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首页> 外文期刊>Chemistry: A European journal >Thioaldehydes from Aldehyde-Hydrogen Sulfide Interaction Under Organocatalysis
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Thioaldehydes from Aldehyde-Hydrogen Sulfide Interaction Under Organocatalysis

机译：来自有机成分分解的醛 - 硫化氢相互作用的硫代醛

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摘要

Thioaldehydes are an important class of sulfur compounds involved in atmospheric, synthetic organic, and biological chemistry. Traditionally, they are believed to be formed by the nucleophilic attack of bisulfide anion on the carbonyl compounds. Herein, we suggest a new mechanism that does not require the formation of bisulfide anion, but rather involves an interaction between hydrogen sulfide and an aldehyde. Though the uncatalyzed or the water-catalyzed reactions involve high barriers, the formic acid-catalyzed reactions involve moderate barriers that should be accessible in planetary atmospheres. Under acid catalysis, thioaldehydes are formed in a hydrogenbonded state, which is at least 6.8 kcalmol~(-1) more stable than separated product and catalyst. This may have implications for the solution-phase synthesis of simpler thioaldehydes, which has been a challenge because of their tendency to oligomerize. Another important implication of these results is for the aspartate semialdehyde→aspartate semithioaldehyde conversion, which is a key biosynthetic reaction in methanogen archaea. The unique ability of the active site aspartate or glutamate residue to catalyze hydrosulfidation of semialdehyde may explain catalysis inside these enzymes.
机译：硫代醛是涉及大气，合成有机和生物化学的重要硫化合物。传统上，据信它们被双硫化物阴离子对羰基化合物的亲硫酸酯侵蚀形成。在此，我们建议一种不需要形成双硫化物阴离子的新机制，而是涉及硫化氢与醛之间的相互作用。虽然未催化或水催化的反应涉及高屏障，但甲酸催化的反应涉及应在行星大气中可进入的中等屏障。在酸催化下，硫代醛形成为氢粘稠状态，其比分离的产物和催化剂更稳定，至少6.8千卡莫醇〜（-1）。这可能对溶液相合成的溶液相合成具有较简单的硫代醛，这是由于它们倾向于寡聚化的挑战。这些结果的另一个重要含义适用于天冬氨酸半醛→天冬氨酸二氧化醛转化，这是甲烷酮古代植物的关键生物合成反应。活性位点天冬氨酸或谷氨酸残基催化半醛氢化的独特能力可以解释这些酶内的催化。

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