41158-32-1

Upstream product

• 33553-90-1 4-hydroxy-4-phenyl-but-2-ynoic acid methyl ester 
• 43165-51-1 sodium benzoylformate 
• 100-52-7 benzaldehyde 
• 20913-05-7 (Benzoylmethylene)triphenylphosphorane 
• 25726-04-9 phenylglyoxylyl chloride 
• 98-88-4 benzoyl chloride 
• 922-67-8 propynoic acid methyl ester 
• 144823-67-6 methyl 3,4-dioxo-4-phenyl-2-triphenylphosphoranylidenebutanoate 
• 152126-74-4 methyl 2,4-dioxo-4-phenyl-3-triphenylphosphoranylidenebutanoate 

Downstream Products

• 5817-92-5 2,4-dioxo-4-phenylbutanoic acid 
• 56426-35-8 methyl 5-phenyl-1H-pyrazole-3-carboxylate 
• 51677-09-9 methyl 5-phenylisoxazole-3-carboxylate 
• 19522-28-2 (Z)-4-oxo-4-phenyl-but-2-enoic acid methyl ester 
• 25333-24-8 3-benzoylpropionic acid methyl ester 
• 117794-12-4 2-amino-4-oxo-4-phenyl-crotonic acid methyl ester 
• 122439-37-6 2-benzoyl-cyclohexa-1,4-dienecarboxylic acid methyl ester 
• 113416-21-0 methyl 4-oxo-4-phenyl-2-(phenylamino)but-2-enoate 
• 107551-24-6 7-(1,3-Dioxo-1,3-dihydro-isoindol-2-yl)-5-methoxy-2,2,3,3-tetramethyl-7-phenyl-1,4,6-trioxa-5λ⁵-phospha-spiro[4.4]non-8-ene-9-carboxylic acid methyl ester 
• 135765-07-0 5-Benzoyl-2-[1-methoxycarbonyl-3-oxo-3-phenyl-2-(tributyl-λ⁵-phosphanylidene)-prop-(E)-ylidene]-[1,3]dithiole-4-carboxylic acid methyl ester 
• 107551-17-7 (E)-2-(2,2-Dimethoxy-4,4,5,5-tetramethyl-2λ⁵-[1,3,2]dioxaphospholan-2-yl)-4-oxo-4-phenyl-but-2-enoic acid methyl ester 
• 107598-00-5 5,7-Dimethoxy-2,2,3,3-tetramethyl-7-phenyl-1,4,6-trioxa-5λ⁵-phospha-spiro[4.4]non-8-ene-9-carboxylic acid methyl ester 
• 245068-91-1 methyl 2-benzoyl-5-(4-methoxybenzylsulfanyl)-3-methylbenzoate 
• 245068-88-6 methyl 2-benzoyl-3-tert-butyl-5-(4-methoxybenzylsulfanyl)benzoate 

Relevant academic research and scientific papers

A Self-Catalyzed Visible Light Driven Thiol Ligation

We introduce a highly efficient ligation system based on a visible light-induced rearrangement affording a thiophenol which rapidly undergoes thiol-Michael additions. Unlike conventional light-triggered thiol-ene/yne systems, which rely on the use of photocaged bases/nucleophiles, (organo)-photo catalysts, or radical photoinitiators, our system provides a light-induced reaction in the absence of any additives. The ligation is self-catalyzed via the pyridine mediated deprotonation of the photochemically generated thiophenol. Subsequently, the thiol-Michael reaction between the thiophenol anion and electron deficient alkynes/alkenes proceeds additive-free. Hereby, the underlying photoinduced rearrangement of o-thiopyrinidylbenzaldehyde (oTPyB) generating the free thiol is described for the first time. We studied the influence of various reactions conditions as well as solvents and substrates. We exemplify our findings in a polymer end group modification and obtained macromolecules with excellent end group fidelity.

Light-induced Ligation of o-Quinodimethanes with Gated Fluorescence Self-reporting

We introduce a highly efficient photoligation system, affording a pro-fluorescent Diels-Alder product that, on demand, converts into an intensively fluorescent naphthalene via E1 elimination in the presence of catalytic amounts of acid. The Diels-Alder reaction of the photocaged diene (o-quinodimethane ether or thioether) with electron-deficient alkynes is induced by UV or visible light. In contrast to previously reported ligation techniques directly leading to fluorescent products, the fluorescence is turned on after the photoligation. Thus, the light absorption of the fluorophore does not undermine the photoligation via competitive absorption, and as a result, photobleaching or side reactions of the fluorophore are not observed. Critically, the gated generation of a fluorescent product allows for fluorometric determination of the conversion. We employ a simple synthesis strategy for heterobifunctional electron-deficient alkynes allowing for facile functionalization of payload molecules.

Relative Rates of Metal-Free Azide-Alkyne Cycloadditions: Tunability over 3 Orders of Magnitude

The thermal (3 + 2) dipolar azide-alkyne cycloaddition, proceeding without copper or strained alkynes, is an underutilized ligation with potential applications in materials, bioorganic, and synthetic chemistry. Herein, we investigate the effects of alkyne substitution on the rate of this reaction, both experimentally and computationally. Electron-withdrawing groups accelerate the reaction, providing a range of relative rates from 1.0 to 2100 between the slowest and fastest alkynes studied. Unexpectedly, aryl groups conjugated to the alkyne significantly retard the reaction rate. In contrast, a sulfonyl, ester-substituted alkyne is reactive enough that it couples with an azide at room temperature in a few hours. This reactivity scale should provide a guide to those who wish to use this ligation under mild conditions.

Relative Rates of Metal-Free Azide-Alkyne Cycloadditions: Tunability over 3 Orders of Magnitude

The thermal (3 + 2) dipolar azide-alkyne cycloaddition, proceeding without copper or strained alkynes, is an underutilized ligation with potential applications in materials, bioorganic, and synthetic chemistry. Herein, we investigate the effects of alkyne substitution on the rate of this reaction, both experimentally and computationally. Electron-withdrawing groups accelerate the reaction, providing a range of relative rates from 1.0 to 2100 between the slowest and fastest alkynes studied. Unexpectedly, aryl groups conjugated to the alkyne significantly retard the reaction rate. In contrast, a sulfonyl, ester-substituted alkyne is reactive enough that it couples with an azide at room temperature in a few hours. This reactivity scale should provide a guide to those who wish to use this ligation under mild conditions.

Synthesis of New γ-Lactams with gem-Difluorinated Side Chains

A short and efficient approach has been designed for the synthesis of new γ-lactams that feature gem-difluorinated side-chains in position 4. The key steps involve 1,4-addition of nitroalkane anions on electrophilic gem-difluoroalkenes, followed by a cascade nitro reduction-heterocyclization. This flexible strategy also allows easy introduction of substituents in positions 3 or 5.

Regioselective synthesis of 3,4,5-trisubstituted 2-aminofurans

Three series of methyl 5-substituted 2-aminofuran-4-keto-3-carboxylates have been prepared following a multicomponent reaction strategy by the addition of an isocyanide to 4-oxo-2-butynoate in the presence of an aldehyde. The cycloaddition regioselectivit

Synthesis of fluorenone and anthraquinone derivatives from aryl- and aroyl-substituted propiolates

Fluorenone derivatives were generated from aryl-substituted propiolates via a cobalt-catalyzed Diels-Alder reaction/DDQ-oxidation and Friedel-Crafts-type cyclization. Several functional groups are tolerated, and good to excellent overall yields (up to 89%) could be achieved. For the synthesis of anthraquinone derivatives, aroyl-substituted propiolates were applied in a zinc iodide catalyzed Diels-Alder reaction with 1,3-dienes. The subsequent DDQ oxidation and Friedel-Crafts-type cyclization led to symmetrical as well as some unsymmetrical anthraquinones in good to excellent yields of up to 87% over the three-step reaction sequence.

Transposing molecular fluorescent switches into the near-IR: Development of luminogenic reporter substrates for redox metabolism

This study reports the development of a Nd(III)-based near-IR luminescent probe for monitoring aldo-ketoreductase (AKR) enzyme activity. We have adapted a coumarin-based reporter substrate for the AKR1C2 to a near-IR emitting format by tethering the former to a macrocyclic Nd(III) moiety via an alkyl linker. Enzymatic reduction of the ketone functionality on the coumarin alters the energy transfer efficiency from the fluorophore to the emitting lanthanide species, resulting in emission at ～1060 nm from the alcohol product. The efficiency of sensitization is not significantly affected by extending the alkyl tether from two to three carbons, and even a six-carbon linker still supports viable sensitized luminescence. In addition, the suitability of these complexes to act as enzyme substrates improves with longer linker length. We have thus developed long wavelength luminogenic reporter substrates for a redox enzyme and also a general platform for transposing molecular fluorescence into the more desirable near-IR region. Copyright

Metal-free access to fully substituted skipped diynes. An efficient chemodifferentiating A2BB′ 4CR manifold

(Chemical Equation Presented) A metal-free chemodifferentiating A 2BB′ 4CR manifold for the modular synthesis of tertiary skipped diynes is described. The manifold performs a triethylamine triggered reaction of alkyl propiolates and acid chlori

LIGANDS FOR ALDOKETOREDUCTASES

The present invention relates to compounds useful for detecting the activity of human aldoketoreductase 1Cs, compounds useful for competitively inhibiting human aldoketoreductase 1Cs and compounds useful for treating human aldoketoreductase 1C-related can