A novel cascade reaction has been described for the synthesis of Carbolines via palladium‐catalyzed successive C–C/C–N formation from O‐methylketoximes and styrenes. The oxime ether auxiliary not only serves as a traceless directing group, but is also partly transformed into the value‐added pharmacophore in a two‐step, one‐pot fashion.

A novel route for tandem C−C/C−N formation via palladium-catalyzed C−H activation/styrenation and annulation of O-methylketoxime with styrenes to synthesize benzothienopyridines and benzofuropyridines has been developed. Furthermore, the intermolecular alkenylation of the ketoxime with acrylates produces 3-alkenyl O-methylketoximes in good to excellent yields. The method features mild reaction conditions and good functional group tolerance, providing a direct approach for the preparation of fused heterocycles.O ver the past decades, the directing group protocol of transition-metal-catalyzed C−H bond functionalization has become a powerful method for C−C and C−X bond formation reactions. 1 The value of this strategy achieves high regio-and stereoselectivity in terms of atom-and stepeconomic nature. As one of the most widely used protocols, the oxidative functionalizations of alkenes have attracted more attention in recent years. 2 Ortho alkenylation with the assistance of various directing groups such as carboxyl, 3 amide, 4 ester, 5 pyridine, 6 and others 7 has been extensively reported.Oxime ethers possess an excellent directing ability for C−H bond activation. 8 Previous works have demonstrated palladium-catalyzed oxime-ether-directed ortho C(sp 2 )−H functionalization, 9 such as arylation, 9a,c acylation, 9b acyloxylation, 9d,h alkoxylation, 9h and hydroxylation. 9g Aside from the above functionalized reactions, the alkenylation assisted by oxime ether has not been well explored. In 2011, Ellman and co-workers 9e reported the oxidative coupling of oxime ethers with unactivated alkenes using a cationic Rh (III) catalyst. Sun's group 9f demonstrated the ortho olefination of arylaldehyde oximes with activated olefins through a Pd(II) catalyst. More recently, Jeganmohan's group 9i described the rutheniumcatalyzed oxidant-free ortho alkenylation of aromatic amides, ketoximes, and anilides with alkenes (Scheme 1). Despite

A method for ortho-C−H borylation of diphenylamines using BBr 3 as the boron source has been reported. The noncatalytic adamantane-1-carbonyl directed reaction exhibited site exclusivity and good functional group tolerance. Generally, the borylation occurred at the more electron-rich aromatic ring and the borylated products could be converted to various useful intermediates. Besides, the derived arylation and removal of auxiliary of the product could be achieved in a one-pot fashion.A s a highly important class of chemicals, diphenylamines are frequently found among drugs, dyes, agrochemicals, explosive stabilizers, and radical trapping antioxidants, such as diclofenac sodium, mefenamic acid, and clausine E (Figure 1). 1

A novel route for ruthenium(II)-catalyzed αfluoroalkenylation of oxime ethers with gem-difluorostyrenes via C−H activation and C−F cleavage has been developed for the first time. Notably, the alkenyl units of products exhibit exclusive Zconfiguration. This reaction features a broad substrate scope and good functional group tolerance. A plausible reaction mechanism is confirmed by an available cycloruthenated intermediate. Besides, the O-methyl oximyl-directing group can be readily removed to access the α-fluoroalkenylated acetophenones.

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