Robby Vroemans

Nature, Published online: 14 June 2022; doi:10.1038/d41586-022-01612-3

A new nickel-catalyzed four-component carbonylation of ethers with olefins to synthesize γ-substituted carbonyl compounds has been developed. A variety of γ-substituted carbonyl compounds were produced in excellent yields under 1 atm pressure of CO. Notably, this strategy has been successfully applied to the one-step synthesis of the drug molecule Naftidrofuryl, which is a medicine for the treatment of cerebrovascular disease (CVD).

Abstract

Multi-component carbonylation of olefins, a reaction that installs both a carbon–carbon(heteroatom) bond and a carbonyl group across the double bond, is an attractive strategy for alkene functionalization. Herein, we developed a novel nickel-catalyzed four-component carbonylation of olefins with ethers under low CO gas pressure. Using alcohols and amines as the reaction partner, diverse γ-oxy-substituted esters and amides were produced in good yields with excellent functional group tolerance. Notably, Naftidrofuryl, a medicine for the treatment of cerebrovascular disease (CVD), can be synthesized by this process straightforwardly.

Nature Materials, Published online: 23 May 2022; doi:10.1038/s41563-022-01263-9

Nature Materials, Published online: 23 May 2022; doi:10.1038/s41563-022-01252-y

Synthesis
DOI: 10.1055/s-0040-1719924

An efficient heterogeneous palladium-catalyzed carbonylative annulation of 2-iodoanilines, trimethyl orthoformate, and amines has been developed. The reaction proceeds smoothly in toluene at 110 °C using N,N-diisopropylethylamine (DiPEA) as base and 2 mol% of MCM-41-anchored bidentate phosphine palladium complex [MCM-41-2P-Pd(OAc)2] as catalyst under 10 bar of carbon monoxide and provides a general and practical method for the construction of a wide variety of quinazolin-4(3H)-ones in good to excellent yields from commercially easily available starting materials. This heterogenized palladium catalyst can be easily recovered via a simple centrifugation process and reused more than nine times with almost consistent catalytic efficiency.
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Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart, Germany

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Synlett
DOI: 10.1055/a-1828-1678

Herein, we describe the synthesis of a wide variety of imines through oxidative coupling of alcohols and aromatic amines catalyzed by Mn complexes bearing N^N triazole ligands. A wide variety of imines in excellent yields (up to 99%) have been prepared. Mn-based catalysts proved to be highly efficient and versatile, allowing for the first time the preparation of several imines containing N-based heterocycles.
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Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart, Germany

Article in Thieme eJournals:
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Synlett
DOI: 10.1055/a-1828-1217

Functionalized cyclic amines are essential structural motifs in synthetic chemistry and pharmaceutical chemistry, and Shono-type oxidation is a well-developed electrochemical approach for the synthesis of α- amines. In sharp contrast, electrochemically driven direct β-C(sp3)–H functionalization of amines has been far proven elusive. Herein, we outline the recent advances in this field and highlight our group’s effort to achieve electrochemical β-C(sp3)–H functionalization assisted by ferrocene as molecular electrocatalyst under mild conditions.1 Introduction2 Case studies of α-Functionalization (Shono-Type Oxidation)3 Electrochemical β-C(sp3)–H Acylation4 Conclusion
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Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart, Germany

Article in Thieme eJournals:
Table of contents  |  Abstract  |  Full text