σ-Alkynyl Adsorption Enables Electrocatalytic Semihydrogenation of Terminal Alkynes with Easy-Reducible/Passivated Groups over Amorphous PdSx Nanocapsules,Journal of the American Chemical Society

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σ-Alkynyl Adsorption Enables Electrocatalytic Semihydrogenation of Terminal Alkynes with Easy-Reducible/Passivated Groups over Amorphous PdSx Nanocapsules
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2022-10-05 , DOI: 10.1021/jacs.2c07742
Huizhi Li ₁ , Ying Gao ₁ , Yongmeng Wu ₁ , Cuibo Liu _{1,

2} , Chuanqi Cheng ₃ , Fanpeng Chen ₁ , Yanmei Shi ₁ , Bin Zhang _{1,

2}

Affiliation

Highly chemo- and regioselective semihydrogenation of alkynes is significant and challenging for the synthesis of functionalized alkenes. Here, a sequential self-template method is used to synthesize amorphous palladium sulfide nanocapsules (PdS_x ANCs), which enables electrocatalytic semihydrogenation of terminal alkynes in H₂O with excellent tolerance to easily reducible groups (e.g., C–I/Br/Cl, C═O) and the metal center deactivating skeletons (e.g., quinolyl, carboxyl, and nitrile). Mechanistic studies demonstrate that specific σ-alkynyl adsorption via terminal carbon and negligible alkene adsorption on isolated Pd²⁺ sites ensure successful synthesis of various alkenes with outstanding time-irrelevant selectivity in a wide potential range. The key hydrogen and carbon radical intermediates are validated by electron paramagnetic resonance and high-resolution mass spectrometry. Gram-scale synthesis of 4-bromostyrene and expedient preparation of deuterated alkene precursors and drugs with D₂O show promising applications. Impressively, PdS_x ANCs can be applied to the prevailing thermocatalytic semihydrogenation of functionalized alkyne using H₂.

中文翻译：

σ-炔基吸附使具有易还原/钝化基团的末端炔烃在无定形 PdSx 纳米胶囊上的电催化半氢化成为可能

炔烃的高度化学选择性和区域选择性半氢化对于功能化烯烃的合成具有重要意义和挑战性。在这里，连续自模板法用于合成无定形硫化钯纳米胶囊 (PdS _x ANCs )，它能够在 H ₂ O 中对末端炔烃进行电催化半氢化，并且对易还原基团（例如，C-I/Br/Cl）具有出色的耐受性, C=O) 和金属中心失活骨架 (如喹啉基、羧基和腈基)。机理研究表明，特定的 σ-炔基通过末端碳吸附，而烯烃在分离的 Pd ^{2+上的吸附可忽略不计}站点确保在广泛的潜在范围内成功合成具有出色的与时间无关的选择性的各种烯烃。关键的氢和碳自由基中间体通过电子顺磁共振和高分辨率质谱法进行了验证。克级合成 4-溴苯乙烯和用 D ₂ O 快速制备氘代烯烃前体和药物显示出有前途的应用。令人印象深刻的是，PdS _x ANCs可以应用于使用 H ₂的功能化炔烃的主要热催化半氢化。

更新日期：2022-10-05

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