Polycyclization Enabled by Relay Catalysis: One‐Pot Manganese‐Catalyzed C−H Allylation and Silver‐Catalyzed Povarov Reaction

Abstract

In this study, a Mn /Ag -based relay catalysis process is described for the one-pot synthesis of polycyclic products by a formal [3+2] and [4+2] cycloaddition reaction cascade. A manganese(I) complex catalyzed the first example of directed C-H allylation with allenes, setting the stage for an in situ Povarov cyclization catalyzed by silver(I). The reaction proceeds with high bond-forming efficiency (three C-C bonds), broad substrate scope, high regio- and stereoselectivity, and 100 % atom economy.

Expedient Synthesis of 2‐Iminothiazolidines via Telescoping Reactions Including Iron‐Catalyzed Nitrene Transfer and Domino Ring‐Opening Cyclization (DROC)

“…Their operation simplicity and solvent‐ and time‐saving make them more economically attractive [16] . As a matter of fact, they were described as the best way to ‘‘clean up’’ organic synthesis [17] and have sharply emerged as a synthetic route for the construction of a large range of compounds, [18–27] including numerous heterocycles of pharmaceutical and agrochemical interest [28–30] …”

“…[15] Their operation simplicity and solvent-and time-saving make them more economically attractive. [16] As a matter of fact, they were described as the best way to ''clean up'' organic synthesis [17] and have sharply emerged as a synthetic route for the construction of a large range of compounds, [18][19][20][21][22][23][24][25][26][27] including numerous heterocycles of pharmaceutical and agrochemical interest. [28][29][30] Therefore, we intended to use telescoping reactions integrating the in situ generation of the aziridine followed by its ring-opening and insertion of an organic isothiocyanate.…”

Manganese(I)‐Catalyzed Regio‐ and Stereoselective 1,2‐Diheteroarylation of Allenes: Combination of C−H Activation and Smiles Rearrangement

“…Recently, we reported a highly efficient direct allylation reaction with allenes by using the cheap metal manganese as catalyst . To further extend the scope, a tri‐substituted allenyl ester was then subjected using our previously reported reaction conditions.…”

Electrochemical Synthesis of Tetrahydroquinolines from Imines and Cyclic Ethers via Oxidation/Aza‐Diels‐Alder Cycloaddition

“…[1] This reaction is traditionally catalyzed by Bronsted [2] and Lewis acids [3] . Also Mn/Ag system, [4] CAN, [5] TfOH/CuI, [6] Co(III) complexes, [7] Ph 3 P ⋅ HClO 4 , [8] chiral urea catalyst, [9] Tf 2 NH/TfOH, [10] fluoroalcohols, [11] α‐chymotrypsin from bovine pancreas, [12] piperidine, [13] molecular sieves, [14] heterogeneous acidic catalysts, [15] I 2 in aqueous micelles [16] were applied as the catalyst in the Povarov reaction. Reverse regioselectivity was achieved by photocatalytic methods [17] .…”