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钌催化的1,5-二烯氧化环化反应：共氧化剂的前所未有的作用。

Ru-catalysed oxidative cyclisation of 1,5-dienes: an unprecedented role for the co-oxidant.

作者信息

Hussein Aqeel A

机构信息

School of Chemistry, University of Southampton Southampton Hampshire SO17 1BJ UK

College of Dentistry, University of Al-Ameed PO Box 198 Karbala Iraq.

出版信息

RSC Adv. 2020 Apr 17;10(26):15228-15238. doi: 10.1039/d0ra02303e. eCollection 2020 Apr 16.

DOI:10.1039/d0ra02303e
PMID:35495449
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC9052297/
Abstract

The Ru-mediated oxidative cyclisation of 1,5-dienes to furnish 2,5-dihydroxyalkyl-substituted tetrahydrofuran-diols (THF-diols) represents a practical approach for the synthesis of many bioactive natural products. In the current study, we reported profound findings obtained by density functional theory (DFT) simulations, and they were consistent with the experimental conditions. The results set out a catalytic cycle within intermediacy of NaIO-complexed Ru(vi) species. Importantly, the co-oxidant played a critical role in the cyclisation step and subsequently the release of THF-diols. Following the formation of Ru(vi) glycolate, cyclisation and THF-diol release proceeded through NaIO-coordinated Ru(vi) intermediates, outpacing the Ru(viii) glycolate or THF-diolate intermediates and subsequently entering "second cycle" type pathways. The results indicated a cycle involving Ru(viii)/Ru(vi)/Ru(iv)/Ru(vi) rather than Ru(viii)/Ru(vi)/Ru(viii)/Ru(vi)/Ru(viii). Additionally, the existence of an electron-withdrawing group (EWG) on one of the double bonds of 1,5-dienes revealed that the regioselectivity of the Ru-catalysed oxidative cyclisation was predominantly initiated at the electron-rich alkene. Overall, this study offers new insights, which were ignored by earlier experimentalists and theoreticians, into the Ru-catalysed functionalizations of alkenes and 1,5-dienes.

摘要

钌介导的1,5 - 二烯氧化环化反应生成2,5 - 二羟基烷基取代的四氢呋喃二醇（THF - 二醇），为许多生物活性天然产物的合成提供了一种实用方法。在本研究中，我们报告了通过密度泛函理论（DFT）模拟获得的深刻发现，这些发现与实验条件一致。结果展示了一个在NaIO络合的Ru(vi)物种中间体存在下的催化循环。重要的是，共氧化剂在环化步骤以及随后THF - 二醇的释放中起着关键作用。在形成Ru(vi)乙醇酸酯之后，环化和THF - 二醇的释放通过NaIO配位的Ru(vi)中间体进行，其速度超过Ru(viii)乙醇酸酯或THF - 二醇盐中间体，随后进入“第二循环”类型的途径。结果表明存在一个涉及Ru(viii)/Ru(vi)/Ru(iv)/Ru(vi)而非Ru(viii)/Ru(vi)/Ru(viii)/Ru(vi)/Ru(viii)的循环。此外，1,5 - 二烯的一个双键上存在吸电子基团（EWG）表明，Ru催化的氧化环化反应的区域选择性主要在富电子烯烃处起始。总体而言，本研究为Ru催化的烯烃和1,5 - 二烯的官能化反应提供了新的见解，而这些见解被早期的实验人员和理论人员所忽视。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/b297/9052297/5501f08a0881/d0ra02303e-f7.jpg
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https://cdn.ncbi.nlm.nih.gov/pmc/blobs/b297/9052297/694f3d4e7c6f/d0ra02303e-s1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/b297/9052297/c473e004527f/d0ra02303e-f1.jpg
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