O → S Relay Deprotection: A General Approach to Controllable Donors of Reactive Sulfur Species
O → S Relay Deprotection: A General Approach to Controllable Donors of Reactive Sulfur Species
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DOI：
10.1002/anie.201802845
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发表时间：
2018-05-14
影响因子：
16.6
通讯作者：
Xian, Ming
中科院分区：
文献类型：
--
作者：
Kang, Jianming;Xu, Shi;Xian, Ming
活性硫物种（RSS）是重要的生物分子。其中，H2S、多硫化氢（H2Sn，n > 1）、过硫化物（RSSH）和HSNO被认为在硫相关氧化还原生物学中起调节作用。然而，这些分子是不稳定的并且难以处理。获得可靠、可控的前体（或供体）是研究这些硫物种的前提。报道了一系列O-甲硅烷基-硫醇基含硫分子的制备和评价，这些分子经历pH或F-介导的脱硅作用，以受控方式释放相应的H2S、H2Sn、RSSH和HSNO。这种O -> S继电器去保护作用作为设计pH或F-触发的RSS供体的一般策略。此外，我们已经证明，在供体的O-甲硅烷基基团可以变成其他保护基团，如酯。这项工作应允许RSS捐助者与其他激活机制（如酯酶激活的捐助者）的发展。
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).