Synthesis of Deuterated γ-Lactones for Use in Stable Isotope Dilution Assays
摘要:
Two syntheses of deuterated gamma-lactones for use as internal standards in stable isotope dilution assays (SIDA) were developed. [2,2,3,3-H-2(4)]-gamma-Octa-, -gamma-deca-, and -gamma-dodecalactones with > 89% deuterium incorporation were prepared in 27, 17, and 19% overall yields, respectively, by the reduction of a doubly protected hydroxypropiolic acid with deuterium gas. [3,3,4-H-2(3)]-gamma-Octa- and -gamma-dodecalactones were prepared in 6 and 23% yields with > 92% deuterium incorporation by the free radical addition of 2-iodoacetamide to [1,1,2-H-2(3)]-1-hexene and [1,1,2-H-2(3)]-1-decene, respectively. Reaction yields were highly dependent upon the purity of the 1-alkene starting material. The deuterated gamma-lactones were evaluated as internal standards for SIDA.
Transition-Metal-Free, Selective Reductive Deuteration of Terminal Alkynes with Sodium Dispersions and EtOD-<i>d</i><sub>1</sub>
作者:Minhui Han、Yuxuan Ding、Yuhao Yan、Hengzhao Li、Shihui Luo、Adila Adijiang、Yun Ling、Jie An
DOI:10.1021/acs.orglett.8b01036
日期:2018.5.18
A transition-metal-free single electron transfer reaction has been developed for the synthesis of [D3]-alkenes from terminalalkynes using sodium dispersions as the electron donor and EtOD-d1 as the deuterium source. Both reagents are cost-effective and bench-stable. This practical method exhibits remarkable terminalalkyne selectivity and exclusive alkene selectivity. Excellent deuterium incorporations
已经开发了无过渡金属的单电子转移反应,用于使用钠分散体作为电子供体,并使用EtOD- d 1作为氘源,从末端炔烃中合成[D 3 ]-烯烃。两种试剂均具有成本效益且稳定。这种实用的方法表现出显着的末端炔烃选择性和专有的烯烃选择性。在没有烯烃异构化的情况下,在各种末端炔烃中都实现了出色的氘掺入和收率。值得注意的是,该反应高度依赖溶剂。ñ正己烷提供了独特的增强,这个还原过程氘。
CRUZ, DE, MALDONADO, V.;LARSON, G. L., SYNTH. COMMUN., 1983, 13, N 14, 1163-1167