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Borane‐Catalyzed Hydrogenation of Tertiary Amides Activated by Oxalyl Chloride: DFT Mechanistic Insights
European Journal of Organic Chemistry ( IF 2.5 ) Pub Date : 2019-06-25 , DOI: 10.1002/ejoc.201900827
Hui Zhu 1 , Zheng-Wang Qu 1 , Stefan Grimme 1
Affiliation  

Amide activation and hydrogenation: Fast electrophilic activation of tertiary amides by (COCl)2 is favoured by exergonic gas release, affording the separated chloroiminium and Cl ions in chloroform. The B(2,6‐F2C6H3)3/Cl frustrated Lewis pair may then cleave H2 over a barrier of 24.3 kcal/mol as rate‐limiting step, leading to transient hydridoborate for rapid hydride reduction of chloroiminium. A stepwise amide activation and reduction is suggested to realize milder reaction conditions and improved product yield.
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中文翻译:

硼烷催化的草酰氯活化的叔酰胺加氢:DFT机理的见解

酰胺激活和氢化:由(氯化钴)叔酰胺的快速电活化2被放能释放气体的青睐,得到分离的氯代和Cl -在氯仿中的离子。的B(2,6-F 2 C ^ 6 ħ 33 /氯-沮丧路易斯一对可随后裂开ħ 2上的24.3阻挡千卡/摩尔作为限速步骤,导致瞬时化硼酸快速氢化物还原氯代的。建议逐步进行酰胺活化和还原,以实现较温和的反应条件并提高产物收率。
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更新日期:2019-06-25
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