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Asymmetric Alkynylation of Seven-Membered Cyclic Imines by Combining Chiral Phosphoric Acids and Ag(I) Catalysts: Synthesis of 11-Substituted-10,11-dihydrodibenzo[b,f][1,4]oxazepine Derivatives
The Journal of Organic Chemistry ( IF 3.3 ) Pub Date : 2014-11-14 00:00:00 , DOI: 10.1021/jo5022037
Yuan-Yuan Ren 1 , You-Qing Wang 1 , Shuang Liu 1
Affiliation  

Asymmetric alkynylation of seven-membered cyclic imine dibenzo[b,f][1,4]oxazepines is successfully achieved by combining chiral phosphoric acid and Ag(I) catalysts. Various arylacetylenes, conjugated enynes, and terminal 1,3-diynes are good substrates for this reaction, and aliphatic hexyne is also a suitable donor at elevated temperature. Optimization of this approach has provided a facile method to synthesize optically active 11-substituted-10,11-dihydrodibenzo[b,f][1,4]oxazepine derivatives containing a carbon–carbon triple bond with 63–99% ee. Subsequent transformations of the carbon–carbon triple bond for the heterocyclic products have been disclosed.

中文翻译:

手性磷酸和Ag(I)催化剂结合组成的七元环亚胺的不对称炔基化反应:合成11-取代的10,11-二氢二苯并[ bf ] [1,4]氧杂氮平衍生物

通过结合手性磷酸和Ag(I)催化剂成功地实现了七元环亚胺二苯并[ bf ] [1,4]氧杂氮杂烷的不对称炔基化反应。各种芳基乙炔,共轭烯炔和末端1,3-二炔是该反应的良好底物,脂族己炔在高温下也是合适的供体。这种方法的优化提供了一种简便的方法,可以合成具有63-99%ee的碳-碳三键的光学活性11-取代的10,11-二氢二苯并[ bf ] [1,4]奥氮平衍生物。已公开了杂环产物的碳-碳三键的后续转变。
更新日期:2014-11-14
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