可活化的硒代氨基甲酸盐直接释放硒化氢 (H2Se),Chemical Science

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可活化的硒代氨基甲酸盐直接释放硒化氢 (H2Se)
Chemical Science ( IF 7.6 ) Pub Date : 2023-06-20 , DOI: 10.1039/d3sc01936e
Turner D Newton ₁ , Keyan Li ₁ , Jyoti Sharma ₂ , Pier Alexandre Champagne ₂ , Michael D Pluth ₁

Affiliation

硒化氢（H ₂ Se）是一种可能的生物调节剂、潜在的气体递质和生物有机硒化合物合成的重要前体。_{H 2} Se 研究的早期工具受益于对用于检测或递送 H ₂ S 的类似小分子的现有机制的理解。目前 H ₂ S 递送的常见方法是使用小分子硫代氨基甲酸盐，它可以被设计为释放 COS，它被碳酸酐酶快速转化为H _{2 S。}_{扩大我们对 H 2}化学基础的理解在 Se 输送过程中，我们研究了硒代氨基甲酸盐是否经历类似的化学反应来释放羰基硒 (COSe)。使用光激活和水解激活系统，我们证明与较轻的硫代氨基甲酸酯同系物不同，硒代氨基甲酸酯直接释放H ₂ Se并伴随异氰酸酯形成，而不是通过中间释放COSe。这种直接释放 H ₂ Se 的反应机制得到了计算研究的进一步支持，计算研究确定了在不存在质子溶剂的情况下H ₂ Se 和 COSe 释放途径之间的 ΔΔ G ^‡ ∼ 25 kcal mol ^{-1 。}_{这项工作突出了 H 2}的全新方法小分子释放硒，促进了对活性硫和硒物种之间反应性差异的理解。

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Direct hydrogen selenide (H2Se) release from activatable selenocarbamates

Hydrogen selenide (H₂Se) is a possible bioregulator, potential gasotransmitter, and important precursor in biological organoselenium compound synthesis. Early tools for H₂Se research have benefitted from available mechanistic understanding of analogous small molecules developed for detecting or delivering H₂S. A now common approach for H₂S delivery is the use of small molecule thiocarbamates that can be engineered to release COS, which is quickly converted to H₂S by carbonic anhydrase. To expand our understanding of the chemical underpinnings that enable H₂Se delivery, we investigated whether selenocarbamates undergo similar chemistry to release carbonyl selenide (COSe). Using both light- and hydrolysis-activated systems, we demonstrate that unlike their lighter thiocarbamate congeners, selenocarbamates release H₂Se directly with concomitant isocyanate formation rather than by the intermediate release of COSe. This reaction mechanism for direct H₂Se release is further supported by computational investigations that identify a ΔΔG^‡ ∼ 25 kcal mol⁻¹ between the H₂Se and COSe release pathways in the absence of protic solvent. This work highlights fundamentally new approaches for H₂Se release from small molecules and advances the understanding of reactivity differences between reactive sulfur and selenium species.

更新日期：2023-06-20

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