The design of organometallic catalysts is crucial in the development of catalytic reactions. Herein, we describe a heterometallic [Os-Cu] complex with the characteristics of bimetallics, metallaaromatics, and pincer complexes. This complex serves as a highly effective catalyst for selective amino-and oxyselenation of unactivated alkenes. More than 80 examples including challenging substrates of unsymmetric aliphatic alkenes and amine-based nucleophiles in such reactions are provided. These reactions produce 1,2-difunctionalized products with good yields and high levels of chemo-, regio-, and stereoselectivity. Our studies revealed the following: (i) The usually inert osmium center activates the N-or O-centered nucleophiles. (ii) The copper−osmium bonding and its cooperative effects play essential roles in control the selectivity by bringing the reaction components into close proximity. (iii) The metallaaromatic moiety helps to stabilize the intermediate. These findings provide a versatile platform for catalyst design based on metal−metallaaromatic cooperative effects that have not been attained previously with bimetallic complexes.

A metal-free nitration of the C(sp 3 )ÀH bonds of 2-oxindoles with t-BuONO through radical coupling reaction at room temperature has been developed. Using t-BuONO both as a nitrating reagent and as an oxidant, to couple with the C(sp 3 )ÀH bonds of 2-oxindoles, thus forming a new CÀN bond without using any other reagents. This reaction provides a green and straightforward approach to some useful 3-nitro-2-oxindoles in moderate to good yields.

A novel metal-free C­(sp 3)–H amination of 2-oxindoles with alkylamines to afford C–N coupling products under mild conditions has been exploited. A series of 3-substituted 2-oxindoles and primary/secondary amines substrates were found to be well tolerated, affording the corresponding 3-substituted 3-aminooxindoles in 43%–92% yields. This method uses the economical and environmentally friendly “I2–TBHP” system, and the mechanistic studies revealed that the procedure undergoes through a radical pathway.

A new pattern for nitrative cyclization of 1,6-enynes with t-BuONO has been reported for the synthesis of various 2pyrrolidinone derivatives in 45−88% yields. This novel method is operationally simple and proceeds under very mild conditions without using any additives. The reaction pathway involves nitro radical addition toward an alkenyl group/5-exo-cyclization/Habstraction sequence, allowing a highly regioselective and practical protocol toward the formation of new C−N and C−C bonds.

A novel and environmentally attractive C(sp)-H azidation of 2-oxindoles involving the formation of a C-N bond was developed. This methodology achieved for the first time 3-azido-2-oxindole construction under metal-free conditions at room temperature via a radical strategy. PhI(OAc) was used as the oxidant and EtN was used as the additive in this transformation. Furthermore, the mechanistic study indicated that this azidation involved a radical process.