A5045393584- Synthesis and Characterization of Pyrroles
- Fluorine in Organic Chemistry
- Catalytic Alkyne Reactions
- X-ray Diffraction in Crystallography
- Crystallization and Solubility Studies
- Synthetic Organic Chemistry Methods
- Catalytic C–H Functionalization Methods
- Asymmetric Synthesis and Catalysis
- Chemical Synthesis and Analysis
- Cyclopropane Reaction Mechanisms
- Organic Chemistry Cycloaddition Reactions
- Click Chemistry and Applications
- Oxidative Organic Chemistry Reactions
- Organophosphorus compounds synthesis
- Synthesis and Reactivity of Sulfur-Containing Compounds
- Catalysis for Biomass Conversion
- Radical Photochemical Reactions
- Asymmetric Hydrogenation and Catalysis
- Synthesis and Catalytic Reactions
- Phosphorus compounds and reactions
- Sulfur-Based Synthesis Techniques
- Synthesis of Organic Compounds
- Carbohydrate Chemistry and Synthesis
- Photochromic and Fluorescence Chemistry
- Chemical Synthesis and Reactions
A.E. Favorsky Irkutsk Institute of Chemistry
2016-2025
Russian Academy of Sciences
2012-2015
Stable pyrrole-tailored selones, 1,2,5-trisubstituted-1,2-dihydro-3H-pyrrole-3-selones, have been synthesized in up to 75% yield from aminoacetylenic ketones and elemental selenium (KOH/EtOH, room temperature, 10-11 h). The work is mainly focused on the one-pot synthesis of these compounds (50-75% yields). This has achieved via reactions propargyl amines with acyl chlorides presence a Pd/Cu catalyst (toluene, 40-45 °C, 2-3 h) followed by addition pre-heated mixture Se/KOH (SnCl2)/EtOH at...
A one‐pot transition metal‐free synthesis of propargylamines in good to excellent yield from ketone‐derived imines and aryl‐ hetarylacetylenes the presence KOBu t /DMSO superbase system (40 °C, 10 min) has been developed. The reaction involves a nucleophilic addition acetylenic carbanions C=N bond, thus for first time featuring aza‐Favorsky reaction.
A new Csp 3 –Csp bond forming reaction is reported: the C=N of widespread imines reacts with acetylene gas in presence superbase KO t Bu/DMSO at room temperature to afford terminal α‐aminoacetylenes up 94 % yield. The allows nitrogen heterocycles, e.g. 3H‐indoles, be directly cross‐coupled gas.
Aldimines react with aryl- and hetarylacetylenes in the presence of KOBut/dimethyl sulfoxide (DMSO) or NaOBut/DMSO systems under exceptionally mild conditions (14 °C, 1 h) to afford C-H-vinylated products, 1-azadienes E configuration relative C-C bond, up 72% yield. Vinylation involves unprecedentedly fast multiposition proton transfer intermediate adducts acetylene C═N bond. This new Csp2-Csp2 bond-forming reaction opens a straightforward pot-, atom-, step-, energy-economic access...
N-Benzyl ketimines undergo [3 + 2] cycloaddition with arylacetylenes in the KOBut/DMSO solution to 2,3,5-triarylpyrrolines, which are oxidized (chloranil, DDQ) situ 2,3,5-triaryl-2H-pyrroles 53–71% yields. The intermediate 1-pyrrolines can be isolated 31–91% yields and separately corresponding 2H-pyrroles.
Acetylene reacts with methylaryl(hetaryl)ketones in the presence of 6.5 mol % KOH DMSO to give diastereoselectively single operationally functionalized cyclopentenes. This domino cyclization involving two molecules acetylene and ketone proceeds formation four C–C bonds. The complementary assembly cyclopentenes similar functionalities from acetylenes 1,5-diketones has been developed.
Semistabilized diazatrienyl anions are generated by the reaction of 2-pyridylarylimines with arylacetylenes in superbase systems MOtBu (M = Li, Na, K)/DMSO at ambient temperature for 15 min. The initial intermediate N-centered propargyl-1,3-diaza-1,3,5-trienyl undergo intermolecular cyclization to benzyl imidazopyridine (formally [3 + 2] cycloaddition), further intercepting a second molecule starting pyridylimines or proton medium afford (Z)-stilbene/imidazopyridine ensembles and...
Abstract 1,5‐Diketones are readily cyclized in the presence of various alkali‐metal superbases with acetylenes at 70 °C a one‐pot cascade reaction to give methylene‐6,8‐dioxabicyclo[3.2.1]octanes up 92 % yield. In case symmetrical 1,5‐diketones, only one diastereomer is formed, whereas unsymmetrical diketones afford two diastereomers ratio corresponding that starting ketones. This result indicates key cyclization sequence stereoselective.
Abstract The Favorsky reaction of a wide range aldehydes and ketones with alkynes has been implemented under mild conditions (5–20 °C). Using Bu 4 NOH/H 2 O/DMSO catalytic system, propargylic alcohols are formed cleanly in 39–93 % (mostly 72–93 %) yields ca. 100 selectivity. method is suitable for aliphatic, aromatic, heteroaromatic ketones, functionalized acetylenes. Thus, this represents the most general efficient protocol to achieve reaction.
Several imines, readily derived from aryl methyl ketones and benzylamines, react with acetylene gas in KOBut/DMSO system to afford 2-azadienes stereoselectively. This new C-C bond constructing reaction involves, instead of the expected ethynylation C═N bond, addition azaallyl anions triple acetylene.
Ketones with bulky aromatic, heteroaromatic and ferrocene substituents react acetylene in the presence of a KOH/DMSO super-base suspension (90 °C, 15 min) to give polysubstituted furans up 86 % isolated yields one-pot fashion. This assembly furan scaffold involves domino sequence which one molecule ketone reacts two molecules acetylene.
The products of the one-pot assembly acetylene and ketones in KOH/DMSO system, 7-methylene-6,8-dioxabicyclo[3.2.1]octanes, undergo an acid-catalyzed (CF3COOH, room temperature) rearrangement to rarely substituted cyclopentadienes good-to-excellent yields. mechanism has been supported by isolation corresponding transformations two intermediates.
Abstract Pd/Cu‐catalyzed cross‐coupling of propargylamines with aromatic acyl chlorides (PdCl 2 , CuI, Ph 3 P, 40–45 °C) provides α‐aryl(hetaryl)aminoacetylenic ketones in a yield up to 97%. The latter undergo cyclization 1,2,5‐triaryl(hetaryl)‐1,2‐dihydro‐3 H ‐pyrrol‐3‐ones 93% after the treatment KOH or Et NH (40–55 °C, aqueous ethanol). one‐pot synthesis pyrrol‐3‐ones (in 62% yields) by consecutive above /CuI/Ph P) and base (KOH) ethanol has been also developed. magnified image
A one-pot synthesis of 1,2,5-trisubstituted-1,2-dihydro-3 H -pyrrole-3-thiones (up to 91% yield) by the successive treatment available propargylamines with acyl chlorides (PdCl 2 /CuI/Ph 3 P/Et N, toluene, 40–45 °C, h) and sodium sulfide (Na S·9H O, EtOH, 20–25 7 has been developed.
By using a quantum-chemical approach, B2PLYP-D2/6-311+G**//B3LYP/6-31+G*, we have carried out detailed study of the assembly 1-pyrrolines from N-benzyl-1-phenylmethanimine and phenylacetylene in superbasic medium KOtBu/dimethyl sulfoxide (DMSO). In this way, considered, both theoretically experimentally, mechanisms through concerted stepwise nucleophilic cycloaddition addressed side processes accompanying assembly. It is found that via kinetically more favorable than cycloaddition. At same...
Pharmaceutically prospective 2‐substituted‐4,5‐dimethyloxazoles are synthesized in up to 58% yield via unprecedented cascade assembly of one molecule primary amide with two molecules acetylene gas the KOH/MeOH/DMSO (90 oC, 2 h) catalytic triad. This oxazoles self‐organization demonstrates unexpected successful competition alkaline hydrolysis amides. The mechanism involving N‐vinylation, enamine‐imine isomerization, imine ethynylation and intramolecular О‐vinylation sequence has been deduced...