Photochemical syntheses, transformations, and bioorthogonal chemistry of trans-cycloheptene and sila trans-cycloheptene Ag(i) complexes.
Photochemical syntheses, transformations, and bioorthogonal chemistry of trans-cycloheptene and sila trans-cycloheptene Ag(i) complexes.
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DOI：
10.1039/c7sc04773h
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发表时间：
2018-02-21
期刊：
影响因子：
8.4
通讯作者：
Fox JM
中科院分区：
文献类型：
--
作者：
Fang Y;Zhang H;Huang Z;Scinto SL;Yang JC;Am Ende CW;Dmitrenko O;Johnson DS;Fox JM
本文报道了反式环庚烯（TCH）和反式-1-硅杂-4-环庚烯（Si-TCH）衍生物的硝酸银配合物的合成和转化。描述了反式环庚烯（TCH）和反式-1-硅杂-4-环庚烯（Si-TCH）衍生物的AgNO 3配合物的光化学合成。设计了一种低温流动光反应器，以使碳环TCH衍生物的合成，由于它们的热敏性，在没有金属配位。与游离碳环不同，TCH·AgNO 3复合物可以在室温下处理，并在冰箱（-18 °C）中储存数周。Si-TCH·AgNO 3复合物特别耐用，在室温下可稳定放置数天，在冰箱中可稳定放置数月。首次用X射线晶体学方法对Si-TCH·AgNO 3配合物进行了表征。随着AgNO 3原位解络合，无金属TCO和Si-TCH衍生物可以参与一系列环加成反应以及二羟基化反应。计算用于预测Si-TCH将参与比最具反应性的反式环辛烯更快的生物正交反应。无金属的Si-TCH衍生物在溶液中显示出良好的稳定性，并参与迄今为止报道的最快的生物正交反应（在9：1的H2O：MeOH中，k2为1.14 × 107 M-1 s-1）。描述了在活细胞中生物正交蛋白质标记中的实用性，包括用非天然含四嗪的氨基酸标记GFP。还使用HaloTag平台评价了Si-TCH试剂与四嗪在活哺乳动物细胞中的反应性和特异性。细胞标记实验表明，Si-TCH衍生物最适合作为细胞环境中的探针分子。
Synthesis and transformations of AgNO3 complexes of trans-cycloheptene (TCH) and trans-1-sila-4-cycloheptene (Si-TCH) derivatives are described. A photochemical synthesis of AgNO3 complexes of trans-cycloheptene (TCH) and trans-1-sila-4-cycloheptene (Si-TCH) derivatives is described. A low temperature flow photoreactor was designed to enable the synthesis of carbocyclic TCH derivatives due to their thermal sensitivity in the absence of metal coordination. Unlike the free carbocycles, TCH·AgNO3 complexes can be handled at rt and stored for weeks in the freezer (–18 °C). Si-TCH·AgNO3 complexes are especially robust, and are bench stable for days at rt, and for months in the freezer. X-ray crystallography was used to characterize a Si-TCH·AgNO3 complex for the first time. With decomplexation of AgNO3in situ, metal-free TCO and Si-TCH derivatives can engage in a range of cycloaddition reactions as well as dihydroxylation reactions. Computation was used to predict that Si-TCH would engage in bioorthogonal reactions that are more rapid than the most reactive trans-cyclooctenes. Metal-free Si-TCH derivatives were shown to display good stability in solution, and to engage in the fastest bioorthogonal reaction reported to date (k2 1.14 × 107 M–1 s–1 in 9 : 1 H2O : MeOH). Utility in bioorthogonal protein labeling in live cells is described, including labeling of GFP with an unnatural tetrazine-containing amino acid. The reactivity and specificity of the Si-TCH reagents with tetrazines in live mammalian cells was also evaluated using the HaloTag platform. The cell labeling experiments show that Si-TCH derivatives are best suited as probe molecules in the cellular environment.
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影响因子：
15
作者：
Blackman, Melissa L.;Royzen, Maksim;Fox, Joseph M.
通讯作者：
Fox, Joseph M.
影响因子：
15
作者：
COPE, AC;WINKLER, HJS;GANELLIN, CR
通讯作者：
GANELLIN, CR
影响因子：
15
作者：
Hoffmann, R;Inoue, Y
通讯作者：
Inoue, Y
影响因子：
5.2
作者：
de Almeida, Gabriela;Townsend, Lisa C.;Bertozzi, Carolyn R.
通讯作者：
Bertozzi, Carolyn R.
DOI：
10.1002/cber.19801131114
发表时间：
1980-01-01
期刊：
CHEMISCHE BERICHTE-RECUEIL
影响因子：
--
作者：
JENDRALLA, H
通讯作者：
JENDRALLA, H