Coote Susannah C, O'Brien Peter, Whitwood Adrian C
Department of Chemistry, University of York, Heslington, York, UKYO10 5DD.
Org Biomol Chem. 2008 Dec 7;6(23):4299-314. doi: 10.1039/b811137e. Epub 2008 Oct 8.
The stereoselective aziridination of a range of cyclic allylic alcohols using two different chloramine salts (4-MeC(6)H(4)SO(2)NClNa, TsNClNa and t-BuSO(2)NClNa, BusNClNa) has been explored. The stereoselectivity of these reactions was highly dependent on the structure of the allylic alcohol and the chloramine salt. Generally, mixtures of cis- and trans-hydroxy aziridines were obtained, in which the major diastereomer was the cis-hydroxy aziridine, whilst complete cis-diastereoselectivity was observed in the aziridination of 1,3-disubstituted allylic alcohols. In each case studied, aziridination using BusNClNa gave higher cis-stereoselectivity than that observed for the same reaction using TsNClNa. Unexpectedly, application of the aziridination conditions to 1-substituted cyclopen-2-en-1-ols did not generate the aziridines. Instead, epoxy sulfonamides were obtained.
已对一系列环状烯丙醇使用两种不同的氯胺盐（对甲苯磺酰氯胺钠，TsNClNa和叔丁基磺酰氯胺钠，BusNClNa）进行立体选择性氮杂环丙烷化反应的研究。这些反应的立体选择性高度依赖于烯丙醇和氯胺盐的结构。通常，会得到顺式和反式羟基氮杂环丙烷的混合物，其中主要的非对映异构体是顺式羟基氮杂环丙烷，而在1,3-二取代烯丙醇的氮杂环丙烷化反应中观察到了完全的顺式非对映选择性。在所研究的每种情况下，使用BusNClNa进行氮杂环丙烷化反应比使用TsNClNa进行相同反应时具有更高的顺式立体选择性。出乎意料的是，将氮杂环丙烷化反应条件应用于1-取代的环戊-2-烯-1-醇时并未生成氮杂环丙烷。相反，得到了环氧磺酰胺。
