24808-73-9

Upstream product

• 21087-29-6 trans-3-phenylprop-2-enyl chloride 
• 77-78-1 dimethyl sulfate 
• 4407-36-7 (2E)-3-phenyl-2-propen-1-ol 
• 74-88-4 methyl iodide 
• 22554-02-5 ethyl cinnamylcarbamate 
• 124-41-4 sodium methylate 
• 67-56-1 methanol 
• 300-57-2 allylbenzene 
• 201230-82-2 carbon monoxide 
• 21040-45-9 Cinnamyl acetate 
• 108-86-1 bromobenzene 
• 110388-16-4 (E)-tributyl(3-methoxyprop-1-en-1-yl)stannane 
• 4364-06-1 (E)-cinnamaldehyde dimethylacetal 
• 75712-76-4 dicinnamyldimethylammonium bromide 

Downstream Products

• 99857-56-4 (1RS,2SR)-2-bromo-1,3-dimethoxy-1-phenyl-propane 
• 99359-87-2 1-chloro-3-methoxy-1-phenyl-acetone oxime 
• 61062-66-6 1-Chloro-4-(2-chloro-1-methoxymethyl-2-phenyl-ethylsulfanyl)-benzene 
• 114701-68-7 (4E)-3-methoxy-1,5-diphenylpent-4-en-1-one 
• 114701-66-5 (E)-⁽²⁾-methoxy-4-phenyl-3-butenenitrile 
• 51985-30-9 4-Methyl-N-[(E)-3-phenyl-prop-2-en-(E)-ylidene]-benzenesulfonamide 
• 82053-18-7 1-[(E)-3-methoxyhexa-1,5-dienyl]benzene 
• 120342-90-7 trans-2-Methoxymethyl-3-phenyl-ethoxycarbonylcyclopropane 
• 120342-93-0 (2S,3S)-2-Methoxy-1,3-diphenyl-pent-4-en-1-one 
• 120342-93-0 (2S,3R)-2-Methoxy-1,3-diphenyl-pent-4-en-1-one 
• 120342-91-8 ((2R,3R)-2-Methoxymethyl-3-phenyl-cyclopropyl)-phenyl-methanone 
• 120342-92-9 ((2R,3R)-2-Methoxymethyl-3-phenyl-cyclopropyl)-(4-methoxy-phenyl)-methanone 
• 120342-95-2 (2S,3R)-2-Methoxy-1-(4-methoxy-phenyl)-3-phenyl-pent-4-en-1-one 
• 120342-95-2 (2S,3S)-2-Methoxy-1-(4-methoxy-phenyl)-3-phenyl-pent-4-en-1-one 

Relevant academic research and scientific papers

Decarboxylative cross-nucleophile coupling via ligand-to-metal charge transfer photoexcitation of Cu(ii) carboxylates

Reactions that enable carbon–nitrogen, carbon–oxygen and carbon–carbon bond formation lie at the heart of synthetic chemistry. However, substrate prefunctionalization is often needed to effect such transformations without forcing reaction conditions. The development of direct coupling methods for abundant feedstock chemicals is therefore highly desirable for the rapid construction of complex molecular scaffolds. Here we report a copper-mediated, net-oxidative decarboxylative coupling of carboxylic acids with diverse nucleophiles under visible-light irradiation. Preliminary mechanistic studies suggest that the relevant chromophore in this reaction is a Cu(ii) carboxylate species assembled in situ. We propose that visible-light excitation to a ligand-to-metal charge transfer (LMCT) state results in a radical decarboxylation process that initiates the oxidative cross-coupling. The reaction is applicable to a wide variety of coupling partners, including complex drug molecules, suggesting that this strategy for cross-nucleophile coupling would facilitate rapid compound library synthesis for the discovery of new pharmaceutical agents. [Figure not available: see fulltext.].

Oxoammonium-Mediated Allylsilane–Ether Coupling Reaction

A new C(sp3)?H functionalization reaction consisting of the oxidative α-allylation of allyl- and benzyl- methyl ethers has been developed. The C?C coupling could be carried out under mild conditions thanks to the use of cheap and green oxoammonium salts. The scope of the reaction was studied over 27 examples, considering the nature of the substituents on the two coupling partners.

Stereoselective Rhodium-Catalyzed Isomerization of Stereoisomeric Mixtures of Arylalkenes

A new efficient method for the synthesis of a high ratio of E -alkenes from E / Z mixtures of alkenes with B 2pin 2in the presence of a rhodium catalyst is described. This reaction features mild reaction conditions, broad functional group tolerance, and highly great application potential.

Photocatalyzed Diastereoselective Isomerization of Cinnamyl Chlorides to Cyclopropanes

Endergonic isomerizations are thermodynamically unfavored processes that are difficult to realize under thermal conditions. We report a photocatalytic and diastereoselective isomerization of acyclic cinnamyl chlorides to strained cyclopropanes. Quantum mechanical calculations (uM06-2X and DLPNO), including TD-DFT calculations, and experimental studies provide evidence for the energy transfer from an iridium photocatalyst to the allylic chloride substrate followed by C-Cl homolytic cleavage. Subsequent Cla￠ radical migration forms a localized triplet 1,3-diradical intermediate that, after intersystem crossing, undergoes ring-closing to form the desired product. The mild reaction conditions are compatible with a broad range of functional groups to generate chlorocyclopropanes in high yields and diastereoselectivities. A more efficient process is developed by addition of a catalytic amount of a nickel complex, and we propose a novel role for this cocatalyst to recycle an allyl chloride byproduct generated in the course of the reaction. The reaction is also shown to be stereoconvergent, as an E/Z mixture of cinnamyl chlorides furnish the anti-chlorocyclopropane product in high diastereoselectivity. We anticipate that the use of a visible light activated photocatalyst to transform substrates in combination with a transition metal catalyst to recycle byproducts back into the catalytic cycle will provide unique opportunities for the discovery of new reactivity.

Design, Synthesis, and Application of Chiral C2-Symmetric Spiroketal-Containing Ligands in Transition-Metal Catalysis

We present an expedient and economical route to a new spiroketal-based C2-symmetric chiral scaffold, termed SPIROL. Based on this spirocyclic scaffold, several chiral ligands were generated. These ligands were successfully employed in an array of stereoselective transformations, including in iridium-catalyzed hydroarylations (up to 95 % ee), palladium-catalyzed allylic alkylations (up to 97 % ee), intermolecular palladium-catalyzed Heck couplings (up to 94 % ee), and rhodium-catalyzed dehydroalanine hydrogenation (up to 93 % ee).

Iron-Catalyzed Grignard Cross-Couplings with Allylic Methyl Ethers or Allylic Trimethylsilyl Ethers

We have found that cross-coupling between aryl Grignard reagents and allylic methyl ethers proceeded well in the presence of a catalytic amounts of Fe(acac) 3 to afford the corresponding allylic substitution products in good yields. Under the same conditions, allylic trimethylsilyl ethers also reacted with Grignard reagents to give the corresponding cross-coupling products.

Auto-Tandem Catalysis with Frustrated Lewis Pairs for Reductive Etherification of Aldehydes and Ketones

Herein we report that a single frustrated Lewis pair (FLP) catalyst can promote the reductive etherification of aldehydes and ketones. The reaction does not require an exogenous acid catalyst, but the combined action of FLP on H2, R-OH or H2O generates the required Br?nsted acid in a reversible, “turn on” manner. The method is not only a complementary metal-free reductive etherification, but also a niche procedure for ethers that would be either synthetically inconvenient or even intractable to access by alternative synthetic protocols.

Practical Photocatalytic Trifluoromethylation and Hydrotrifluoromethylation of Styrenes in Batch and Flow

Styrenes represent a challenging class of substrates for current radical trifluoromethylation and hydrotrifluoromethylation methods due to a myriad of potential side reactions. Herein, we describe the development of mild, selective and broadly applicable photocatalytic trifluoromethylation and hydrotrifluoromethylation protocols for these challenging substrates. The methods use fac-Ir(ppy)3, visible light and inexpensive CF3I and can be applied to a diverse set of vinylarene substrates. The use of continuous-flow photochemical reaction conditions allowed to reduce the reaction time and increase the reaction selectivity.

Oxidative cleavage of allyl ethers by an oxoammonium salt

A method to oxidatively cleave allyl ethers to their corresponding aldehydes mediated by an oxoammonium salt is described. Using a biphasic solvent system and mild heating, cleavage proceeds readily, furnishing a variety of α,β-unsaturated aldehydes and ketones.

Toward a Unified Mechanism for Oxoammonium Salt-Mediated Oxidation Reactions: A Theoretical and Experimental Study Using a Hydride Transfer Model

A range of oxoammonium salt-based oxidation reactions have been explored computationally using density functional theory (DFT), and the results have been correlated with experimentally derived trends in reactivity. Mechanistically, most reactions involve a formal hydride transfer from an activated C-H bond to the oxygen atom of the oxoammonium cation. Several new potential modes of reactivity have been uncovered and validated experimentally.