Wonneberger Peter, König Nils, Kraft Fabian B, Sárosi Menyhárt B, Hey-Hawkins Evamarie
Universität Leipzig, Faculty of Chemistry and Mineralogy, Institute of Inorganic Chemistry, Johannisallee 29, 04103, Leipzig, Germany.
Angew Chem Int Ed Engl. 2019 Mar 4;58(10):3208-3211. doi: 10.1002/anie.201811673. Epub 2018 Dec 6.
The unprecedented phospha-aza-Diels-Alder reaction between an activated electron-poor imine and 2H-phospholes yields 1-phospha-2-azanorbornenes in a highly chemoselective and moderately diastereoselective reaction. The intermediate 2H-phospholes, which act as dienes, are formed in situ from the corresponding 1H-phospholes. Theoretical calculations confirm that the phospha-aza-Diels-Alder reaction is of normal electron demand. The reactive P-N bond in 1-phospha-2-azanorbornenes can be cleaved by nucleophiles leading to the formation of 2,3-dihydrophospholes.
活化的缺电子亚胺与2H-磷杂环戊二烯之间发生了前所未有的磷杂氮杂狄尔斯-阿尔德反应，在高度化学选择性和中等非对映选择性反应中生成了1-磷杂-2-氮杂降冰片烯。作为双烯体的中间体2H-磷杂环戊二烯由相应的1H-磷杂环戊二烯原位生成。理论计算证实，磷杂氮杂狄尔斯-阿尔德反应具有正常的电子需求。1-磷杂-2-氮杂降冰片烯中的活性P-N键可被亲核试剂裂解，从而导致2,3-二氢磷杂环戊二烯的形成。
