Expedient (3+3)-annulation of carbonyl ylides with azaoxyallyl cations: formal access to oxa-benzo[]azepin-3-ones.

The cascade carbon-carbon and carbon-nitrogen bond formation between generated carbonyl ylides and azaoxyallyl cations, facilitated by Rh-catalysis and a base, has been achieved to furnish oxa-benzo[]azepin-3-ones. Substrate scope, functional group diversity, scale-up and post-synthetic utilities are the important practical features.

Ru-Catalyzed Redox-Neutral Coupling of -Chlorobenzamides with Unsymmetrical Alkynes in Water.

In water, Ru-catalyzed annulation of -chlorobenzamides with unsymmetrical internal alkynes bearing aryl, hydroxy, ester, and sulfonyl functionalities has been accomplished to afford isoquinolone scaffolds under external oxidant-free conditions at room temperature. Use of water as reaction medium, redox-neutral conditions, regioselectivity, and substrate scope are important practical features.

Diastereocontrolled Construction of Spiroindolenines via Hexafluoroisopropanol-Promoted Dearomative Epoxide-Indole Cyclization.

Herein, we report the discovery of the -selective, dearomatizing spirocyclization of indole-tethered epoxides as a fundamentally new approach for constructing spiroindolenines equipped with three contiguous stereogenic centers under complete diastereocontrol (dr >99:1) and in high yields. Promoted by hexafluoroisopropanol, the protocol features a broad substrate scope, easy scale-up, and versatile transformations of the synthesized spiroindolenines.

Expedient C-H allylation of sulfoxonium ylides: merging C-H and C-C/C-het bond activation.

Sulfoxonium ylide chelation-assisted C-H allylation of arenes has been accomplished utilizing strained vinyl carbo/heterocycles as the allyl surrogates sequential C-H and C-C/het bond activation. Broad substrate scope, Co-catalysis, selectivity, and late-stage drug mutation are the important practical features.

Sc(OTf)-Catalyzed Domino C-C/C-N Bond Formation of Aziridines with Quinones via Radical Pathway.

Sc(III)-catalyzed domino C-C and C-N bond formation of -sulfonyl aziridines with quinones has been accomplished to furnish functionalized indolines at a moderate temperature. The umpolung reactivity of aziridines, radical pathway, mild reaction conditions, substrate scope, and coupling of drug molecules in a postsynthetic application are the important practical features.

Redox-Neutral Site-Selective C-H Allylation and Iodolactonization of Benzoic Acids Using Morita-Baylis-Hillman Adducts in Water.

A Ru-catalyzed carboxylate directed C-H allylation and iodolactonization of benzoic acids has been accomplished with Morita-Baylis-Hillman adducts as the coupling partner in environmentally benign water as solvent. The redox-neutral conditions, use of water as a solvent, substrate scope, functional group tolerance, and mutation of natural products and drug molecules are the important practical features.