Herein we report the synthesis of imidazo[1,5-a]pyridine heterocycles via a Cu(II)-mediated functionalization of α’-C(sp3)–H bonds of pyridinylaldimines and subsequent cyclization. This strategy exploits the inherent directing ability of heteroleptic aldimine...
A direct and highly enantioselective reaction of N‐azidoacetyl‐1,3‐thiazolidine‐2‐thione with trimethyl orthoformate catalyzed by Tol‐BINAPNiCl2 in the presence of TESOTf and 2,6‐lutidine is reported. The heterocyclic scaffold can be easily removed by addition of a wide array of amines to give the corresponding enantiomerically pure 2‐azido‐3,3‐dimethoxypropanamides in high yields. Appropriate manipulation of the N‐benzyl amide derivative provides an efficient access to the antiepileptic agent lacosamide through a new enantioselective C−C bond‐forming process. DFT computational studies uncover clues for the understanding of the remarkable stereocontrol of the addition of a nickel(II) enolate to a putative oxocarbenium intermediate from trimethyl orthoformate.
Well-defined Cu-based nanoparticles represent a valuable catalytic tool for synthesis purposes due to their structural and electronic versatility, requiring thorough mechanistic understanding inputs into their rational design.
Green Chemistry concepts have directed chemists to conceive and develop AQ1 sustainable procedures, from the starting materials choice through reaction and analysis conditions, including suitable engineering aspects, to the impact of products, comprising recycling, and waste management. Industrial processes in Fine and Pharmaceutical Chemistry sector have high E factors compared to oil and bulk chemicals industry. Thus, the development of catalytic methods leading to high added value products is crucial, as well as waste minimization through selective transformations. Catalysts from 3d metals, compared to "heavy" metals, are greener, although a combination of different approaches is needed for efficient and viable processes. In contrast to 4d and 5d metals, catalysis with earth-abundant metals is less developed, even less concerning nanocatalysts. Metal nanoparticles, due to their unique electronic and structural properties, induce original reactivities allowing a plethora of transformations. Besides, solvents, present in most steps, represent a major economic and environmental concern. In addition, they can have a dramatic influence on the stabilization of MNP and hence, a huge impact on catalytic activity and recycling. This chapter gives a perspective on 3d metal-based nanocatalysts in polyols applied in couplings, reactions present in many methodologies to produce fine chemicals in a sustainable fashion. Keywords 3d metals • Metal nanoparticles • Catalysis • Couplings • Polyols Dedicated to Prof. Guillermo Muller for his thorough contributions in Organometallic Chemistry and Homogeneous Catalysis.
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