Doherty Katrina E, Sandoval Arturo L, Politano Fabrizio, Witko Mason L, Schroeder Chelsea M, Brydon William P, Wadey Geoffrey P, Ohlhorst Kristiane K, Leadbeater Nicholas E
Department of Chemistry, University of Connecticut, 55 North Eagleville Road, Storrs, CT 06269-3060, USA.
Department of Organic Chemistry, Faculty of Chemical Sciences, National University of Córdoba, Córdoba, Argentina.
Curr Org Synth. 2024;21(7):941-946. doi: 10.2174/1570179421666230831105337.
Oxidation is a valuable tool in preparative organic chemistry. Oxoammonium salts and nitroxides have proven valuable as reagents and catalysts in this endeavor.
The objective of this study is to scale up the oxidative amidation, ester formation, and nitrile formation using nitroxide as an organocatalyst.
Oxidative functionalization reactions were scaled from the 1 mmol to the 1 mole level. Sodium persulfate was used as the primary oxidant, and a nitroxide was employed as a catalyst. The products of the reactions were isolated in analytically pure form by extraction with no need for column chromatography.
The oxidative amidation and esterification of aldehydes can be scaled up from 1 mmol to 1 mole effectively, with comparable product yields being obtained at each increment. This work shows that conditions developed on a small scale can be transferred to a larger scale without reoptimization. The oxidative functionalization of aldehydes to prepare nitriles is not amenable to direct scale-up due to the concomitant formation of significant quantities of the corresponding carboxylic acid, thereby compromising the product yield.
Two of the three oxidative transformations studied here can be scaled up successfully from the 1 mmol to the 1 mole level.
氧化反应是有机合成化学中的一项重要手段。氧鎓盐和氮氧化物已被证明在这一领域作为试剂和催化剂具有重要价值。
本研究旨在扩大以氮氧化物作为有机催化剂的氧化酰胺化、酯化和腈化反应规模。
氧化官能团化反应规模从1 mmol扩大至1 mol。以过硫酸钠作为主要氧化剂，氮氧化物作为催化剂。反应产物通过萃取分离得到分析纯形式，无需柱色谱法。
醛的氧化酰胺化和酯化反应能够有效地从1 mmol扩大至1 mol规模，每次扩大规模时产物收率相当。本研究表明，小规模条件下开发的反应无需重新优化即可扩大至更大规模。醛氧化制备腈的官能团化反应由于同时生成大量相应的羧酸，从而影响产物收率，因此不适于直接扩大规模。
本研究中所考察的三种氧化转化反应中的两种能够成功地从1 mmol规模扩大至1 mol规模。
