156091-01-9

Upstream product

• 123-11-5 4-methoxy-benzaldehyde 
• 556-56-9 allyl iodid 
• 591-31-1 3-methoxy-benzaldehyde 
• 6325-63-9 (E)-3,3'-dimethoxystilbene 
• 40101-17-5 3,3'-dimethoxybenzil 
• 106-95-6 allyl bromide 
• 2386-64-3 ethylmagnesium chloride 
• 693-04-9 butyl magnesium bromide 
• 100-52-7 benzaldehyde 

Downstream Products

• 40101-17-5 3,3'-dimethoxybenzil 
• 591-31-1 3-methoxy-benzaldehyde 

Relevant academic research and scientific papers

Metal-free thermal organocatalytic pinacol coupling of arylaldehydes using an isonicotinate catalyst with bis(pinacolato)diboron

The metal-free thermal organocatalytic pinacol coupling of arylaldehydes has been developed. The intermolecular coupling of arylaldehydes catalyzed byt-butyl isonicotinate with bis(pinacolato)diboron as the co-reducing agent afforded 1,2-diphenylethane-1,2-diols. This reaction was also applicable to the intramolecular coupling of 1,1′-biphenyl-2,2′-dicarbaldehydes to afford 9,10-dihydrophenanthrene-9,10-diols. Various functional groups were tolerated under this coupling condition.

Reductive Coupling of Aromatic Aldehydes and Ketones under Electrochemical Conditions

Reductive coupling of o-substituted carbonyl compounds and m-substituted carbonyl compounds by the direct transfer of electron to carbonyl group respectively gave 1-(4-(1-hydroxy-1-phenylethyl/methyl)phenyl)ethanones/methanones and 2,3-bis(3-substitutedph

Crystal-to-Crystal Synthesis of Photocatalytic Metal–Organic Frameworks for Visible-Light Reductive Coupling and Mechanistic Investigations

Postmodification of reticular materials with well-defined catalysts is an appealing approach to produce new catalytic functional materials with improved stability and recyclability, but also to study catalysis in confined spaces. A promising strategy to this end is the postfunctionalization of crystalline and robust metal–organic frameworks (MOFs) to exploit the potential of crystal-to-crystal transformations for further characterization of the catalysts. In this regard, two new photocatalytic materials, MOF-520-PC1 and MOF-520-PC2, are straightforwardly obtained by the postfunctionalization of MOF-520 with perylene-3-carboxylic acid (PC1) and perylene-3-butyric acid (PC2). The single crystal-to-crystal transformation yielded the X-ray diffraction structure of catalytic MOF-520-PC2. The well-defined disposition of the perylenes inside the MOF served as suitable model systems to gain insights into the photophysical properties and mechanism by combining steady-state, time-resolved, and transient absorption spectroscopy. The resulting materials are active organophotoredox catalysts in the reductive dimerization of aromatic aldehydes, benzophenones, and imines under mild reaction conditions. Moreover, MOF-520-PC2 can be applied for synthesizing gram-scale quantities of products in continuous-flow conditions under steady-state light irradiation. This work provides an alternative approach for the construction of well-defined, metal-free, MOF-based catalysts.

Ring Closing Metathesis Approach for the Synthesis of o-Terphenyl Derivatives

A linear synthesis of o-terphenyl derivatives has been delineated using ring closing metathesis (RCM) as the key step. In this approach, benzil derivatives upon allyl Grignard addition provides diphenyl-1,2-diallyl dihydroxy derivatives which undergo ring closing metathesis to afford tetrahydro terphenyl derivatives. Aromatization-driven dehydration then leads to a diverse set of electron rich and electron deficient o-terphenyls. Furthermore, oxidative coupling of electron rich o-terphenyls provides the corresponding triphenylene derivatives.

Stereoselective Barbier-Type Allylations and Propargylations Mediated by CpTiCl3

CpTiCl2, prepared in situ by manganese reduction of CpTiCl3, is an excellent new system for the Barbier-type allylation and propargylation of carbonyl compounds. It can be used in catalytic amounts when combined with Et3N·HBr/TMSBr, which acts as a regenerating system. The high regio- and stereoselectivity shown by this system makes it useful for prenylation and crotylation processes in the synthesis of natural products.

Selective Pinacol Coupling on Regeneratable Supported Acids in Sole Water

Efficient pinacol coupling was developed in sole water, using a reusable heterogeneous supported acid source and zinc as cheap available metal source. This medium can be easily regenerated up to 10-fold without loss of activity. Moreover, supported acids enhance the selectivity of the pinacol coupling reaction compared with homogeneous acids.

First pinacol coupling in emulsified water: Key role of surfactant and impact of alternative activation technologies

For the first time, the influence of surfactants on the radical pinacol coupling reaction is investigated. The rate and selectivity of this reductive C-C coupling are compared under three different activation technologies: thermal activation, microwave irradiation, and sonication. The use of IgepalCO520, a neutral surfactant, led to the successful conversion of aromatic or α,β-unsaturated aliphatic carbonyl compounds in moderate to excellent yield (55-90 %). An insight on the potential mechanism involved in the reaction is also proposed, based on microscopic observations and particle size measurement.

Biocatalyzed asymmetric reduction of benzils to either benzoins or hydrobenzoins: pH dependent switch

Enantiopure benzoins and hydrobenzoins are precursors of various pharmaceuticals and biologically active compounds. In addition, hydrobenzoins are precursors of chiral ligands and auxiliaries in stereoselective organic synthesis. Biocatalytic reduction of benzils is a straightforward approach to prepare these molecules. However, known methods are not selective and lead to formation of a mixture of benzoin and hydrobenzoin, requiring expensive separation procedures. Here, we describe an enzyme system Talaromyces flavus, which exhibited excellent pH dependent selectivity for the conversion of benzil to either benzoin or hydrobenzion in high ee. Thus, (S)-benzoin was the exclusive product at pH 5.0 (ee >99%), whereas at pH 7.0, (S,S)-hydrobenzoin (ee >99%, dl/meso 97 : 3) was the exclusive product. The observed pH dependent selectivity was shown to be due to the presence of multiple enzymes in Talaromyces flavus, which specifically accepted either benzil or benzoin as a substrate and exhibited different pH profiles of their activity. The biocatalyst efficiently reduced a variety of symmetrical and unsymmetrical benzils. Moreover, a 36.4 kDa benzoin reductase was purified, the N-terminal sequence of which did not show a significant similarity to any of the known reductase/dehydrogenase in the database. The protein therefore appears to be a novel reductase.

The scalable pinacol coupling reaction utilizing the inorganic electride [Ca2N]+·e- as an electron donor

The scalable pinacol coupling reaction is realized utilizing the inorganic electride [Ca2N]+·e- as an electron donor in organic solvents. The bond cleavages of the [Ca2N] + layers by methanol play a vital role in transferring anionic electrons to electrophilic aldehydes, accompanying the formation of Ca(OMe) 2 and ammonia. The Royal Society of Chemistry 2014.

Synthesis of ferrocene derivatives with planar chirality via palladium-catalyzed enantioselective C-H bond activation

The first catalytic and enantioselective C-H direct acylation of ferrocene derivatives has been developed. A series of 2-acyl-1-dimethylaminomethylferrocenes with planar chirality were provided under highly efficient and concise one-pot conditions with up to 85% yield and 98% ee. The products obtained could be easily converted to various chiral ligands via diverse transformations.