Oxidative coupling of tetraalkynyltin with aldehydes leading to alkynyl ketones

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.

Tetraalkynylstannanes in Synthesis of α,β-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…”

“…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].…”

Crystal structure of 3-(4-methoxyphenyl)-1-phenylprop-2-yn-1-one, C16H12O2

“…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].…”

“…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.…”

Copper-Catalyzed Hydroalumination of Allenes with Diisobutylaluminum Hydride: Synthesis of Allylic Ketones with α-Quaternary Centers via Tandem Allylation/Oppenauer Oxidation

“…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 .…”