Unitat de Recerca en Síntesi Asimètrica (URSA-PCB), Institute for Research in Biomedicine and Departament de Química Orgànica, Universitat de Barcelona, C/Baldiri Reixac 10, E-08028 Barcelona, Spain.
J Am Chem Soc. 2011 Apr 20;133(15):5740-3. doi: 10.1021/ja200988c. Epub 2011 Mar 29.
A highly diastereoselective and efficient synthesis of P-stereogenic bulky alkyl and aryl aminophosphines that relies on ring opening of tert-butyl-oxazaphospholidine 2 is described. Ring opening with several organometallic reagents takes place with inversion of configuration at the phosphorus center as it has been demonstrated by X-ray analysis of two ring-opened intermediates. The unprecedented reactivity observed is attributed to the presence of a free NH functionality that facilitates the attack of the organometallic reagent in an S(N)2@P-type process.
描述了一种高度非对映选择性和高效的 P-手性大体积烷基和芳基膦胺的合成方法，该方法依赖于叔丁基恶唑磷杂环戊烷 2 的开环反应。通过对两个开环中间体的 X 射线分析表明，与几种有机金属试剂的开环反应在磷中心发生构型翻转。观察到的前所未有的反应活性归因于游离 NH 官能团的存在，该官能团促进了亲核试剂在 S(N)2@P 型反应中的进攻。
