36650-44-9

Upstream product

• 186581-53-3 diazomethane 
• 528-34-7 β-truxinic acid 
• 103-26-4 Methyl cinnamate 
• 67-56-1 methanol 
• 103-30-0 (E)-1,2-diphenyl-ethene 
• 77734-69-1 methyl l-bornyl fumarate 
• 80754-71-8 methyl (R)-2-methyl-1-butyl fumarate 
• 77-78-1 dimethyl sulfate 
• 78392-59-3 di-<(1S)-endo>-(-)-borneyl fumarate 
• 19713-73-6 methyl (2Z)-3-phenylprop-2-enoate 
• 490-16-4 dl-neotruxinic acid 
• 103-26-4 methyl cinnamate 
• 18509-03-0 sodium trans-cinnamate 
• 490-16-4 (1R,2R,3S,4S)-3,4-Diphenyl-cyclobutane-1,2-dicarboxylic acid 

Downstream Products

• 528-34-7 β-truxinic acid 
• 898816-23-4 3c,4c-diphenyl-cyclobutane-1r,2c-dicarboxylic acid 
• 490-16-4 μ-truxinic acid 
• 490-16-4 (1R,2R,3S,4S)-3,4-Diphenyl-cyclobutane-1,2-dicarboxylic acid 
• 19043-31-3 r-1,t-2-dimethyl-t-3,c-3,4-diphenylcyclobutane 

Relevant academic research and scientific papers

Heteroleptic copper(I) complexes as energy transfer photocatalysts for the intermolecular [2 + 2] photodimerization of chalcones, cinnamates and cinnamamides

The [2 + 2] photodimerization of chalcones, cinnamates and cinnamamides can be effectively catalyzed by heteroleptic copper(I) complexes. The reactions were carried out under mild reaction conditions and the products were obtained in 20–72% yield under visible light irradiation. The copper-based photocatalyst comprised of the rigid phenanthroline ligand with substituents at the 2,9-positions and the 4,7-positions showed high activity in the photodimerization via an energy transfer pathway.

Photocatalytic Oxidative [2+2] Cycloelimination Reactions with Flavinium Salts: Mechanistic Study and Influence of the Catalyst Structure

Flavinium salts are frequently used in organocatalysis but their application in photoredox catalysis has not been systematically investigated to date. We synthesized a series of 5-ethyl-1,3-dimethylalloxazinium salts with different substituents in the positions 7 and 8 and investigated their application in light-dependent oxidative cycloelimination of cyclobutanes. Detailed mechanistic investigations with a coumarin dimer as a model substrate reveal that the reaction preferentially occurs via the triplet-born radical pair after electron transfer from the substrate to the triplet state of an alloxazinium salt. The very photostable 7,8-dimethoxy derivative is a superior catalyst with a sufficiently high oxidation power (E=2.26 V) allowing the conversion of various cyclobutanes (with Eox up to 2.05 V) in high yields. Even compounds such as all-trans dimethyl 3,4-bis(4-methoxyphenyl)cyclobutane-1,2-dicarboxylate can be converted, whose opening requires a high activation energy due to a missing pre-activation caused by bulky adjacent substituents in cis-position.

Donor-acceptor fluorophores as efficient energy transfer photocatalysts for [2 + 2] photodimerization

Mild [2 + 2] photodimerization of enone substrates was induced by donor-acceptor fluorophores. Enone substrates were activated efficiently for anti-head to head dimerizations with a high yield (up to 83%) and high selectivity. The adjustable excited state potential also allows donor-acceptor fluorophores to be used for isomerization of the above substrates, confirming the potential of donor-acceptor fluorophores as energy transfer photocatalysts.

Method for constructing four-membered ring through visible light catalytic [2+2] reaction

The invention discloses a method for constructing a four-membered ring through visible light catalytic [2+2] reaction. The method comprises the following steps: 1.1) adding an unsaturated double-bondcompound and a photosensitizer into a solvent to obtain a solution A; 1.2) irradiating the solution A by using visible light under the argon atmosphere to obtain a dimerized[2+2]cyclobutane product; or 2.1) adding the unsaturated double-bond compound, a styrene compound and the photosensitizer into a solvent to obtain a solution B; and 2.2) irradiating the solution B by using visible light under the argon environment to obtain a crossed [2+2]cyclobutane product. The visible light sensitizer is utilized for the first time and non-rigid double-bond intermolecular[2+2]cyclization reaction is realized; the use amount of the light sensitizer is small, the reaction can be realized under the argon environment by utilizing the visible light or sunlight, and the reaction condition is mild; and thewhole process is simple and efficient, and potential application in organic reaction and industrial production is embodied.

Hydrogen Atom Transfer Reactions via Photoredox Catalyzed Chlorine Atom Generation

The selective functionalization of chemically inert C?H bonds remains to be fully realized in achieving organic transformations that are redox-neutral, waste-limiting, and atom-economical. The catalytic generation of chlorine atoms from chloride ions is one of the most challenging redox processes, where the requirement of harsh and oxidizing reaction conditions renders it seldom utilized in synthetic applications. We report the mild, controlled, and catalytic generation of chlorine atoms as a new opportunity for access to a wide variety of hydrogen atom transfer (HAT) reactions owing to the high stability of HCl. The discovery of the photoredox mediated generation of chlorine atoms with Ir-based polypyridyl complex, [Ir(dF(CF3)ppy)2(dtbbpy)]Cl, under blue LED irradiation is reported.

General and Efficient Intermolecular [2+2] Photodimerization of Chalcones and Cinnamic Acid Derivatives in Solution through Visible-Light Catalysis

[2+2] Photocycloaddition, for example, the dimerization of chalcones and cinnamic acid derivatives, is a unique strategy to construct cyclobutanes, which are building blocks for a variety of biologically active molecules and natural products. However, most attempts at the above [2+2] addition have focused on solid-state, molten-state, or host–guest systems under ultraviolet-light irradiation in order to overcome the competition of facile geometric isomerization of nonrigid olefins. We report a general and simple method to realize the intermolecular [2+2] dimerization reaction of these acyclic olefins to construct cyclobutanes in a highly regio- and diastereoselective manner in solution under visible light, which provides an efficient solution to a long-standing problem.

Photosensitised regioselective [2+2]-cycloaddition of cinnamates and related alkenes

An efficient method for the synthesis of substituted cyclobutanes from cinnamates, chalcones, and styrenes has been developed utilizing a visible-light triplet sensitisation mode. This reaction provides a diverse range of substituted cyclobutanes in high yields under mild conditions without the need of external additives. Good regioselectivity is obtained due to strong π-π-stacking of arene moieties, whereas diastereoselectivity relies on the electronic effects or ortho-substitution of the arene substrate. The utility of this transformation is demonstrated by the formal synthesis of the lignane natural product (±)-Tanegool.

Using non-covalent interactions to direct regioselective 2+2 photocycloaddition within a macrocyclic cavitand

The relative orientation of guests within ternary inclusion complexes is governed by the host-guest and guest-guest supramolecular interactions. Selectivity in 2+2 photocycloaddition between two alkenes included within a macrocyclic cavitand (γ-cyclodextrin) can be controlled using non-covalent interactions. In this manuscript, we report cavitand-mediated control of regioselectivity between alkyl cinnamates using non-covalent interactions. Using this method, we have shown that regioselectivity can be switched completely from a head-to-head dimer to a head-to-tail dimer. The reactions were also stereoselective in most cases. Stoichiometry experiments were performed to explore relative stabilities of the complexes, which indicate that the ternary complex is more stable than others. Selectivity in the photocycloaddition reaction was also applied retrospectively to deduce intermolecular orientations. Time-dependent conversion study we performed indicates that the observed reactivity of alkenes is representative of the intermolecular orientations in the bulk of the complex medium. Experimental observations and computational studies were used to qualitatively understand the complex structures, and relative magnitudes of the weak interactions. The reactions of complexes were studied in slurry form, and the extent of reaction control suggests a solid-state-like behavior.

Photocycloaddition of Cinnamates in Flow and Development of a Thiourea Catalyst

Cyclobutanes derived from the dimerization of cinnamic acids are the core scaffolds of many molecules with potentially interesting biological activities. By utilizing a powerful flow photochemistry platform developed in our laboratory, we have evaluated t

Templating photodimerization of trans-cinnamic acid esters with a water-soluble Pd nanocage

A water-soluble octahedral Pd nanocage acting as a reaction vessel templates the photodimerization of substituted trans-cinnamic acid methyl esters in water. Irradiation of the host-guest complexes of trans-cinnamic acid methyl esters with the Pd nanocage resulted in selective formation of a syn head-head dimer in addition to the corresponding cis isomer. These results suggest that the guest molecules are preoriented in a selective fashion with the hydrophilic ester group facing water and the hydrophobic aryl group tucked within the cavity of the host. Such an orientation occurs at the hydrophobic-hydrophilic interface between the nanocage exterior and interior. Weak intermolecular C-H-π and π-π interactions between the host and the guest(s) are likely to be responsible for the lack of mobility of the reactant olefins during their short excited-state lifetime.