O-H insertion and tandem N-H insertion/cyclization reactions using an iron porphyrin as catalyst with diazo compounds as carbene sources
O-H insertion and tandem N-H insertion/cyclization reactions using an iron porphyrin as catalyst with diazo compounds as carbene sources
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DOI：
10.1142/s1088424610001982
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发表时间：
2010-03-01
影响因子：
1.5
通讯作者：
Woo, L. Keith
中科院分区：
文献类型：
--
作者：
Mbuvi, Harun M.;Klobukowski, Erik R.;Woo, L. Keith
四苯基氯化铁(Fe(TPP)Cl)能有效催化2-苯基重氮乙酸甲酯衍生的卡宾插入脂肪醇和芳香醇的O-H键，产率一般在80%以上。虽然类似的N-H插入反应在室温下很快，但O-H插入反应较慢，需要在回流二氯甲烷中使用1.0mol.%催化剂加热约8小时。当1，2-二胺和1，2-醇胺与重氮试剂反应得到哌嗪酮和吗啉酮以及相关类似物如喹恶烷酮和苯并恶嗪-2-酮时，Fe(TPP)Cl对串联N-H插入/环化反应也是有效的。该方法为合成这类杂环化合物提供了一条新的一锅法路线。
Iron(III) tetraphenylporphyrin chloride, Fe(TPP)Cl, efficiently catalyzed the insertion of carbenes derived from methyl 2-phenyldiazoacetates into O-H bonds of aliphatic and aromatic alcohols, with yields generally above 80%. Although the analogous N-H insertions are rapid at room temperature, the O-H insertion reactions are slower and required heating in refluxing methylene chloride for about 8 hours using 1.0 mol.% catalyst. Fe(TPP)Cl was also found to be effective for tandem N-H insertion/cyclization reactions when 1,2-diamines and 1,2-alcoholamines were treated with diazo reagents to give piperazinones and morpholinones and related analogs such as quinoxalinones and benzoxazin-2-ones. This approach provides a new one-pot route for synthesizing these classes of heterocyclic compounds.