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The first copper-catalyzed enantioselective [4 + 1] annulation of yne-allylic esters with 1,3-dicarbonyl compounds was realized through an elegant remote stereocontrol strategy. The very remote ε regioselective nucleophilic substitution was developed by employing a novel chiral copper-vinylvinylidene species from the new C4 synthon yne-allylic esters. Thus, greatly diverse spirocycles were obtained with ample scope and excellent levels of chemo-, regio-, and enantioselectivities. Moreover, detailed mechanistic studies suggest an yne-allylic substitution and Conia-ene cascade pathway on the remote stereochemical induction progress.

Anthrones are key structural motifs in many natural products, bioactive compounds and pharmaceutical chemicals. Earth-abundant-metal-catalyzed asymmetric functionalization of anthrones has not proved to be viable. Herein, we disclosed a highly enantioselective propargylic substitution of anthrones with propargylic esters using copper salts with chiral N, N, P-ligand. This strategy is amenable to a broad range of substrates, uses readily available starting materials, provides excellent yields with remarkable enantioselectivity under mild conditions, and enables attractive products diversification routes.

Catalyst-free, direct electrooxidative phenol derivatives C(sp3)–H mono- and di-alkylation reaction have been developed.

Distinct regio- and enantioselectivity control in copper-catalyzed vinylogous and bisvinylogous propargylic substitution has been accomplished by using a novel chiral

Efficient and selective molecular syntheses are paramount to inter alia biomolecular chemistry and material sciences as well as for practitioners in chemical, agrochemical, and pharmaceutical industries. Organic electrosynthesis has undergone a considerable renaissance and has thus in recent years emerged as an increasingly viable platform for the sustainable molecular assembly. In stark contrast to early strategies by innate reactivity, electrochemistry was recently merged with modern concepts of organic synthesis, such as transition-metal-catalyzed transformations for inter alia C–H functionalization and asymmetric catalysis. Herein, we highlight the unique potential of organic electrosynthesis for sustainable synthesis and catalysis, showcasing key aspects of exceptional selectivities, the synergism with photocatalysis, or dual electrocatalysis, and novel mechanisms in metallaelectrocatalysis until February of 2021., Organic electrosynthesis has unique potential and showcases exceptional selectivities, synergism with photocatalysis, or dual electrocatalysis, and novel mechanisms in metallaelectrocatalysis.

Rhodium(III) catalysis has set the stage for a plethora of oxidative C–H functionalizations over the last decade, which have predominantly employed stoichiometric amounts of toxic and expensive met...

Electrochemical C(sp

Distinct selectivity control in Cp*CoIII-catalyzed domino C–H activation/pyridine directing group migration/alkyne annulation has been accomplished through the nucleophilicity of an organometallic ...

Despite major advances, organometallic C−H transformations are dominated by precious 5d and 4d transition metals, such as iridium, palladium and rhodium. In contrast, the unique potential of less toxic Earth‐abundant 3d metals has been underexplored. While iron is the most naturally abundant transition metal, its use in oxidative, organometallic C−H activation has faced major limitations due to the need for superstoichiometric amounts of corrosive, cost‐intensive DCIB as the sacrificial oxidant. To fully address these restrictions, we describe herein the unprecedented merger of electrosynthesis with iron‐catalyzed C−H activation through oxidation‐induced reductive elimination. Thus, ferra‐ and manganaelectro‐catalyzed C−H arylations were accomplished at mild reaction temperatures with ample scope by the action of sustainable iron catalysts, employing electricity as a benign oxidant., Electro with Ironman: Electricity‐enabled resource‐economic C−H activations by iron and manganese catalysis, avoiding precious metals and toxic chemical oxidants.

Low-valent manganese-catalyzed C-H alkylation of pyridine derivatives with both primary and challenging secondary alkyl halides was established by amide assistance. The strategy provided expedient access to alkylated pyridines with wide functional group tolerance and ample scope through weak chelation. Mechanistic studies provided strong support for a rate-determining C-H activation and a SET-type C-X scission.

Versatile manganese-catalyzed C–H arylations on synthetically meaningful pyridines were accomplished with sustainable MnCl2 as the catalyst. The oxidative C–H functionalizations proved viable with a user-friendly and safe continuous flow setup by weak amide-assisted C–H cleavage via a facile C–H activation regime.

Methods for positionally selective remote C−H functionalizations are in high demand. Herein, we disclose the first heterogeneous ruthenium catalyst for meta-selective C−H functionalizations, which enabled remote halogenations with excellent site selectivity and ample scope. The versatile heterogeneous Ru@SiO2 catalyst was broadly applicable and could be easily recovered and reused, which set the stage for the direct fluorescent labeling of purines. In contrast to palladium, rhodium, iridium, or cobalt complexes, solely the ruthenium catalysis manifold provided access to meta-halogenated purine derivatives, illustrating the unique power of ruthenium C−H activation catalysis.

Ruthenium(II)-catalyzed meta-selective C-H (di)fluoromethylation was accomplished by phosphine and carboxylate cooperation. The remote C-H functionalization was characterized by ample substrate scope, thereby setting the stage for meta-(di)fluoromethylation through facile C-H cleavage.

Complexity-increasing Domino reactions comprising C-H allenylation, a Diels-Alder reaction, and a retro-Diels-Alder reaction were realized by a versatile catalyst derived from earth-abundant, non-toxic manganese. The C-H activation/Diels-Alder/retro-Diels-Alder alkyne annulation sequence provided step-economical access to valuable indolone alkaloid derivatives through a facile organometallic C-H activation manifold with transformable pyridines.

Low-valent manganese-catalyzed C-H alkylation of pyridine derivatives with both primary and challenging secondary alkyl halides was established by amide assistance. The strategy provided expedient access to alkylated pyridines with wide functional group tolerance and ample scope through weak chelation. Mechanistic studies provided strong support for a rate-determining C-H activation and a SET-type C-X scission.

The unprecedented carbodiimide-mediated condensation between pyridines and anthranilic acids via pyridine dearomatization at room temperature has been developed to provide a straightforward approach to pyridoquinazolones. The value of this approach has further been demonstrated by its application to one-step, gram-scale syntheses of a series of pyridoquinazolone-based natural products and their analogues from readily available starting materials.

meta-Selective C-H alkylations of bioactive purine derivatives were accomplished by versatile ruthenium catalysis. Thus, the arene-ligand-free complex [Ru(OAc)2 (PPh3 )2 ] enabled remote C-H functionalizations with ample scope and excellent levels of chemo- and positional selectivities. Detailed experimental and computational mechanistic studies provided strong support for a facile C-H activation within a ruthenium(II/III) manifold.

C–H arylations of weakly coordinating benzoic acids were achieved by versatile ruthenium(II) catalysis with ample substrate scope. Thus, user-friendly ruthenium(II) biscarboxylate complexes modified with tricyclohexylphosphine enabled C–H functionalizations with aryl electrophiles. The unique versatility of the ruthenium(II) catalysis manifold was reflected by facilitating effective C–H activations with aryl, alkenyl and alkynyl halides. peerReviewed