Abstract:The reaction of tetraalkynyltin with aldehydes was studied for the first time. The reaction was shown to proceed as a tandem process of nucleophilic addition of tin acetylide to aldehyde followed by Oppenauer-type oxidation of produced tin alcoholates, and may be used as a convenient one-pot approach to acetylenic ketones. The advantages and limitations of the proposed method are discussed.149 Stavropolskaya str., 350040 Krasnodar, Russian Federation.
“…41.4 to 41.8 °C. 1 H NMR (400 MHz, CDCl3) δ 0.87 (t, 3H, CH3), 1.21 to 1.37 (m, 24H, CH2), 1.73 (quint, 2H, C 5 H2), 2.65 (t, 2H, C 4 H2), 7.35 to 7.39 (m, 2H, ArH), 7.42 to 7.46 (m, 1H, ArH), 7.55 to 7.57 (m, 2H, ArH); 13…”
Section: Typical Procedures For the Synthesis Of Alkynyl Ketonesmentioning
confidence: 99%
“…These drawbacks can be avoided with the replacement of monoalkynylstannanes with tetraalkynyltin reagents, as they are far less toxic and the molecular weight of the tin residue is significantly lower in comparison with trialkyltin reagents. Recently, we reported the Stille-type coupling reaction of tetraalkynylstannanes with aryl halides leading to aryl acetylenes and SnHal4 [12] and aldehydes leading to alkynyl ketones [13,14]. Earlier, we developed convenient methods for preparation of tetraalkinyltin species from either SnCl4 [15] or tin tetra(N,N-diethylcarbamate) [16].…”
Akynyl ketones were synthesized from tetraalkinylstannanes and both aliphatic and aromatic acyl chlorides under Lewis acid catalysis. The structure of products was confirmed by means of NMR, IR, GC-MS. The method is suitable for the synthesis of long-chain acetylenic ketones.
“…41.4 to 41.8 °C. 1 H NMR (400 MHz, CDCl3) δ 0.87 (t, 3H, CH3), 1.21 to 1.37 (m, 24H, CH2), 1.73 (quint, 2H, C 5 H2), 2.65 (t, 2H, C 4 H2), 7.35 to 7.39 (m, 2H, ArH), 7.42 to 7.46 (m, 1H, ArH), 7.55 to 7.57 (m, 2H, ArH); 13…”
Section: Typical Procedures For the Synthesis Of Alkynyl Ketonesmentioning
confidence: 99%
“…These drawbacks can be avoided with the replacement of monoalkynylstannanes with tetraalkynyltin reagents, as they are far less toxic and the molecular weight of the tin residue is significantly lower in comparison with trialkyltin reagents. Recently, we reported the Stille-type coupling reaction of tetraalkynylstannanes with aryl halides leading to aryl acetylenes and SnHal4 [12] and aldehydes leading to alkynyl ketones [13,14]. Earlier, we developed convenient methods for preparation of tetraalkinyltin species from either SnCl4 [15] or tin tetra(N,N-diethylcarbamate) [16].…”
Akynyl ketones were synthesized from tetraalkinylstannanes and both aliphatic and aromatic acyl chlorides under Lewis acid catalysis. The structure of products was confirmed by means of NMR, IR, GC-MS. The method is suitable for the synthesis of long-chain acetylenic ketones.
“…Ongoing research in α,β-acetylenic ketones is driven by their versatile use as valuable precursors in organic synthesis with the syntheses of polycyclic and heterocyclic compounds [5]. These compounds include isoxazoles, chromones, triazoles, quinolones, indenones, thiazoles, 1,5-benzodiazepines, and spirocyclic compounds [5][6][7].…”
Section: Commentmentioning
confidence: 99%
“…Ongoing research in α,β-acetylenic ketones is driven by their versatile use as valuable precursors in organic synthesis with the syntheses of polycyclic and heterocyclic compounds [5]. These compounds include isoxazoles, chromones, triazoles, quinolones, indenones, thiazoles, 1,5-benzodiazepines, and spirocyclic compounds [5][6][7]. Apart from the plethora of fine chemicals attainable from these acetylenic ketones, their increasing use as electron-rich ligands in organometallic chemistry [8] warrants continued research into their syntheses, properties, and molecular structure.…”
“…This form of oxidation was proposed to proceed by transfer of the hydride to the aldehyde from in situ-generated metal alkoxide intermediates obtained from nucleophilic attack of the aldehyde. Various types of organometallic reagents, such as nucleophiles based on organomagnesium, -zinc, -aluminum, -tin, -boron, -indium, and -zirconium, are involved in this transformation. Among them, allylmetal reagents are particularly attractive because they can be used to prepare synthetically useful allylic ketones bearing α-tertiary and even difficult-to-access α-quaternary stereogenic centers under simple and mild reaction conditions .…”
An efficient and straightforward
approach to allylaluminum reagent
synthesis through Cu-catalyzed hydroalumination of readily accessible
allenes with diisobutylaluminum hydride is described. The N-heterocyclic
carbene-based copper complex promotes hydride addition to various
functionalized allenes under mild reaction conditions. The catalytic
reaction is applied to a highly selective one-pot synthesis of allylic
ketones with α-tertiary and α-quaternary centers through
tandem nucleophilic addition of in situ-generated allylaluminums to
aldehydes/Oppenauer oxidation.
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