Chiral [16]-ane P<sub>4</sub>N<sub>2</sub> macrocycles: stereoselective synthesis and unexpected intermolecular exchange of endocyclic fragments
作者:E. I. Musina、R. N. Naumov、K. B. Kanunnikov、A. B. Dobrynin、S. Gómez-Ruiz、P. Lönnecke、E. Hey-Hawkins、A. A. Karasik、O. G. Sinyashin
DOI:10.1039/c8dt03214a
日期:——
Chiral 1,9-diaza-3,7,11,15-tetraphosphacyclohexadecanes were stereoselectively synthesized as pure RPSPSPRP isomers via a one-pot Mannich-type condensation reaction of 1,3-bis(arylphosphino)propane, formaldehyde and optically active, as well as racemic, primary amines. An unprecedented intermolecular exchange of endocyclic amino fragments of 1,9-diaza-3,7,11,15-tetraphosphacyclohexadecanes was observed
手性1,9-二氮杂- 3,7,11,15- tetraphosphacyclohexadecanes被立体选择性地作为纯合成- [R P小号P小号P - [R P异构体通过的1,3-双一锅曼尼希型缩合反应(芳基膦)丙烷,甲醛,旋光性以及外消旋伯胺。观察到前所未有的1,9-二氮杂3,7,11,15-四磷杂环十六烷的环内氨基片段的分子间交换。P–CH 2的可靠性大环氨基甲基膦中的-N片段是立体异构化,中型循环产物形成以及内环氨基片段交换的原因。讨论了这些转化的机理,包括形成亚甲基phosph中间体以及进一步的分子内和分子间亲核取代。