Institute of Organic Chemistry, University of Vienna, Währinger Straße 38, 1090 Wien, Austria.
Institute of Chemical Catalysis, University of Vienna, Währinger Straße 38, 1090 Wien, Austria.
Molecules. 2019 Aug 26;24(17):3098. doi: 10.3390/molecules24173098.
A short approach to chiral diaza-olefines from protected 2,2'-diamino-1,1'-binaphthyl is presented. - and -olefines can be selectively obtained by twofold -allylation followed by RCM or by bridging a 2,2'-diamino-1,1'-binaphthyl precursor with -1,4-dibromo-2-butene. Deprotection afforded - and -dihydro[1,6]diazecines in 58 and 64% overall yield. The reactivity of the but-2-ene-1,4-diyl fragment was investigated yielding corresponding epoxides, diols, and mono- and dibromo products. In several cases rearrangements and participation of the proximate -Boc group was observed. In no case could allylic substitution be accomplished. From 13 compounds X-ray structure analyses could be obtained.
从保护的 2,2'-二氨基-1,1'-联萘出发，介绍了一种获得手性二氮杂烯烃的短途径。通过两次烯丙基化，然后 RCM 或通过桥联 2,2'-二氨基-1,1'-联萘前体与 1,4-二溴-2-丁烯，可以选择性地获得 - 和 - 烯烃。脱保护后，以 58%和 64%的总收率得到 - 和 - 二氢[1,6]二氮杂环[4,3-b]吡嗪。研究了丁-2-烯-1,4-二基片段的反应性，得到了相应的环氧化物、二醇、单溴和二溴产物。在几种情况下，观察到重排和邻近的 Boc 基团的参与。在任何情况下都不能完成烯丙基取代。从 13 种化合物中获得了 X 射线结构分析数据。
