Enantioselective Aminative Dearomatization of Indoles via Electrophilic 1,6-Addition of -Quinone Diimides (-QDIs).

Herein we report the first use of -quinone diimide for the aminative dearomatization of 2,3-disubstituted indoles to furnish C3 aza-quaternary chiral indolenines. This approach, which proceeds via an electrophilic 1,6-addition of -quinone diimide, allows the synthesis of an array of optically active aza-quaternary indolenines with high yields and excellent enantioselectivities. A one-pot approach of the same has also been established to further improve the synthetic accessibility of this protocol.

Sustainable Organic Photocatalysis for Site-Selective Hydrazocoupling of Electron-Rich Arenes.

An efficient photocatalytic - and selective amination and aminative dearomatization of phenols, naphthols, and anilines with azodicarboxylates was developed using riboflavin tetraacetate (RFTA) as an organic photocatalyst. The site selectivity was controlled using tetrabutylammonium bromide (TBAB), which also acts as a phase transfer catalyst. The reaction conditions are simple and mild, giving high regioselectivity with good to excellent yields.

Enantioselective Dearomative [4+2] Cycloaddition Reaction of 1-Naphthols with In-Situ Generated ortho-Quinone Methides.

We disclose a catalytic, enantioselective dearomative reaction of non-functionalized 1-naphthols, which poses a synthetic challenge to organic chemists because of the relative ease of rearomatization via the elimination of a proton. In this work, the direct dearomatization of non-functionalized 1-naphthols was achieved through a chiral phosphoric acid (CPA) catalyzed enantioselective dearomative [4+2] cycloaddition reaction with in-situ generated ortho-quinone methides (o-QMs). The reported convergent method allows the use of readily available simple 1-naphthols without pre-functionalization, furnishing a variety of naphthopyran derivatives in good yields (up to 96 %) and moderate to excellent enantioselectivities (up to >99 % ee) under mild reaction conditions.

Brønsted Acid Catalyzed Friedel-Crafts Alkylation of Naphthols with In Situ Generated Naphthol-Derived -Quinone Methides: Synthesis of Chiral and Achiral Xanthene Derivatives.

We disclose herein an enantioselective protocol for the Brønsted acid catalyzed addition of naphthols to in situ generated naphthol-derived -quinone methides (-QMs) followed by intramolecular cyclization, which delivers substituted chiral xanthene derivatives, in a one-pot reaction sequence under mild conditions. This process serves to convert naphthol-derived -hydroxyl benzylic alcohols into reactive naphthol-derived -QMs using a chiral phosphoric acid (CPA) catalyst. Moreover, it is helpful in controlling the enantioselectivity of the carbon-carbon bond-forming event via hydrogen-bonding followed by intramolecular cyclization.

Temperature-Controlled Chemoselective Synthesis of Multisubstituted 4-Alkynyl/ 4-Alkenyl Coumarins.

A temperature-controlled facile synthesis of multisubstituted 4-alkynyl/ 4-alkenyl coumarins with a metal salt cascade approach is reported. HO serves both as a nucleophile and hydrogen source. The presence of metal salt facilitates the reduction of alkyne.

Copper(i) catalyzed synthesis of selanyl methylene 4-chromanol and aurone derivatives.

An efficient copper-catalyzed cyclization cascade approach towards highly functionalized methylene 4-chromanol and aurone derivatives has been developed from reactions of ynols via 6-exo-dig and 5-exo-dig cyclization respectively. The catalysis involves alkyne activation via diorgano-diselenides and also their regioselective incorporation into the methylene 4-chromanol and aurone derivative core and is an open-air transformation.

Copper(I)-Catalyzed Synthesis of Functionalized Indolizinones from Substituted Pyridine Homologated Ynones.

An efficient two-component copper-catalyzed cyclization cascade approach toward highly functionalized indolizinone heterocycles has been developed from reactions of pyridine-, isoquinoline-, and quinoline ynones, via 5-- cyclization. The catalysis involves the activation by diorgano diselenide and diorgano disulfide and also their incorporation into the indolizinone core. In addition, the obtained substituted indolizinones were readily transformed into 1-(organochalcogenyl)indolizin-2-ols, which are important building blocks in organic synthesis.