Selective functionalization of ubiquitous CÀ H bonds of molecules would provide novel retrosynthetic insights and powerful tools for the rapid construction of molecular complexity. In this context, Cp*Ir(III) complexes have exhibited versatile reactivity towards the selective conversion of CÀ H bonds, with key features that include the use of readily transformable raw materials, great selectivity (chemo-, stereo-and regio-), high efficiency, mild reaction conditions and they enable late-stage modification of complex molecules. Recently, Cp*Ir(III) catalysis has achieved a broad range of reactions such as multiple dehydrogenations and stereoselective CÀ X bond formations. These advancements are valuable to organometallic chemists and enable the efficient synthesis of functionalized architectures.
Primary sulfonamides are widely used structural skeletons in bioactive molecules, however their direct modification via C–H functionalization remains to be developed.
Streamlining the
generation of diverse highly functionalized molecules
from abundant feedstocks holds great synthetic promises and challenges
in pharmaceutical and material discovery. Herein, we report a tunable
selectivity in multiple cascade reactions for the divergent assembly
of fused N-heterocycles, comprising sequential activation
of C–H and C–C bonds. Isolatable indene-type intermediates
might be responsible for the generation of densely substituted fused
pyridines, azepines, and azafluorenones products. The tolerance of
strongly coordinating N-heterocycles, and those readily
applicable for the late-stage modifications of pharmaceuticals and
material molecules precursors, further demonstrated the synthetic
robustness of this transformation.
Medium N-heterocycles, azepines and azocines, serve as important skeletons that occurred widely in natural products, however, due to the lack of efficient synthetic methodologies, their application potential in biologically active molecules, pharmaceuticals and agrochemicals remained to be explored. In this context, rhodium catalysis in this field featured good reactivity and functional group tolerance, with readily available starting materials, and enabled rapid access to the azepines and azocines. Delightfully, great achievements in the concise construction of these 7 and 8-membered N-heterocycles under rhodium catalysis have been made, which mainly included cycloisomerization of unsaturated CÀ X bonds (which might also combine the ring-opening strategy on strained rings), metal carbenoid or nitrene insertion involved transformations and direct CÀ H activation reactions. Considering the great performance of rhodium catalyst in the synthesis of azepines and azocines, herein, we summarized the recent results in this field, and wish to give further insight and inspired more encouraging methodologies and new drug discovery based on these 7 and 8membered N-heterocycles.
The exploration of synthetic versatile, while weak coordinated amine derivatives enabled regioselective C‒H functionaliza-tion, remained challenging due to the elusive achievement of reactivity and selectivity simultaneously. Herein, with the assis-tance...
Modular construction of ployfunctional arenes from abundant feedstocks, stands as an unremitting pursue goal in synthetic chemistry, accelerating the discovery of drugs and materials. Herein, by using multiple C-H activation...
A switchable C‒H alkylation and N-alkylation with great chemo- and site-selectivity enbaled by N-nitrosoanilines was developed, affording functionalized anilines, hydrazines and heterocycles. The exploration of strain-release as key driving force...
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<p>Modular construction of multiple
functionalized arenes from abundant feedstocks, stands as an unremitting pursue
goal in synthetic chemistry, which would accelerate the discovery of new drugs
an advanced materials. Herein, by using multiple C-H activation strategy,
through judicious choice of versatile imidate ester as the key directing group,
expedi-ent delivery of molecular libraries of densely functionalized
sulfur-contained arenes. Further synthetic application was demonstrated by
multiple C-H modification of fused arenes and pharmaceuticals such as
Ibuprofen, and concise con-struction of biologically active molecules, Madam
dihydrochloride and Bipenamol, was also achieved.</p>
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