Abstract

N-Acylpyrrole-type amides are a class of versatile building blocks in asymmetric synthesis. We report that by employing Ni(COD)₂/2,2′-bipyridine (5 mol%) catalytic system, the direct, catalytic alcoholysis of N-acylpyrrole-type aromatic and aliphatic amides with both primary and secondary alcohols can be achieved efficiently under very mild conditions (rt, 1 h) even at gram scale. By increasing the catalyst loading to 10 mol%, prolonging reaction time (18 h), and/or elevating reaction temperature to 50 °C/80 °C, the reaction could be extended to both complex and hindered N-acylpyrroles as well as to N-acylpyrazoles, Nacylindoles, and to other (functionalized) primary and secondary alcohols. In all cases, only 1.5 equiv. of alcohol were used. The value of the method has been demonstrated by the racemization-free, catalytic alcoholysis of chiral amides yielded from other asymmetric methodologies.

中文翻译：

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Ni在温和条件下直接催化N-酰基吡咯型叔酰胺的醇解

摘要

N-酰基吡咯型酰胺是不对称合成中的一类通用结构单元。我们报告说，通过使用Ni（COD）₂ / 2,2'-联吡啶（5 mol％）催化体系，可以有效地实现N-酰基吡咯型芳香族和脂肪族酰胺与伯醇和仲醇的直接催化醇解在非常温和的条件下（室温，1小时），甚至以克为单位。通过将催化剂负载量增加到10 mol％，延长反应时间（18小时）和/或将反应温度提高到50°C / 80°C，该反应可以扩展到络合和受阻的N-酰基吡咯以及N-酰基吡唑类acylindoles，以及其他（功能化的）伯醇和仲醇。在所有情况下，只有1.5当量。使用酒精。该方法的价值已通过其他非对称方法产生的无消旋，手性酰胺催化醇解得到证明。