One-Pot Access to peri-Condensed Heterocycles via Manganese-Catalyzed Cascade C–N and C–C Bond Formation

Abstract

A Mn(III)-catalyzed three-component cascade C-H/N-H functionalization of 2-aminopyridines with 2 equiv of dialkyl butyndioates leads to peri-condensed tricylic azines through a selective, but partly destructive, stoichiometry. A wide range of 2,11-diazatricyclo[5.3.1.0]undeca-1(10),4,6,8-tetraen-3-ones were thus obtained with moderate to high yields in a step-economical fashion under mild conditions. This transformation can serve as a concise method for constructing valuable precursors of functional materials and biologically active compounds.

Synthesis of 1,2‐Dicyano‐3‐arylcycl[3.2.2]azines – First 1,2‐Dicarbonitriles Based on Cyclazine Heterocycle

“…There are two general approaches to the synthesis of cycl[3.2.2]azine core: cascade process involving the use of preformed indolizinesand the process without the use of preformed indolizines , . Since our main research interests lie in the field of tetrapyrrolic macrocycles, in particular, phthalocyanines, which are assembled based on phthalic acid derivatives, we focused our efforts on ortho ‐dicarboxylic acid derivatives of cycl[3.2.2]azines.…”

“…There are two general approaches to the synthesis of cycl[3.2.2]azine core: cascade process involving the use of preformed indolizines [15][16][17][18][19][20] and the process without the use of preformed indolizines. [21,22] Since our main research interests lie in the field of tetrapyrrolic macrocycles, in particular, phthalocyanines, [23] which are assembled based on phthalic acid derivatives, we focused our efforts on ortho-dicarboxylic acid derivatives of cycl[3.2.2]azines. Recently, we reviewed this issue [24] and showed that mainly diesters are reported to date with only few publications describing the acids themselves, as well as their anhydrides and hydrazides.…”

Bio-based captodative ligands for redox polymerization of Elium® thermoplastic composites under mild conditions

“…Ability of the captodative ligands to chelate first-row transition metals such as manganese, iron, cobalt, nickel, zinc or cadmium is well documented in the literature. [18][19][20] The chelating effect comes from the two oxygen atoms acting to form dative bonds with the metal centers. 21 In parallel, many dinuc- lear complexes have been reported in which one of the chelating ligands acts as a bridge between two metal centers.…”

Practical Approach for Clean Preparation of Z-β-Thiocyanate Alkenyl Esters

“…β-Thiocyanate alkenyl esters represent highly valuable multifunctional compounds because both alkenyl ester − and alkenyl thiocyanate − moieties are broadly utilized in various fields such as organic synthesis, pharmacy, and material science. Directly converting propargylic carboxylates into β-thiocyanate alkenyl esters through multicomponent reaction − represents a highly attractive transformation in organic synthesis, given the easily available raw materials.…”