Metal-free C-H Borylation and Hydroboration of Indoles.

The C-H borylation and hydroboration reactions have emerged as promising synthetic tools to construct organoboron compounds. Organoboron compounds of N-heterocycles, particularly indole derivatives, have found widespread application in a variety of fields. As a result, considerable advancement in the area of C-H borylation and hydroboration reactions of indoles was observed in the last few decades. Among the various synthetic methods applied, the metal-free approach has received special attention. This mini-review discusses the recent progress in the area of C-H borylation and hydroboration reactions of indoles under metal-free conditions, their scope, and brief mechanistic studies.

Dual Role of TiO(acac)2 as a Reagent and an Activator/Catalyst: A Study on the Solvent Dependent Product Formation.

The dual operation of a chemical species in synthetic chemistry is an intriguing and relatively unexplored phenomenon. The application of such a species is expected to reduce the use of multiple reaction partners and catalysts/activators. Herein, we report a simple and easy-to-use protocol for the twin application of TiO(acac)2 , as a reagent and an activator to synthesize ß-enamino ketones with amines in acetonitrile. The same early transition metal precursor when employed in N,N-dimethylformamide with the amines, resulted in the formation of the substituted amides. Both reactions were explored with various substrates to check the viability of the present protocol. Moreover, experimental studies were conducted to understand the mechanism of both reactions.

A Lewis Acid-Base Pair Catalyzed Dearomative Transformation of Unprotected Indoles via B-H Bond Activation.

A sustainable and metal-free protocol has been described for the reduction of unprotected indoles. The catalytic system consists of B(C6 F5 )3 and THF as a Lewis acid-base pair that can activate the B-H bond of pincolborane (HBpin). The catalytic system encompasses a broad substrate scope. Control experiments were conducted to understand the possible catalytic intermediates involved during the present protocol.

Catalytic and Mechanistic Approach to the Metal-Free N-Alkylation of 2-Aminopyridines with Diketones.

N-alkylation of amines is an important catalytic reaction in synthetic chemistry. Herein, we report a simple strategy for the N-alkylation of 2-aminopyridines with 1,2-diketones using BF3·OEt2 as a catalyst. The reaction proceeds under aerobic conditions, leading to the formation of a diverse range of substituted secondary amines in good to excellent yields. A close inspection of the mechanistic pathway using various spectroscopic techniques and the computational study revealed that the reaction proceeds through the formation of an iminium-keto intermediate with the liberation of CO2.

Mechanistic Understanding of KOt Bu-Mediated Direct Amidation of Esters with Anilines: An Experimental Study and Computational Approach.

A sustainable and cost-effective protocol has been reported for the synthesis of amide bonds from unactivated esters and non-nucleophilic amines promoted by potassium tert-butoxide under aerobic conditions. The reaction proceeds under relatively mild conditions, encompassing wide substrate scope. A combined experimental and quantum chemical study has been performed to shed light on the mechanism, which implied that a radical pathway is operating for the present protocol.