33356-85-3

Upstream product

• 64141-10-2 1-chloro-4-p-tolyl-but-2ξ-ene 
• 106-99-0 buta-1,3-diene 
• 4294-57-9 para-methylphenylmagnesium bromide 
• 104-87-0 4-methyl-benzaldehyde 
• 627-15-6 1,3-dibromopropene 
• 67-63-0 isopropyl alcohol 
• 15854-64-5 3-chloro-1-p-tolyl-but-2ξ-ene 
• 111-34-2 -butyl vinyl ether 
• 156423-16-4 (E)-1-(2-iodovinyl)-4-methylbenzene 
• 1097191-48-4 1-allyl-2-(4-methylbenzylidene)hydrazine 
• 78-08-0 Triethoxyvinylsilane 
• 60655-80-3 (E)-4-methylstyrenyl bromide 
• 73839-44-8 (Z)-1-[2-bromovinyl]-4-methylbenzene 
• 1560-54-9 allyltriphenylphosphonium bromide 

Downstream Products

• 33356-90-0 2,6-di-p-tolyl-3,6-dihydro-2H-[1,2]oxazine 
• 100036-21-3 3-p-Tolyl-cyclohex-4-ene-1,1,2,2-tetracarbonitrile 
• 100036-07-5 2-p-Tolyl-6,6-bis-trifluoromethyl-cyclohex-3-ene-1,1-dicarbonitrile 
• 54372-58-6 2-(trans-2-p-tolyl-ethenyl)-1,1-dichlor-cyclopropan 
• 1234489-97-4 (3S)-(E)-6,6-diisopropyl-6-[dimethyl(phenyl)siloxy]-3-methyl-1-[4-methylphenyl]hex-1-en-4-yne 
• 1638238-64-8 (E)-2-(4-methylstyryl)-4-phenyl-1-tosyl-2,3-dihydro-1H-pyrrole 

Relevant academic research and scientific papers

Palladium-Catalyzed Asymmetric Hydrosulfonylation of 1,3-Dienes with Sulfonyl Hydrazides

A highly enantio- and regioselective hydrosulfonylation of 1,3-dienes with sulfonyl hydrazides has been realized by using a palladium catalyst containing a monodentate chiral spiro phosphoramidite ligand. The reaction provided an efficient approach to synthetically useful chiral allylic sulfones. Mechanistic studies suggest that the reaction proceeds through the formation of an allyl hydrazine intermediate and subsequent rearrangement to the chiral allylic sulfone product. The transformation of the allyl hydrazine intermediate to the product is the enantioselectivity-determining step.

Asymmetric Counteranion Directed Catalytic Heck/Tsuji-Trost Annulation of Aryl Iodides and 1,3-Dienes

A chiral anion-mediated asymmetric Heck/Tsuji-Trost reaction of aryl iodides and 1,3-dienes is presented. Chiral indoline derivatives could be afforded with remarkably higher yields and enantioselectivities than our previous chiral ligand-based method. Silver carbonate is employed as both base and halide scavenger to ensure fast and recyclable exchange of the catalytic amount of chiral anions. Fast salt metathesis, as well as the acceleration effect of the chiral anion, could both benefit the stereocontrol of the reaction.

Photoinduced Copper-Catalyzed Asymmetric C-O Cross-Coupling

The construction of carbon-heteroatom bonds is one of the most active areas of research in organic chemistry because the function of organic molecules is often derived from the presence of heteroatoms. Although considerable advances have recently been achieved in radical-involved catalytic asymmetric C-N bond formation, there has been little progress in the corresponding C-O bond-forming processes. Here, we describe a photoinduced copper-catalyzed cross-coupling of readily available oxime esters and 1,3-dienes to generate diversely substituted allylic esters with high regio- and enantioselectivity (>75 examples; up to 95% ee). The reaction proceeds at room temperature under excitation by purple light-emitting diodes (LEDs) and features the use of a single, earth-abundant copper-based chiral catalyst as both the photoredox catalyst for radical generation and the source of asymmetric induction in C-O coupling. Combined experimental and density functional theory (DFT) computational studies suggest the formation of π-allylcopper complexes from redox-active oxime esters as bifunctional reagents and 1,3-dienes through a radical-polar crossover process.

Direct 1,2-Dicarbonylation of Alkenes towards 1,4-Diketones via Photocatalysis

1,4-Dicarbonyl compounds are intriguing motifs and versatile precursors in numerous pharmaceutical molecules and bioactive natural compounds. Direct incorporation of two carbonyl groups into a double bond at both ends is straightforward, but also challenging. Represented herein is the first example of 1,2-dicarbonylation of alkenes by photocatalysis. Key to success is that N(n-Bu)4+ not only associates with the alkyl anion to avoid protonation, but also activates the α-keto acid to undergo electrophilic addition. The α-keto acid is employed both for acyl generation and electrophilic addition. By tuning the reductive and electrophilic ability of the acyl precursor, unsymmetric 1,4-dicarbonylation is achieved for the first time. This metal-free, redox-neutral and regioselective 1,2-dicarbonylation of alkenes is executed by a photocatalyst for versatile substrates under extremely mild conditions and shows great potential in biomolecular and drug molecular derivatization.

Ni-Catalyzed Regioselective Hydroarylation of 1-Aryl-1,3-Butadienes with Aryl Halides

An efficient nickel-catalyzed regioselective hydroarylation of 1,3-dienes with aryl halides and a silane has been developed, affording a range of allylic arenes in good to excellent yields under mild conditions. This method exhibits broad substrate scope,

Photoinduced Palladium-Catalyzed Carbofunctionalization of Conjugated Dienes Proceeding via Radical-Polar Crossover Scenario: 1,2-Aminoalkylation and beyond

A photoinduced palladium-catalyzed 1,2-carbofunctionalization of conjugated dienes has been developed. This mild modular approach, which does not require employment of exogeneous photosensitizers and external oxidants, allows for efficient and highly regio- and stereoselective synthesis of a broad range of allylic amines from readily available 1,3-dienes, alkyl iodides, and amines. Employment of O- and C-nucleophiles toward oxyalkylation and dialkylation products was also demonstrated. A putative π-allyl palladium radical-polar crossover path is proposed as a key event in this three-component coupling process. The utility of this protocol is highlighted by its application for derivatization of several amine-containing drugs.

Cu-Catalyzed highly regioselective 1,2-hydrocarboxylation of 1,3-dienes with CO2

A practical copper-catalyzed highly regioselective 1,2-hydrocarboxylation of terminal 1,3-diene with carbon dioxide has been developed. Under mild reaction conditions, this chemistry afforded 2-benzyl-β,γ-unsaturated acid derivatives as products, which are a kind of important unit for bio-active molecules and versatile precursors for organic synthesis, with good functional group tolerance. The key intermediate in this transformation is illustrated by control experiments.

Nickel-catalyzed allyl-allyl coupling reactions between 1,3-dienes and allylboronates

A regiospecific allyl-allyl coupling reaction between 1,3-dienes and allylboronates has been demonstrated under nickel catalysis. Salient features of this method include the earth-abundant metal catalyst, excellent regioselectivity and good functional group tolerance. Notably, even congested allyl substrates can also be applied to this protocol, thus allowing for the rapid preparation of a series of valuable 1,5-dienes. This journal is

Radical-Mediated Heck-Type Alkylation: Stereoconvergent Synthesis of Functionalized Polyenes

The stereospecific synthesis of polyenes is of great synthetic value. Disclosed herein is a new, efficient, stereoconvergent approach for the synthesis of functionalized polyenes via a radical-mediated Heck-type alkylation. The easily accessed Z- and E-mixed alkenes are harnessed as starting material, leading to a unique stereoisomer of polyenes. In addition, the transformation features mild reaction conditions and broad functional group compatibility. A variety of valuable 1,3-dienes and 1,3,5-trienes are afforded in useful yields.

Iron(III)/O2-Mediated Regioselective Oxidative Cleavage of 1-Arylbutadienes to Cinnamaldehydes

A simple, efficient, and environmentally benevolent regioselective oxidative cleavage of 1-arylbutadienes to cinnamaldehydes mediated by iron(III) sulfate/O2 has been developed. The reaction offered good yields and excellent regioselectivity and showed good functional group tolerance (31 examples). The method is important, as few reports with limited substrate scope are available for such excellent oxidative cleavage of conjugated dienes.