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O→S Relay Deprotection: A General Approach to Controllable Donors of Reactive Sulfur Species
Angewandte Chemie International Edition ( IF 16.6 ) Pub Date : 2018-04-19 , DOI: 10.1002/anie.201802845
Jianming Kang 1 , Shi Xu 1 , Miles N. Radford 1 , Wenjia Zhang 1 , Shane S. Kelly 1 , Jacob J. Day 1 , Ming Xian 1
Affiliation  

Reactive sulfur species (RSS) are biologically important molecules. Among them, H2S, hydrogen polysulfides (H2Sn, n>1), persulfides (RSSH), and HSNO are believed to play regulatory roles in sulfur‐related redox biology. However, these molecules are unstable and difficult to handle. Having access to their reliable and controllable precursors (or donors) is the prerequisite for the study of these sulfur species. Reported in this work is the preparation and evaluation of a series of O‐silyl‐mercaptan‐based sulfur‐containing molecules which undergo pH‐ or F‐mediated desilylation to release the corresponding H2S, H2Sn, RSSH, and HSNO in a controlled fashion. This O→S relay deprotection serves as a general strategy for the design of pH‐ or F‐triggered RSS donors. Moreover, we have demonstrated that the O‐silyl groups in the donors could be changed into other protecting groups like esters. This work should allow the development of RSS donors with other activation mechanisms (such as esterase‐activated donors).

中文翻译:

O→S继电器脱保护:反应性硫物种可控供体的一般方法

活性硫(RSS)是生物学上重要的分子。其中,H 2 S,多硫化氢(H 2 S n n > 1),过硫化物(RSSH)和HSNO被认为在与硫有关的氧化还原生物学中起调节作用。但是,这些分子是不稳定的并且难以处理。获得这些可靠且可控的前体(或供体)是研究这些硫物种的前提。报道在这项工作是一系列其经历pH的或F O型甲硅烷基硫醇基的含硫分子的制备和评价-介导的脱甲硅烷基以释放相应ħ 2 S,H 2小号Ñ,RSSH和HSNO以受控方式进行。将此O→S继电器脱充当pH的或F的设计的总体战略- -triggered RSS捐助者。此外,我们已经证明供体中的O-甲硅烷基可以变成其他保护基团,例如酯。这项工作应允许开发具有其他激活机制的RSS供体(例如酯酶激活的供体)。
更新日期:2018-04-19
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