The cobalt-catalyzed alkoxylation of C(sp(2) )H bonds in aromatic and olefinic carboxamides has been developed. The reaction proceeded under mild conditions in the presence of Co(OAc)2 ⋅4H2 O as the catalyst and tolerates a wide range of both alcohols and benzamide substrates, including even olefinic carboxamides. In addition, this reaction is the first example of the direct alkoxylation of alkenes through CH bond activation.

A highly efficient cobalt(II)-catalyzed alkynylation/annulation of terminal alkynes assisted by an N,O-bidentate directing group is described. This protocol is characterized by wide substrate scope utilizing cheap cobalt catalysts, and offers a new approach to 3-methyleneisoindolin-1-one, which can be converted into an oxadiazine salt in one step. Moreover, the directing group could be removed in three steps.

A nickel(II)-catalyzed alkynylation/annulation cascade via double C-H cleavage has been successfully achieved. This methodology adopted a removable N,O-bidentate directing group with a broad range of amide substrates and terminal alkynes being well tolerated. The catalytic system allowed for atom-economical and environmentally benign one-pot construction of the corresponding 3-methyleneisoindolin-1-one derivatives using O2 as the external oxidant.

The cobalt-catalyzed alkoxylation of C(sp 2 ) À H bonds in aromatic and olefinic carboxamides has been developed. The reaction proceeded under mild conditions in the presence of Co(OAc) 2 ·4H 2 O as the catalyst and tolerates a wide range of both alcohols and benzamide substrates, including even olefinic carboxamides. In addition, this reaction is the first example of the direct alkoxylation of alkenes through CÀH bond activation.

Ahighly efficient cobalt(II)-catalyzed alkynylation/ annulation of terminal alkynes assisted by an N,O-bidentate directing group is described. This protocol is characterized by wide substrate scope utilizing cheap cobalt catalysts,and offers anew approach to 3-methyleneisoindolin-1-one,whichcan be converted into an oxadiazine salt in one step.M oreover,t he directing group could be removed in three steps.

Cobalt(II)-Catalyzed C(sp 2 )-H Alkynylation/Annulation with TerminalAlkynes: Selective Access to 3-Methyleneisoindolin-1-one. -The cobalt(II)-oxalate-catalyzed reaction between arylacetylenes and N-protected arylamides with pyridin N-oxide as the directing group furnishes the title compounds in good to high yields and in a E/Z-selective manner (Z). -(ZHANG, L.-B.; HAO, X.-Q.; LIU, Z.-J.; ZHENG, X.-X.; ZHANG, S.-K.; NIU*, J.-L.; SONG, M.-P.; Angew. Chem., Int. Ed. 54 (2015) 34, 10012-10015, http://dx.doi.org/10.1002/anie.201504962 ; Coll. Chem. Mol. Eng., Zhengzhou Univ., Zhengzhou, Henan 450001, Peop. Rep. China; Eng.) -M. Tismer 52-104

A broad spectrum of amide substituents bearing the removable bidentate directing group ‐Pyo is treated with terminal aromatic acetylenes and the aliphatic analogue (XVIa) to produce the desired ring system, required as framework for the synthesis of alkaloids and bioactive compounds.

Cobalt-Catalyzed C(sp 2 )-H Alkoxylation of Aromatic and Olefinic Carboxamides. -The reaction proceeds under mild conditions in the presence of Co(OAc) 2·4H2O as the catalyst and tolerates a wide range of both alcohols and benzamide substrates, including even olefinic carboxamides. In addition, this reaction is the first example of the direct alkoxylation of alkenes through C-H bond activation. -(ZHANG, L.-B.; HAO, X.-Q.; ZHANG, S.-K.; LIU, Z.-J.; ZHENG, X.-X.; GONG, J.-F.; NIU*, J.-L.; SONG, M.-P.; Angew. Chem., Int. Ed. 54 (2015) 1, 272-275, http://dx.