Cobalt-Catalyzed Synthesis of Alkenyl Heterocycles via Regioselective Intramolecular 1,4-Hydrofunctionalization of Dienes.

We report a novel cobalt-catalyzed intramolecular 1,4-hydrofunctionalization of dienes. The reaction proceeds under mild conditions and is amenable to N- and O-nucleophiles. The protocol exhibits exclusive regioselectivity, yielding a number of different alkenyl heterocycles, including but not limited to dihydroisobenzofurans, isochromanes, tetrahydrofurans, morpholines, lactones, and isoindolines.

Palladium-catalyzed ring-opening [5+2] annulation of vinylethylene carbonates (VECs) and C5-substituted Meldrum's acids: rapid synthesis of 7-membered lactones.

A novel approach for the synthesis of unsaturated 7-membered lactones by Pd-catalyzed [5+2] dipolar cycloaddition of vinylethylene carbonates (VECs) and C5-substituted Meldrum's acid derivatives has been developed. Various Meldrum's acid derivatives worked well in this reaction under mild reaction conditions. A variety of 7-membered lactones can be accessed in a facile manner in moderate to good yields by employing easily prepared Meldrum's acid derivatives.

Diastereoselective Synthesis of 1,2-Dihydrobenzofuro[3,2-]pyridines via a Carbon-Carbon Double-Bond Cleavage/Rearrangement Cascade.

A new Lewis acid-catalyzed [2 + 2] cycloaddition/retroelectrocyclization (CA-RE)/1,6-addition relay of aurone-derived 1-azadienes and 1-alkynylnaphthalen-2-ols has been reported, leading to the regio- and diastereoselective synthesis of 1,2-dihydrobenzofuro[3,2-]pyridine with a chiral carbon center and an axial chirality in good yields. This protocol enables the C-C double-bond scission/recombination to rapidly construct aza-heterocyclic architectures and features 100% atom utilization, a wide substrate scope, good compatibility with substituents, and excellent diastereoselectivity.

Electrochemical Annulation-Iodosulfonylation of 1,5-Enyne-containing -Quinone Methides (-QMs) to Access ()-Spiroindenes.

A new electrochemical three-component annulation-iodosulfonylation of 1,5-enyne-containing -quinone methides (-QMs) has been established by using available arylsulfonyl hydrazides and potassium iodide under environmentally benign conditions. The electrosynthesis offers sustainable and efficient access to construct spirocyclohexadienone-containing ()-indenes without any additional catalyst or oxidant through a sulfonyl-radical-triggered 1,6-addition and an I-mediated -cyclization cascade. Notably, potassium iodide plays the triple role of an electrolyte, a redox catalyst, as well as an iodination reagent.

Pd(II)-Catalyzed Carbonyl-Directing Activation of Alkenes: Selective Fluorosulfonylation and Aminosulfonylation of 1,7-Enynes.

A new Pd(II)-catalyzed carbonyl-directing activation of alkenes has been established, enabling radical-induced selective fluorosulfonylation and aminosulfonylation of carbonyl-tethered 1,7-enynes with sulfinic acids and N-fluorobenzenesulfonimide (NFSI) under mild and redox neutral conditions to access densely functionalized ( E)-3,4-dihydronaphthalen-1(2 H)-ones with generally good yields and high stereoselectivity. The selectivity of these bifunctionalizations relies on the electronic nature of substituents on both aryl rings of 1,7-enynes.