105728-75-4

Upstream product

• 579-49-7 2-(4-fluorobenzoyl)thiophene 
• 80-70-6 N,N,N',N'-tetramethylguanidine 
• 100-10-7 4-dimethylamino-benzaldehyde 
• 30717-57-8 N, N-dimethylthiophene-2-carboxamide 
• 24167-52-0 N,N-dimethyl-3-chlorobenzamide 
• 121-69-7 N,N-dimethyl-aniline 
• 105728-67-4 2-<4-(Dimethylamino)phenyl>-2-(2-thienyl)-1,3-dithian 
• 586-77-6 4-bromo-N,N-dimethylaniline 
• 88372-95-6 thiophen-2-yl(trimethylsilyl)methanone 

Relevant academic research and scientific papers

The Halogen–Samarium Exchange Reaction: Synthetic Applications and Kinetics

Fast I/Sm and Br/Sm exchanges take place when various aromatic or heterocyclic iodides and bromides are treated with nBu2SmCl?4 LiCl and nBu3Sm?5 LiCl, respectively. The resulting organosamarium reagents were efficiently quenched with aldehydes, ketones, and imines. Also, they undergo acylations when treated with N,N-dimethylamides leading to ketones. The rate of the Br/Sm exchange for a typical aryl bromide was determined and found to be 8.5×105 faster than the Br/Mg exchange, indicating that the rate of a metal-exchange is related to the ionic character of the carbon–metal bond and to the metal electronegativity.

One-pot, modular approach to functionalized ketones via nucleophilic addition/Buchwald-Hartwig amination strategy

A general one-pot procedure for the 1,2-addition of organolithium reagents to amides followed by the Buchwald-Hartwig amination with in situ released lithium amides is presented. In this work amides are used as masked ketones, revealed by the addition of organolithium reagents which generates a lithium amide, suitable for subsequent Buchwald-Hartwig coupling in the presence of a palladium catalyst. This methodology allows for rapid, efficient and atom economic synthesis of aminoarylketones in good yields.

Magnesium salt promoted tandem nucleophilic addition-Oppenauer oxidation of aldehydes with organozinc reagents

A magnesium salt promoted synthesis of ketones via tandem nucleophilic addition-Oppenauer oxidation of aldehydes using organozinc chemistry was demonstrated. Magnesium salts concomitantly generated via magnesium metal mediated organohalide zincation exhibit high efficacy for nucleophilic addition of organozinc reagents to aromatic aldehydes and thereafter Oppenauer oxidation whereby ketones are formed in high to excellent yields.

Reversed-polarity synthesis of diaryl ketones through palladium-catalyzed direct arylation of 2-Aryl-1,3-dithianes

An umpolung approach to the synthesis of diaryl ketones has been developed based on in situ generation of acyl anion equivalents and their catalytic arylation. This method entails the base-promoted, palladium-catalyzed direct C-H arylation of 2- aryl-1,3-dithianes with aryl bromides. Use of ( SiMe3)2 (M=Li, Na) base results in reversible deprotonation of the weakly acidic dithiane. In the presence of a Pd(NiXantphos)-based catalyst and aryl bromide, cross-coupling of the metallated 2-aryl- 1,3-dithiane takes place under mild conditions (2 h at rt) with yields as high as 96%. The resulting 2,2- diaryl-1,3-dithianes were converted into diaryl ketones by either molecular iodine, N-bromo succinimide (NBS) or Selectfluor in the presence of water. The dithiane arylation/hydrolysis can be performed in a one-pot procedure to yield a variety of diaryl ketones in good to excellent yields. This method is suitable for rapid and large-scale synthesis of diaryl ketones. A one-pot preparation of anti-cholesterol drug fenofibrate (TriCor) has been achieved on 10.0 mmol scale in 86% yield.

Reversed-polarity synthesis of Diaryl Ketones through palladium-catalyzed direct Arylation of 2-Aryl-1,3-dithianes

An umpolung approach to the synthesis of diaryl ketones has been developed based on in situ generation of acyl anion equivalents and their catalytic arylation. This method entails the base-promoted, palladium-catalyzed direct C-H arylation of 2- aryl-1,3-dithianes with aryl bromides. Use of MNACHTUNGTRENUNG( SiMe3)2 (M=Li, Na) base results in reversible deprotonation of the weakly acidic dithiane. In the presence of a Pd(NiXantphos)-based catalyst and aryl bromide, cross-coupling of the metallated 2-aryl- 1,3-dithiane takes place under mild conditions (2 h at rt) with yields as high as 96%. The resulting 2,2- diaryl-1,3-dithianes were converted into diaryl ketones by either molecular iodine, N-bromo succinimide (NBS) or Selectfluor in the presence of water. The dithiane arylation/hydrolysis can be performed in a one-pot procedure to yield a variety of diaryl ketones in good to excellent yields. This method is suitable for rapid and large-scale synthesis of diaryl ketones. A one-pot preparation of anti-cholesterol drug fenofibrate (TriCor) has been achieved on 10.0 mmol scale in 86% yield.

Reversed-polarity synthesis of diaryl ketones via palladium-catalyzed cross-coupling of acylsilanes

Acylsilanes serve as acyl anion equivalents in a palladium-catalyzed cross-coupling reaction with aryl bromides to give unsymmetrical diaryl ketones. Water plays a unique and crucial activating role in these reactions. High-throughput experimentation techniques provided successful reaction conditions initially involving phosphites as ligands. Ultimately, 1,3,5,7-tetramethyl-6-phenyl-2,4,8-trioxa-6-phosphaadamantane was identified as giving a longer-lived catalyst with higher turnover numbers. Its use, in conjunction with a palladacycle precatalyst, led to optimal reaction rates and yields. Scope and limitations of this novel method are presented along with initial mechanistic insight.

Unusual aminations with tetramethylguanidine

Heating activated halobenzenes with 1,1,3,3-tetramethylguanidine affords mixtures of dimethylaminobenzenes and 2-aryl-1,1,3,3-tetramethylguanidines.

1,3-Dithienium and 1,3-Dithiolenium Salts, VI. - N,N-Disubstituted 4-Aminobenzophenones from 1,3-Dithian- and 1,3-Dithiolan-2-ylium Tetrafluoroborates, respectively

The 1,3-dithienium- and 1,3-dithiolenium tetrafluoroborates 3 (n =3, 2), respectively, react in good yields with the N,N-dialkylarylamines 4 to give the 2,2-disubstituted cyclic dithio acetals 5, which can be converted after dethioacetalization with HgCl2/HgO into the ketones 7.