Chemoselective Tertiary C-H Hydroxylation for Late-Stage Functionalization with Mn(PDP)/Chloroacetic Acid Catalysis.,Advanced Synthesis & Catalysis

当前位置： X-MOL 学术 › Adv. Synth. Catal. › 论文详情

Our official English website, www.x-mol.net, welcomes your feedback! (Note: you will need to create a separate account there.)

Chemoselective Tertiary C-H Hydroxylation for Late-Stage Functionalization with Mn(PDP)/Chloroacetic Acid Catalysis.
Advanced Synthesis & Catalysis ( IF 4.4 ) Pub Date : 2019-11-27 , DOI: 10.1002/adsc.201901472
Rachel K Chambers _{1,

2} , Jinpeng Zhao _{1,

2,

3} , Connor P Delaney ₁ , M Christina White ₁

Affiliation

Aromatic and heterocyclic functionality are ubiquitous in pharmaceuticals. Herein, we disclose a new Mn(PDP)catalyst system using chloroacetic acid additive capable of chemoselectively oxidizing remote tertiary C(sp 3)-H bonds in the presence of a broad range of aromatic and heterocyclic moieties. Although catalyst loadings can be lowered to 0.1 mol% under a Mn(PDP)/acetic acid system for aromatic and non-basic nitrogen heterocycle substrates, the Mn(PDP)/chloroacetic acid system generally affords 10-15% higher isolated yields on these substrates and is uniquely effective for remote C(sp 3)-H hydroxylations in substrates housing basic nitrogen heterocycles. The demonstrated ability to perform Mn(PDP)/chloroacetic acid C(sp 3)-H oxidations in pharmaceutically relevant complex molecules on multi-gram scales will facilitate drug discovery processes via late-stage functionalization.

中文翻译：

化学选择性叔CH羟基化反应用于Mn（PDP）/氯乙酸催化的后期官能化。

芳香族和杂环官能团在药物中无处不在。在这里，我们公开了一种新的Mn（PDP）催化剂体系，它使用氯乙酸添加剂，能够在宽范围的芳族和杂环基团存在下化学选择性氧化远端C（sp 3）-H键。尽管对于芳香族和非碱性氮杂环底物，在Mn（PDP）/乙酸体系下催化剂负载量可降低至0.1 mol％，但Mn（PDP）/氯乙酸体系通常可将这些化合物的分离产率提高10-15％底物，并且对于容纳碱性氮杂环的底物中的远程C（sp 3）-H羟基化作用特别有效。

更新日期：2019-12-27

点击分享查看原文

点击收藏

公开下载

阅读更多本刊最新论文本刊介绍/投稿指南11