Qian Renzhe, Roller Alexander, Hammerschmidt Friedrich
J Org Chem. 2015 Jan 16;80(2):1082-91. doi: 10.1021/jo502567j.
LiTMP metalated dimethyl N-Boc-phosphoramidates derived from 1-phenylethylamine and 1,2,3,4-tetrahydronaphthalen-1-ylamine highly selectively at the CH3O group to generate short-lived oxymethyllithiums. These isomerized to diastereomeric hydroxymethylphosphonamidates (phosphate–phosphonate rearrangement). However, s-BuLi converted the dimethyl N-Boc-phosphoramidate derived from 1-phenylethylamine to the N-Boc α-aminophosphonate preferentially. Only s-BuLi deprotonated dimethyl hydroxymethylphosphonamidates at the benzylic position and dimethyl N-Boc α-aminophosphonates at the CH3O group to induce phosphonate–phosphinate rearrangements. In the former case, the migration of the phosphorus substituent from the nitrogen to the carbon atom followed a retentive course with some racemization because of the involvement of a benzyllithium as an intermediate.
由1-苯乙胺和1,2,3,4-四氢萘-1-基胺衍生的LiTMP金属化的N-Boc-磷酸二甲酯在CH3O基团处具有高度选择性，生成短寿命的氧甲基锂。这些异构化为非对映体羟基甲基膦酰胺（磷酸酯 - 膦酸酯重排）。然而，s-BuLi优先将由1-苯乙胺衍生的N-Boc-磷酸二甲酯转化为N-Bocα-氨基膦酸酯。只有s-BuLi能使羟基甲基膦酰胺二甲酯在苄基位置去质子化，并使N-Bocα-氨基膦酸二甲酯在CH3O基团处去质子化，从而引发膦酸酯 - 次膦酸酯重排。在前一种情况下，磷取代基从氮迁移到碳原子遵循保留过程，但由于苄基锂作为中间体的参与，会有一些外消旋化。
