56644-04-3

Upstream product

• 21087-29-6 trans-3-phenylprop-2-enyl chloride 
• 762-73-2 trimethyl(allyl)stannane 
• 3052-45-7 allyllithium 
• 592-42-7 1,5-Hexadien 
• 100-56-1 phenylmercury(II) chloride 
• 16212-07-0 trans-cinnamyl phenyl sulfone 
• 4392-24-9 Cinnamyl bromide 
• 762-72-1 allyl-trimethyl-silane 
• 40595-34-4 (E)-trimethyl(3-phenylallyl)silane 
• 100-42-5 styrene 
• 7051-34-5 cyclopropylcarbinyl bromide 
• 75-11-6 diiodomethane 
• 588-72-7 [(E)-2-bromoethenyl]benzene 
• 106-95-6 allyl bromide 

Downstream Products

• 122800-39-9 Acetic acid (2E,5E)-6-phenyl-hexa-2,5-dienyl ester 
• 122800-38-8 Acetic acid 3-[1-phenyl-meth-(E)-ylidene]-cyclopentyl ester 
• 144121-60-8 1-phenylhex-5-en-1-ol 

Relevant academic research and scientific papers

Mercury in Organic Chemistry. 28. Synthesis of (?-Allyl)palladium Compounds by Remote Palladium Migration

A variety of organomercurials react regioselectively with 1,4-, 1,5-, 1,6-, and 1,7-dienes and Li2PdCl4 to form good yields of (?-allyl)palladium compounds.These reactions apparently proceed by organopalladium addition to one of the diene double bonds and subsequent palladium migration.

Arylboronic Acid Catalyzed C-Alkylation and Allylation Reactions Using Benzylic Alcohols

The arylboronic acid catalyzed dehydrative C-alkylation of 1,3-diketones and 1,3-ketoesters using secondary benzylic alcohols as the electrophile is reported, forming new C-C bonds (19 examples, up to 98% yield) with the release of water as the only byproduct. The process is also applicable to the allylation of benzylic alcohols using allyltrimethylsilane as the nucleophile (12 examples, up to 96% yield).

Synthesis method of 1, 5-diene derivative

The invention belongs to the technical field of pharmaceutical and chemical intermediates and related chemistry, and provides a preparation method of a 1, 5-diene derivative. The method comprises thefollowing steps: taking aryl substituted propyne and allyl boron ester as reaction raw materials, adopting 2-10mol% of a palladium catalyst, adding 2mol%-20mol% of acid and 100mol%-300mol% of alcoholas additives, and performing heating and stirring in an organic solvent for a certain period of time to generate the 1, 5-diene compound. The method disclosed by the invention has the beneficial effects that the operation is simple and convenient, the condition is mild, the method is environment-friendly, the catalyst can be recycled, the possibility of industrialization is realized, and the 1, 5-diene compound is obtained at a relatively high yield; and the 1, 5-diene compound synthesized by the method can be further functionalized to obtain various compounds, and is applied to development and research of natural products, functional materials and fine chemicals.

Nickel-Catalyzed Homo- And Cross-Coupling of Allyl Alcohols via Allyl Boronates

A nickel-catalyzed homo- and cross-coupling of allylic alcohols to 1,5-dienes in the presence of B2pin2 with excellent regioselectivity has been developed. Mechanistic studies indicate that the reaction proceeds via sequential nickel-catalyzed borylation of allyl alcohols followed by cross-coupling of the resulting allyl boronates with allyl alcohols. The method was effectively applied to nickel-catalyzed allylation of aldehydes using allylic alcohols directly.

Oxidative Addition to Palladium(0) Made Easy through Photoexcited-State Metal Catalysis: Experiment and Computation

Visible-light induced, palladium catalyzed alkylations of α,β-unsaturated acids with unactivated alkyl bromides are described. A variety of primary, secondary, and tertiary alkyl bromides are activated by the photoexcited palladium metal catalyst to provide a series of olefins at room temperature under mild reaction conditions. Mechanistic investigations and density functional theory (DFT) studies suggest that a photoinduced inner-sphere mechanism is operative in which a barrierless, single-electron transfer oxidative addition of the alkyl halide to Pd0 is key for the efficient transformation.

In Situ Generated Gold Nanoparticles on Active Carbon as Reusable Highly Efficient Catalysts for a Csp3 ?Csp3 Stille Coupling

Gold nanoparticle catalysts are important in many industrial production processes. Nevertheless, for traditional Csp2-Csp2 cross-coupling reactions they have been rarely used and Pd catalysts usually give a superior performance. Herein we report that in situ formed gold metal nanoparticles are highly active catalysts for the cross coupling of allylstannanes and activated alkylbromides to form Csp3-Csp3 bonds. Turnover numbers up to 29 000 could be achieved in the presence of active carbon as solid support, which allowed for convenient catalyst recovery and reuse. The present study is a rare case where a gold metal catalyst is superior to Pd catalysts in a cross-coupling reaction of an organic halide and an organometallic reagent.

P-Chiral Monophosphorus Ligands for Asymmetric Copper-Catalyzed Allylic Alkylation

Asymmetric copper-catalyzed allylic alkylation between allyl bromides and alkyl Grignard reagents using a P-chiral monophosphorus ligand is described. A range of terminal olefins bearing tertiary or quaternary carbon centers were formed in good branched/linear selectivities and excellent enantioselectivities at copper loadings as low as 0.5 mol %.

Iron-Catalyzed Cross-Coupling of Alkynyl and Styrenyl Chlorides with Alkyl Grignard Reagents in Batch and Flow

Transition-metal-catalyzed cross-coupling chemistry can be regarded as one of the most powerful protocols to construct carbon–carbon bonds. While the field is still dominated by palladium catalysis, there is an increasing interest to develop protocols that utilize cheaper and more sustainable metal sources. Herein, we report a selective, practical, and fast iron-based cross-coupling reaction that enables the formation of Csp?Csp3 and Csp2?Csp3 bonds. In a telescoped flow process, the reaction can be combined with the Grignard reagent synthesis. Moreover, flow allows the use of a supporting ligand to be avoided without eroding the reaction selectivity.

Umpolung of Carbonyl Groups as Alkyl Organometallic Reagent Surrogates for Palladium-Catalyzed Allylic Alkylation

Palladium-catalyzed allylic alkylation of nonstabilized carbon nucleophiles is difficult and remains a major challenge. Reported here is a highly chemo- and regioselective direct palladium-catalyzed C-allylation of hydrazones, generated from carbonyls, as a source of umpolung unstabilized alkyl carbanions and surrogates of alkyl organometallic reagents. Contrary to classical allylation techniques, this umpolung reaction utilizes hydrazones prepared not only from aryl aldehydes but also from alkyl aldehydes and ketones as renewable feedstocks. This strategy complements the palladium-catalyzed coupling of unstabilized nucleophiles with allylic electrophiles by providing an efficient and selective catalytic alternative to the traditional use of highly reactive alkyl organometallic reagents.

Photo-induced Decarboxylative Heck-Type Coupling of Unactivated Aliphatic Acids and Terminal Alkenes in the Absence of Sacrificial Hydrogen Acceptors

1,2-Disubstituted alkenes such as vinyl arenes, vinyl silanes, and vinyl boronates are among the most versatile building blocks that can be found in every sector of chemical science. We herein report a noble-metal-free method of accessing such olefins through a photo-induced decarboxylative Heck-type coupling using alkyl carboxylic acids, one of the most ubiquitous building blocks, as the feedstocks. This transformation was achieved in the absence of external oxidants through the synergistic combination of an organo photo-redox catalyst and a cobaloxime catalyst, with H2 and CO2 as the only byproducts. Both control experiments and DFT calculations supported a radical-based mechanism, which eventually led to the development of a selective three-component coupling of aliphatic carboxylic acids, acrylates, and vinyl arenes. More than 90 olefins across a wide range of functionalities were effectively synthesized with this simple protocol.