Chemospecific C3- and C2-Olefinations of Isatins by TfOH-Promoted Tandem Aldol-Grob and Semiacetalization-Grob Fragmentations.

A novel method for TfOH-promoted chemospecific C3- and C2-olefinations of isatins is developed, which offers the first examples of Grob fragmentation using isatins and amides as substrates.

Tandem Synthesis of 2-Azaspiro[4.5]deca-1,6,9-trien-8-ones Based on Tf2O-Promoted Activation of N-(2-Propyn-1-yl) Amides.

Structurally novel 2-azaspiro[4.5]deca-1,6,9-trien-8-ones were synthesized from N-(2-propyn-1-yl) amides and 1,3,5-trimethoxybenzenes by a tandem method consisting of a Tf2O-promoted amide activation and a TfOH-promoted Friedel-Crafts ipso-cyclization. The method offered the first example of using N-(2-propyn-1-yl) amides as substrates in both Tf2O-promoted secondary amide activation and the synthesis of azaspiro[4.5]deca-6,9-diene-8-ones.

Mechanistic Insights into Tf2O-Promoted Electrophilic Activation of 2-Propynamides and a New Synthesis of 2,4-Disubstituted Quinolines.

Direct evidence explaining why 2-propynamides have never been used as substrates in Tf2O-promoted electrophilic activations was obtained. Furthermore, a new method for the synthesis of structurally special 2,4-disubstituted quinolines was developed, by which the substituent at position 2 of quinolines can be diversified easily.

Bischler-Napieralski Synthesis of Polycyclic N-Heteroaromatics Based on Tf2O-Promoted Electrophilic Activation of N-Aryl-2-Propynamides.

2-Propynamides have been never used as substrates in classic and Tf2O-promoted Bischler-Napieralski reactions. In this article, a novel tandem synthesis of benzo[a]acridines is developed from N-aryl-2-propynamides and alkynes consisting of a Tf2O-promoted intermolecular Bischler-Napieralski reaction and a TfOH-promoted intramolecular Friedel-Crafts reaction.

Bischler-Napieralski Synthesis of 6-Alkynyl Phenanthridines Based on Tf2O-Promoted Electrophilic Activation of N-Aryl-2-propynamides.

An efficient method for the synthesis of 6-alkynyl phenanthridines was developed. The method offered the first example to use 2-propynamides as substrates in the Bischler-Napieralski reaction and to create alkynylnitrilium triflates as new active intermediates in organic synthesis.

Tandem Synthesis of 1,3-Disubstituted Naphthalenes via TfOH-Promoted Directed-Aldol and Friedel-Crafts Reactions.

A TfOH-promoted tandem synthesis of 1,3-disubstituted naphthalenes is developed via a directed-aldol reaction and a Friedel-Crafts reaction. Two new C-C bonds and one new benzene ring are created efficiently in one pot due to the discovery of a TfOH-promoted highly chemoselective directed-aldol reaction between two different ketones with α-hydrogens.

General Synthesis of Fully Substituted 4-Aminooxazoles from Amides and 1,4,2-Dioxazol-5-ones Based on Amide Activation and Umpolung Process.

A general and efficient synthesis of fully substituted 4-aminodixazoles was developed based on the strategies of amide activation and umpolung reaction. In this method, 1,4,2-dioxazol-5-ones were introduced as a rare type of umpolung reagent bearing a nucleophilic N-atom that could be used well together with the activating agent Tf2O. Because 1,4,2-dioxazol-5-ones played triple roles as an umpolung reagent, a substrate, and a weak base, the method proceeded smoothly under extremely convenient conditions.

General Synthesis of α-Alkyl Ynones from Morpholine Amides and 1-Copper(I) Alkynes Promoted by Triflic Anhydride.

The first general method for the synthesis of α-alkyl ynones was developed based on the strategy of electrophilic activation of amides. Its distinctive advantages are attributed to the use of air-stable "bare" 1-copper(I) alkyne as a mild nucleophile without any exogeneous ligand.

A Method for Bischler-Napieralski-Type Synthesis of 3,4-Dihydroisoquinolines.

A new method for the Bischler-Napieralski-type synthesis of 3,4-dihydroisoquinolines was developed by a Tf2O-promoted tandem annulation from phenylethanols and nitriles. Its success was mainly due to the fact that a phenonium ion was formed in the process and practically functioned as a stable and reactive primary phenylethyl carbocation.

Metal-Free Method for Direct Synthesis of Functionalized ß-Ketoenamines.

A new method for direct synthesis of ß-ketoenamines was developed by a BF3·OEt2-catalyzed cyclization of 1-iodoalkyne and α-keto acid followed by an amine-mediated ring-opening in one pot. Its metal-free conditions allowed the easy synthesis of those products bearing the transition metal-sensitive functional groups. Its three-component process achieved wide range of functionalized products.