Recent advances in transition metal-catalyzed C–H bond functionalization have profoundly impacted synthetic strategy Since organic substrates typically contain several chemically distinct C–H bonds, controlling the regioselectivity of C–H bond functionalization is imperative to harness its full potential Moreover, the ability to alter reaction pathways to selectively functionalize different C–H bonds in a substrate represents a greater opportunity and challenge The choice of catalysts, ligands, solvents, and even more subtle variations of the reaction conditions have been shown to allow the formation of regioisomeric C–H functionalization products starting from the same precursors This review describes recent advances in transition metal-catalyzed divergent C–H bond functionalization that highlight its potential in organic synthesis

Transition metal-catalyzed site- and regio-divergent C–H bond functionalization

The development of a rational strategy to achieve the complete regioselectivity and the capability to switch regioselectivity is an appealing, yet challenging, puzzle in transition-metal-catalyzed ...

C2/C4 Regioselective Heteroarylation of Indoles by Tuning C–H Metalation Modes

We have developed a novel indole-catalyzed bromolactonization of olefinic acids. The reaction could be conducted in lipophilic solvent through a solid–liquid phase transfer mechanism. This catalytic protocol has been applied to the synthesis of base-sensitive bromolactones.

http://pubs.acs.org/doi/pdf/10.1021/acscatal.5b01182

Indole-Catalyzed Bromolactonization in Lipophilic Solvent: A Solid–Liquid Phase Transfer Approach

The activation of ethyl bromofluoroacetate employing a visible light mediated, Eosin Y catalyzed photoredox transformation is reported. Using indoles and anilines as nucleophiles, the reaction leads to the formation of two Csp2–Csp3 bonds resulting in an efficient synthesis of bisindolyl and bisanilinoyl acetate derivatives. Application of this method to the direct synthesis of unsymmetrical diarylacetates featuring indoles and N-substituted anilines was also demonstrated.

Visible Light Mediated Organocatalytic Activation of Ethyl Bromofluoroacetate: Coupling with Indoles and Anilines

A strategy to the 6-5-6 tricyclic scaffold of taiwaniaquinoids was established on the basis of a one-pot thermal ring expansion/4π-electrocyclization process. The efficiency of this methodology has been demonstrated through its application in the total synthesis of taiwaniaquinone H, which has been accomplished in three steps and 14% overall yield in a protecting-group-free manner starting from commercially available materials.

Protecting-group-free synthesis of taiwaniaquinone H using a one-pot thermal ring expansion/4π-electrocyclization strategy.

The first total synthesis of asterredione was efficiently accomplished over five linear steps and in 21.5% overall yield. As the crucial step, the 2-quaternary 1,3-cyclopentenedione skeleton of asterredione was readily achieved using the Darzens/ring-expansion strategy developed in our laboratory. The structure of synthesized asterredione was fully confirmed by X-ray crystallography.

Total synthesis of asterredione.

The synthesis of the title compound (I) is accomplished over five linear steps in 21.5% overall yield.

Sinan Gai

Papers

Total synthesis of asterredione.

Total Synthesis of Asterredione.