由生成的磷烯和甲醛亚胺立体选择性合成-1,2,4-三氢苯并[][1,2]氮杂磷三环3-氧化物
Stereoselective Synthesis of -1,2,4-Trihydrobenzo[][1,2]azaphosphinine 3-Oxides from Formed Phosphenes and Formaldimines.
作者信息
Xie Wenlai, Xu Jiaxi
机构信息
State Key Laboratory of Chemical Resource Engineering, Department of Organic Chemistry, College of Chemistry, Beijing University of Chemical Technology, Beijing 100029, People's Republic of China.
出版信息
J Org Chem. 2024 Oct 18;89(20):15206-15216. doi: 10.1021/acs.joc.4c01986. Epub 2024 Oct 10.
Various -1,2,4-trihydrobenzo[][1,2]azaphosphinine 3-oxides are synthesized highly stereoselectively from generated phosphenes and formaldimines under microwave irradiation. Aryl(diazo)methyl(diaryl)phosphine oxides first undergo the Wolff rearrangement to generate phosphenes. Imines, generated from 1,3,5-triazinanes or paraformaldehyde and primary amines, nucleophilically attack the phosphenes followed by a tandem stereoelectronic effect-controlled intramolecular nucleophilic addition and aromatization to give final -1,2,4-trihydrobenzo[][1,2]azaphosphinine 3-oxides, exhibiting completely different annuloselectivity from linear nonformaldimines.
在微波辐射下，由生成的磷烯和甲醛亚胺高度立体选择性地合成了各种 -1,2,4-三氢苯并[][1,2]氮杂磷杂环戊烯 3-氧化物。芳基（重氮）甲基（二芳基）氧化膦首先进行沃尔夫重排以生成磷烯。由 1,3,5-三嗪烷或多聚甲醛与伯胺生成的亚胺，亲核进攻磷烯，随后通过串联立体电子效应控制的分子内亲核加成和芳构化反应，得到最终的 -1,2,4-三氢苯并[][1,2]氮杂磷杂环戊烯 3-氧化物，其环化选择性与线性非甲醛亚胺完全不同。
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