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Efficient acceptorless photo-dehydrogenation of alcohols and N-heterocycles with binuclear platinum(ii) diphosphite complexes

机译:用双核双亚铂铂(ii)复合物对醇和N-杂环进行高效无受体光脱氢

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摘要

Although photoredox catalysis employing Ru(ii) and Ir(iii) complexes as photocatalysts has emerged as a versatile tool for oxidative C–H functionalization under mild conditions, the need for additional reagents acting as electron donor/scavenger for completing the catalytic cycle undermines the practicability of this approach. Herein we demonstrate that photo-induced oxidative C–H functionalization can be catalysed with high product yields under oxygen-free and acceptorless conditions via inner-sphere atom abstraction by binuclear platinum(ii) diphosphite complexes. Both alcohols (51 examples), particularly the aliphatic ones, and saturated N-heterocycles (24 examples) can be efficiently dehydrogenated under light irradiation at room temperature. Regeneration of the photocatalyst by means of reductive elimination of dihydrogen from the in situ formed platinum(iii)-hydride species represents an alternative paradigm to the current approach in photoredox catalysis.
机译:尽管使用Ru(ii)和Ir(iii)配合物作为光催化剂的光氧化还原催化已成为在温和条件下氧化CH-H功能化的通用工具,但需要其他试剂作为电子给体/清除剂来完成催化循环,却破坏了这种方法的实用性。在本文中,我们证明了在无氧和无受体条件下,通过双核铂(ii)二亚磷酸酯络合物提取内球原子,可以以高收率催化光诱导的氧化C–H官能化。可以在室温下在光照射下有效地将两种醇(51个实例),特别是脂肪族醇和饱和的N-杂环(24个实例)脱氢。通过从原位形成的氢化铂(iii)物种中还原性消除二氢来再生光催化剂,代表了当前光氧化还原催化方法的另一种范式。

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