General Synthetic Method for Si-Fluoresceins and Si-Rhodamines.
General Synthetic Method for Si-Fluoresceins and Si-Rhodamines.
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DOI：
10.1021/acscentsci.7b00247
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发表时间：
2017-09-27
影响因子：
18.2
通讯作者：
Lavis LD
中科院分区：
文献类型：
--
作者：
Grimm JB;Brown TA;Tkachuk AN;Lavis LD
具有百年历史的荧光素和罗丹明仍然是荧光和荧光化合物的灵活支架。对这些咕吨染料的广泛探索已经产生了一般的结构-活性关系，其中新探针的开发仅受想象力和有机化学的限制。特别是，用硅取代氧杂蒽导致新的红移Si-荧光素和Si-罗丹明，其高亮度和光稳定性使先进的成像实验成为可能。然而，调整这些染料的化学和光谱性质的努力受到困难的合成路线的阻碍。在这里，我们报告了一个通用的策略，从容易合成的双（2-溴苯基）硅烷中间体的Si-荧光素和Si-罗丹明的有效制备。这些二溴化物进行金属/溴化物交换，得到双芳基锂或双（芳基格氏）中间体，其然后可以添加到酸酐或酯亲电试剂中，得到各种Si-咕吨。该策略使得能够有效地（3-5步）合成已知的和新颖的Si-荧光素、Si-罗丹明和相关的染料结构。特别是，我们发现，以前无法访问的底部芳基环的Si-罗丹明的四氢呋喃导致染料在溶液中具有改善的可见光吸光度，并通过氟化物-硫醇取代方便的衍生化。这种模块化、发散性的合成方法将在可见光谱范围内扩大可获得的类黄原胶染料的调色板，从而进一步推动生物成像的前沿。使用二溴化物中间体的一般发散合成使得能够容易地制备已知的和新颖的Si-荧光素、Si-罗丹明和相关的荧光染料结构。
The century-old fluoresceins and rhodamines persist as flexible scaffolds for fluorescent and fluorogenic compounds. Extensive exploration of these xanthene dyes has yielded general structure–activity relationships where the development of new probes is limited only by imagination and organic chemistry. In particular, replacement of the xanthene oxygen with silicon has resulted in new red-shifted Si-fluoresceins and Si-rhodamines, whose high brightness and photostability enable advanced imaging experiments. Nevertheless, efforts to tune the chemical and spectral properties of these dyes have been hindered by difficult synthetic routes. Here, we report a general strategy for the efficient preparation of Si-fluoresceins and Si-rhodamines from readily synthesized bis(2-bromophenyl)silane intermediates. These dibromides undergo metal/bromide exchange to give bis-aryllithium or bis(aryl Grignard) intermediates, which can then add to anhydride or ester electrophiles to afford a variety of Si-xanthenes. This strategy enabled efficient (3–5 step) syntheses of known and novel Si-fluoresceins, Si-rhodamines, and related dye structures. In particular, we discovered that previously inaccessible tetrafluorination of the bottom aryl ring of the Si-rhodamines resulted in dyes with improved visible absorbance in solution, and a convenient derivatization through fluoride-thiol substitution. This modular, divergent synthetic method will expand the palette of accessible xanthenoid dyes across the visible spectrum, thereby pushing further the frontiers of biological imaging. A general divergent synthesis using dibromide intermediates enables facile preparation of known and novel Si-fluoresceins, Si-rhodamines, and related fluorescent dye structures.
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DOI：
10.1002/anie.201403349
发表时间：
2014-09-15
期刊：
Angewandte Chemie (International ed. in English)
影响因子：
--
作者：
Erdmann RS;Takakura H;Thompson AD;Rivera-Molina F;Allgeyer ES;Bewersdorf J;Toomre D;Schepartz A
通讯作者：
Schepartz A
影响因子：
16.6
作者：
Belov, Vladimir N.;Wurm, Christian A.;Hell, Stefan W.
通讯作者：
Hell, Stefan W.
影响因子：
3.1
作者：
Correa, Ivan R., Jr.;Baker, Brenda;Xu, Ming-Qun
通讯作者：
Xu, Ming-Qun
影响因子：
48
作者：
Grimm, Jonathan B.;English, Brian P.;Lavis, Luke D.
通讯作者：
Lavis, Luke D.
DOI：
10.1016/0584-8539(86)80095-2
发表时间：
1986-01-01
影响因子：
4.4
作者：
HINCKLEY, DA;SEYBOLD, PG;BORRIS, DP
通讯作者：
BORRIS, DP