Reported herein is the pyrazole-directed iridium-catalyzed enantioselective borylation of unbiased methylene C-H bonds at the position β to a nitrogen center. The combination of a chiral bidentate boryl ligand, iridium precursor, and pyrazole directing group was responsible for the high regio- and enantioselectivity observed. The method tolerated a vast array of functional groups to afford the corresponding C(sp3 )-H functionalization products with good to excellent enantioselectivity.

Iridium-Catalyzed Regio- and Enantioselective Borylation of Unbiased Methylene C(sp3 )-H Bonds at the Position β to a Nitrogen Center.

Quinuclidine and its derivatives as hydrogen-atom-transfer catalysts in photoinduced reactions

C-H functionalization is one of the most convenient and powerful tools in the arsenal of modern chemistry, deservedly nominated as the "Holy Grail" of organic synthesis. A frequent disadvantage of this method is the need for harsh reaction conditions to carry out transformations of inert C-H bonds, which limits the possibility of its use for modifying less stable substrates. Biomass-derived furan platform chemicals, which have a relatively unstable aromatic furan core and highly reactive side chain substituents, are extremely promising and valuable organic molecules that are currently widely used in a variety of research and industrial fields. The high sensitivity of furan derivatives to acids, strong oxidants, and high temperatures significantly limits the use of classical methods of C-H functionalization for their modification. New methods of catalytic functionalization of non-reactive furan cores are urgently required to obtain a new generation of materials with controlled properties and potentially bioactive substances.

Catalytic C−H Functionalization of Unreactive Furan Cores in Bio‐Derived Platform Chemicals

Herein, we report an efficient methodology for the synthesis of alkyl, benzyl, and phenyl selenoethers of aminopyrazoles and aminouracils by C(sp2)-H functionalization in the presence of visible light and Rose Bengal as an organophotocatalyst. The reaction of amino pyrazole/iosothiazole/isoxazole or amino uracils with 0.5 equivalent of diphenyl/dibenzyl/diethyl diselenides in the presence of visible light in acetonitrile medium and a catalytic amount of Rose Bengal provided the corresponding phenyl, benzyl, or ethyl selenoethers in good to very good yields. We have also utilized some of the selenylated aminopyrazoles for the preparation of pyrazole-fused dihydropyrimidines tethered with arylselenoethers by a catalyst-free one-pot three-component reaction. The notable features of this methodology are metal-free reaction conditions, good to very good yields, use of an organic photocatalyst, and wide substrate scope; it is also applicable to gram-scale synthesis and provides selenoethers of medicinally important heterocycles such amio-pyrazole, isoxazole, isothiazole, and uracils.

Visible Light-Mediated C(sp2)-H Selenylation of Amino Pyrazole and Amino Uracils in the Presence of Rose Bengal as an Organophotocatalyst.

Transition-metal-catalyzed C-H functionalization is one of the fascinating scientific fronts in organic synthesis for the formation of conjugated arenes and has emerged as a benchmark to revolutionize the synthetic enterprise since past decades. In this realm, chelation-guided functionalization of C-H bonds using an exogenous directing group has received considerable attention recently for the expedient regioselective construction of C-C and C-heteroatom bonds as an efficient and sustainable alternative. This article outlines our contribution towards a wide variety of transformations that have been achieved by the directed C-H functionalization through the fine tuning of catalytic systems.

Transition-Metal-Catalyzed Directing Group Assisted (Hetero)aryl C-H Functionalization: Construction of C-C/C-Heteroatom Bonds.

This review describes recent advances in transition-metal-catalyzed C–H functionalization reactions of pyrazoles to form new C–C and C–heteroatom bonds on the pyrazole ring. In contrast to traditional cross-coupling reactions that require pre-functionalized pyrazoles, direct C–H functionalization reactions provide access to a wide range of functionalized pyrazoles in a single step. Various strategies are presented and the efficiency and regioselectivity are described with respect to the types of functional groups that are installed.

Eunsu Kang

Papers

Transition-metal-catalyzed C–H functionalization of pyrazoles

Synthesis of Bidentate Nitrogen Ligands by Rh-Catalyzed C-H Annulation and Their Application to Pd-Catalyzed Aerobic C-H Alkenylation.

Pd-Catalyzed Cyclization of Alkynyl Norbornene Derivatives for the Synthesis of Benzofused Heteroarenes

Sterically controlled C-H alkenylation of pyrroles and thiophenes.

Nondirected Pd-catalyzed aerobic C-H alkenylation of ruthenocene and ferrocene.