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Full-Text Articles in Physical Sciences and Mathematics
One-Pot Synthesis Of 2-Methylfurans From 3- (Trimethylsilyl)Propargyl Acetates Promoted By Trimethylsilyl Trifluoromethanesulfonate, Danielle E. Sklar, Alex V. Helbling, Yiqi Liu, C. Wade Downey
One-Pot Synthesis Of 2-Methylfurans From 3- (Trimethylsilyl)Propargyl Acetates Promoted By Trimethylsilyl Trifluoromethanesulfonate, Danielle E. Sklar, Alex V. Helbling, Yiqi Liu, C. Wade Downey
Chemistry Faculty Publications
In the presence of trimethylsilyl trifluoromethanesulfonate (TMSOTf) and triethylamine, 3-(trimethylsilyl)propargyl carboxylates undergo a one-pot alkylation-cyclization- desilylation reaction with ketones to produce 2-methylfurans. Alkylation at 0 °C in methylene chloride, followed by acid-catalyzed cyclization at room temperature, provides the furans in 52-86% yield. Cyclization and desilylation appear to be promoted by triflic acid generated in situ from the exposure of the reaction mixture to water upon completion of the initial substitution reaction.
One-Pot Silyl Ketene Imine Formation-Nucleophilic Addition Reactions Of Acetonitrile With Acetals And Nitrones, C. Wade Downey, Grace Ann L. Robertson, Jhonmattew Santa, Kari R. Flicker, William M. Stith
One-Pot Silyl Ketene Imine Formation-Nucleophilic Addition Reactions Of Acetonitrile With Acetals And Nitrones, C. Wade Downey, Grace Ann L. Robertson, Jhonmattew Santa, Kari R. Flicker, William M. Stith
Chemistry Faculty Publications
Trimethylsilyl trifluoromethanesulfonate (TMSOTf) and a trialkylamine base promote the conversion of acetonitrile to its silyl ketene imine in situ when acetonitrile is employed as solvent. Residual TMSOTf acts as a Lewis acid catalyst to activate acetals and nitrones in the reaction mixture, yielding β-methoxynitriles and β-(silyloxy)aminonitriles, respectively. Some reaction products undergo elimination under the reaction conditions to provide the α,β-unsaturated nitrile directly.
One-Pot Enol Silane Formation-Mukaiyama Aldol Reactions: Crossed Aldehyde-Aldehyde Coupling, Thioester Substrates, And Reactions In Ester Solvents, C. Wade Downey, Grant J. Dixon, Jared A. Ingersoll, Claire A. Fuller, Kenneth W. Maccormac, Anna Takashima, Rohina Sediqui
One-Pot Enol Silane Formation-Mukaiyama Aldol Reactions: Crossed Aldehyde-Aldehyde Coupling, Thioester Substrates, And Reactions In Ester Solvents, C. Wade Downey, Grant J. Dixon, Jared A. Ingersoll, Claire A. Fuller, Kenneth W. Maccormac, Anna Takashima, Rohina Sediqui
Chemistry Faculty Publications
Trimethylsilyl trifluoromethanesulfonate (TMSOTf) and a trialkylamine base promote both in situ enol silane/silyl ketene acetal formation and Mukaiyama aldol addition reactions between a variety of reaction partners in a single reaction flask. Isolation of the required enol silane or silyl ketene acetal is not necessary. For example, crossed aldol reactions between α-disubstituted aldehydes and non-enolizable aldehydes yield b- hydroxy aldehydes in good yield. In a related reaction, the common laboratory solvent ethyl acetate functions as both an enolate precursor and a green reaction solvent. When thioesters are employed as enolate precursors, high yields for additions to non-enolizable aldehydes are routinely …
Chalcone And Cinnamate Synthesis Via One-Pot Enol Silane Formation-Mukaiyama Aldol Reactions Of Ketones And Acetate Esters, C. Wade Downey, Hadleigh M. Glist, Anna Takashima, Samuel R. Bottum, Grant J. Dixon
Chalcone And Cinnamate Synthesis Via One-Pot Enol Silane Formation-Mukaiyama Aldol Reactions Of Ketones And Acetate Esters, C. Wade Downey, Hadleigh M. Glist, Anna Takashima, Samuel R. Bottum, Grant J. Dixon
Chemistry Faculty Publications
Aryl alkyl ketones, acetate esters, and acetamides undergo facile one-pot enol silane formation, Mukaiyama aldol addition, and dehydrosilyloxylation in the presence of an amine base and excess trimethylsilyl trifluoromethanesulfonate. The chalcone and cinnamate products are generally recovered in high yield. The relative stoichiometry of the trimethylsilyl trifluoromethanesulfonate and amine base reagents determines whether the reaction yields the β- silyloxy carbonyl product or the α, β -unsaturated carbonyl.
Synthesis Of N-Acyl-N,O-Acetals From N-Aryl Amides And Acetals In The Presence Of Tmsotf, C. Wade Downey, Alan S. Fleisher, James T. Rague, Chelsea L. Safran, Megan E. Venable, Robert D. Pike
Synthesis Of N-Acyl-N,O-Acetals From N-Aryl Amides And Acetals In The Presence Of Tmsotf, C. Wade Downey, Alan S. Fleisher, James T. Rague, Chelsea L. Safran, Megan E. Venable, Robert D. Pike
Chemistry Faculty Publications
Secondary amides undergo in situ silyl imidate formation mediated by TMSOTf and an amine base, followed by addition to acetal acceptors to provide N-acyl-N,O-acetals in good yields. An analogous, high-yielding reaction is observed with 2-mercaptothiazoline as the silyl imidate precursor. Competing reduction of the acetal to the corresponding methyl ether via transfer hydrogenation can be circumvented by the replacement of i-Pr2NEt with 2,6-lutidine under otherwise identical reaction conditions.
A Tandem Enol Silane Formation-Mukaiyama Aldol Reaction Mediated By Tmsotf, C. Wade Downey, Miles W. Johnson
A Tandem Enol Silane Formation-Mukaiyama Aldol Reaction Mediated By Tmsotf, C. Wade Downey, Miles W. Johnson
Chemistry Faculty Publications
A slight excess of silyl trifluoromethanesulfonate mediates a tandem enol silane formation-Mukaiyama aldol reaction in the presence of Hunig’s base. Preformation of the enol silane is unnecessary for efficient reactions, which proceed in 75–97% yield for the addition of aryl methyl ketones and acetate esters to non-enolizable aldehydes. Mechanistic data suggests that free amine is crucial for full conversion.