation building on reductive coupling is a powerful method for the preparation of organic compounds. The identification of environmentally benign reductants is key for establishing an efficient reductive coupling reaction. Herein an efficient strategy enabling H2 as the sole reductant for the palladium-catalyzed allyl-allyl reductive coupling reaction is described. A wide range of allylamines and allylic alcohols as well as allylic ethers proceed smoothly to deliver the C-C coupling products under 1 atm of H2. Kinetic studies suggested that the dinuclear palladium species was involved in the catalytic cycle.

Preparation method of alpha,beta-unsaturated alcohol and/or alpha,beta-saturated alcohol

The invention belongs to the technical field of pharmaceutical chemical synthesis, and discloses a preparation method of alpha,beta-unsaturated alcohol and/or alpha,beta-saturated alcohol. The preparation method comprises the following steps: using alpha,beta-unsaturated aldehyde as a raw material and iridium as a catalyst, adding a solvent and a hydrogen source, stirring the obtained solution fora reaction in an air atmosphere at 25-100 DEG C, performing cooling after completion of the reaction, performing extraction on the obtained reaction solution by using ethyl acetate, removing the solvent under reduced pressure so as to obtain a crude product, and performing purification through column chromatography so as to obtain the alpha,beta-unsaturated alcohol and/or alpha,beta-saturated alcohol. The method with high chemical selectivity is adopted to synthesize the alpha,beta-unsaturated alcohol and alpha,beta-saturated alcohol, the synthesis method is simple and easy, has mild reactionconditions, wide adaptability to the substrate, a high product yield and good industrial application prospects.

Highly pH-Dependent Chemoselective Transfer Hydrogenation of α,β-Unsaturated Aldehydes in Water

The pH-dependent selective Ir-catalyzed hydrogenation of α,β-unsaturated aldehydes was realized in water. Using HCOOH as the hydride donor at low pH, the unsaturated alcohol products were obtained exclusively, while the saturated alcohol products were formed preferentially by employing HCOONa as the hydride donor at high pH. A wide range of functional groups including electron-rich as well as electron-poor substituents on the aryl group of α,β-unsaturated aldehydes can be tolerated, affording the corresponding products in excellent yields with high TOF values. High selectivity and yields were also observed for α,β-unsaturated aldehydes with aliphatic substituents. Our mechanistic investigations indicate that the pH value is critical to the chemoselectivity.

Synthesis of Allylsilanes via Nickel-Catalyzed Cross-Coupling of Silicon Nucleophiles with Allyl Alcohols

NiCl2(PMe3)2-catalyzed reaction of allyl alcohols with silylzinc reagents, including PhMe2SiZnCl, Ph2MeSiZnCl, and Ph3SiZnCl, was performed, achieving allylsilanes in high yields. Aryl- and heteroaryl-substituted allyl alcohols, (E)-3-arylprop-2-en-1-ols, 1-aryl-prop-2-en-1-ols, and (E)-1-phenylpent-1-en-3-ol can be employed in the transformation. A range of functional groups as well as heteroaryl groups were tolerated. Reaction exhibited high regioselectivity and E/Z-selectivity when 1- or 3-aryl-substituted allyl alcohols were used as the substrates. Reaction of chiral allyl alcohol, (S,E)-1-phenylpent-1-en-3-ol, yielded a configuration-inversion product (R,E)-dimethyl(phenyl)(1-phenylpent-1-en-3-yl)silane.

Homogeneous Hydrogenation with a Cobalt/Tetraphosphine Catalyst: A Superior Hydride Donor for Polar Double Bonds and N-Heteroarenes

The development of catalysts based on earth abundant metals in place of noble metals is becoming a central topic of catalysis. We herein report a cobalt/tetraphosphine complex-catalyzed homogeneous hydrogenation of polar unsaturated compounds using an air- and moisture-stable and scalable precatalyst. By activation with potassium hydroxide, this cobalt system shows both high efficiency (up to 24 000 TON and 12 000 h-1 TOF) and excellent chemoselectivities with various aldehydes, ketones, imines, and even N-heteroarenes. The preference for 1,2-reduction over 1,4-reduction makes this method an efficient way to prepare allylic alcohols and amines. Meanwhile, efficient hydrogenation of the challenging N-heteroarenes is also furnished with excellent functional group tolerance. Mechanistic studies and control experiments demonstrated that a CoIH complex functions as a strong hydride donor in the catalytic cycle. Each cobalt intermediate on the catalytic cycle was characterized, and a plausible outer-sphere mechanism was proposed. Noteworthy, external inorganic base plays multiple roles in this reaction and functions in almost every step of the catalytic cycle.

Straightforward chemo- and stereoselective fluorocyclopropanation of allylic alcohols: Exploiting the electrophilic nature of the not so elusive fluoroiodomethyllithium

An unprecedented direct fluorocyclopropanation of allylic alcohols is reported. This simple method involves the not so elusive fluoroiodomethyllithium, a carbenoidic intermediate that under the developed conditions discloses its electrophilic nature. Gratifyingly, the reaction turned out to be highly chemo- and stereoselective, and DFT calculations provided insights into the structure and nature of this new type of carbenoid.

Rhodium-Catalyzed Synthesis of α,β-Unsaturated Ketones through Sequential C-C Coupling and Redox Isomerization

A novel Rh(I)-catalyzed sequential C-C coupling and redox isomerization between allylic alcohols and 1,3-dienes has been accomplished. This versatile protocol provides expeditious access to a broad range of polysubstituted α,β-unsaturated ketones with excellent atom economy and regioselectivity.

Gold-Catalyzed [2,3]-Sigmatropic Rearrangement: Reaction of Aryl Allyl Alcohols with Diazo Compounds

A gold-catalyzed [2,3]-sigmatropic rearrangement reaction has been developed. The intermolecular rearrangement occurs between in situ generated donor-acceptor gold-carbenes and cinnamyl alcohols via tandem oxonium ylide formation. The desired rearranged product has been accomplished selectively over more conventional O-H insertion, cyclopropanation, cycloaddition, and C-H functionalization products under mild, open-air conditions. The scope of the work has been illustrated by synthesizing a new class of substrates that can be used for constructing complex molecular targets.

Direct asymmetric α-allylation of ketones with allylic alcohols Via Pd/enamine cooperative function

Direct asymmetric α-allylation of ketones with allylic alcohols is described. The combination of palladium with a new phosphine ligand bearing a chiral proline moiety promoted the reaction to afford the corresponding α-allylated ketones in moderate yield and enantioselectivity.