Moore Joel D, Sprott Kevin T, Hanson Paul R
Department of Chemistry, University of Kansas, Lawrence, Kansas 66045-7582, USA.
J Org Chem. 2002 Nov 15;67(23):8123-9. doi: 10.1021/jo0262208.
A transition metal-catalyzed/Curtius rearrangement sequence toward the development of conformationally constrained alpha-Boc-aminophosphonates 2-6 is described. An approach using the versatile tert-butylphosphonoacetate moieties 1a and 1b to derive an array of mono- and bicyclic alpha-Boc-aminophosphonate systems is presented. Conformational constraint is incorporated using either the ring-closing metathesis reaction catalyzed by the first generation Grubbs catalyst or intramolecular cyclopropanation mediated by Rh2(OAc)4. Using the tert-butyl ester functionality in 1a or 1b as a potential amino group, the Curtius rearrangement provides an efficient route toward the target alpha-Boc-aminophosphonates.
描述了一种用于构建构象受限的α-Boc-氨基膦酸酯2-6的过渡金属催化/Curtius重排序列。提出了一种使用通用的叔丁基膦酰乙酸酯部分1a和1b来衍生一系列单环和双环α-Boc-氨基膦酸酯体系的方法。通过第一代Grubbs催化剂催化的闭环复分解反应或Rh2(OAc)4介导的分子内环丙烷化反应引入构象限制。利用1a或1b中的叔丁酯官能团作为潜在的氨基，Curtius重排为目标α-Boc-氨基膦酸酯提供了一条有效途径。
