RESUMEN
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.
RESUMEN
The structural design and tuning of properties of metallaaromatics are crucial in materials and energy science. Herein, we describe the rapid synthesis of tetracyclic metallaaromatics containing quinoline and pentalene motifs fused by a metal-bridged fragment. These unique compounds display remarkably broad absorption, enabling for the first time the absorption of metallaaromatics to reach the second near-infrared (NIR-II) bio-window. The formation of osmaquinoline unit involves an unconventional C(sp2 )-C(sp3 ) coupling promoted by AgBF4 to achieve [3+3] cycloaddition. The introduction of cyclic dπ -pπ conjugation and extension of the aromatic π-framework can effectively shrink the HOMO-LUMO gap, thus broadening the absorption window. The considerable photothermal conversion efficiency (PCE) in both the NIR-I and NIR-II windows, the high photothermal stability and the excellent electrochemical behavior suggest many potential applications of these condensed metallaquinolines.
RESUMEN
A good regioselective, high atom-economical and transition-metal-free method for the synthesis of α-functionalized ether derivatives via the domino radical cyclization of 1,6-enynes is described. A series of α-functionalized ether derivatives could be easily obtained in good yields with wide functional group tolerance by using less toxic and inexpensive Cs2CO3 as the base. The control experiment results show that the reaction involves a radical process. This strategy provides a regioselective way toward the formation of dual C-C bonds in one step.
RESUMEN
A novel and environmentally attractive C(sp3)-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)2 was used as the oxidant and Et3N was used as the additive in this transformation. Furthermore, the mechanistic study indicated that this azidation involved a radical process.