期刊
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 139, 期 23, 页码 8029-8037出版社
AMER CHEMICAL SOC
DOI: 10.1021/jacs.7b03943
关键词
-
资金
- NIH [R01 GM111412, R01 GM044783, S10 OD012245, P41GM103399, S10RR08438, S10RR029220]
- Arnold and Mabel Beckman Foundation
- NSF [CHE-1048642, CHE-0342998, BIR-0214394]
- [CHE-0840494]
The ability to achieve predictable control over the polarization of strained cycloalkynes can influence their behavior in subsequent reactions, providing opportunities to increase both rate and chemoselectivity. A series of new heterocyclic strained cyclooctynes containing a sulfamate backbone (SNO-OCTs) were prepared under mild conditions by employing ring expansions of silylated methyleneaziridines. SNO-OCT derivative 8 outpaced even a difluorinated cyclooctyne in a 1,3-dipolar cycloaddition with benzylazide. The various orbital interactions of the propargylic and homopropargylic heteroatoms in SNO-OCT were explored both experimentally and computationally. The inclusion of these heteroatoms had a positive impact on stability and reactivity, where electronic effects could be utilized to relieve ring strain. The choice of the heteroatom combinations in various SNO-OCTs significantly affected the alkyne geometries, thus illustrating a new strategy for modulating strain via remote substituents. Additionally, this unique heteroatom activation was capable of accelerating the rate of reaction of SNO-OCT with diazoacetamide over azidoacetamide, opening the possibility of further method development in the context of chemoselective, bioorthogonal labeling.
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据