Department of Applied Chemistry, Graduate School of Engineering , Tokyo University of Agriculture and Technology , 2-24-16 Nakacho , Koganei , Tokyo 184-8588 , Japan.
Org Lett. 2019 Dec 6;21(23):9334-9338. doi: 10.1021/acs.orglett.9b03498. Epub 2019 Nov 11.
Herein we report a diastereoselective synthesis of medium-sized carbocycle-fused piperidines via [1, ( = 6, 7)]-[1,5]-sequential hydride shift triggered double C(sp)-H bond functionalization. When cinnamylidene malonates having ,-dibenzyl propylamine moiety were treated with 5 mol % of Yb(OTf), a [1,6]-[1,5]-sequential hydride shift/cyclization process proceeded to afford seven-membered carbocycle-fused piperidines with excellent diastereoselectivities. This sequential system was applicable to the synthesis of eight-membered carbocycle-fused piperidines by an unprecedented [1,7]-[1,5]-sequential hydride shift/cyclization process.
在此，我们报告了一种通过[1, ( = 6, 7)]-[1,5]顺序氢化物转移引发的双 C(sp)-H 键官能化反应，来立体选择性合成中到大环碳环稠合哌啶的方法。当具有,-二苄基丙基胺部分的肉桂亚胺丙二酸酯与 5 mol %的 Yb(OTf)反应时，[1,6]-[1,5]顺序氢化物转移/环化反应进行，以优异的立体选择性得到七元碳环稠合哌啶。该顺序体系可通过前所未有的[1,7]-[1,5]顺序氢化物转移/环化反应应用于八元碳环稠合哌啶的合成。
