Modifying commodity-relevant unsaturated polymers via Co-catalyzed MHAT

IF 19.1 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Chem Pub Date : 2024-10-10 DOI:10.1016/j.chempr.2024.05.021
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Abstract

The past 2 decades have witnessed the rapid development of CoSalen-catalyzed hydrofunctionalization reactions, mostly on terminal and conjugation-activated olefins. However, the use of 1,2-dialkyl-substituted alkenes continues to pose challenges. In this study, we revisit this substrate class in the context of Carreira-type hydrofunctionalization reactions and introduce a simple yet effective modification (over a 250-fold-increase in turnover number [TON]). Near-quantitative yields can be achieved at a low catalyst loading, typically 0.05 mol %. The key lies in inhibiting the degradation of the salen backbone using molecular sieves. This protocol facilitates a study on the metal hydride hydrogen atom transfer (MHAT) regioselectivity of this type of alkene. We found that allylic electron-negative groups and hyperconjugation have profound effects, yielding regioisomeric ratios ranging from 6.5:1 to < 1:20. The high TONs, mild conditions, and versatility of this method further enable its application in the post-polymerization modification of several olefin-rich, commodity-relevant polymers, demonstrating the rich potential of MHAT hydrofunctionalization in macromolecular settings.

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通过共催化 MHAT 改性与商品相关的不饱和聚合物
在过去的二十年里,CoSalen 催化的加氢官能化反应得到了快速发展,主要用于末端和共轭活化的烯烃。然而,1,2-二烷基取代烯烃的使用仍然面临挑战。在本研究中,我们在 Carreira 型氢官能化反应的背景下重新审视了这一类底物,并介绍了一种简单而有效的改性方法(转化率 [TON] 增加 250 倍以上)。催化剂负载量较低时(通常为 0.05 摩尔%)即可获得接近定量的产量。关键在于利用分子筛抑制沙林骨架的降解。这种方法有助于研究这类烯烃的金属氢化物氢原子转移(MHAT)的区域选择性。我们发现,烯丙基负电子基团和超共轭作用具有深远的影响,可产生从 6.5:1 到 1:20 的区域异构比。这种方法的高通量系数、温和的条件和多功能性使其能够进一步应用于几种富含烯烃、与商品相关的聚合物的聚合后改性,证明了 MHAT 氢功能化在大分子环境中的巨大潜力。
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来源期刊
Chem
Chem Environmental Science-Environmental Chemistry
CiteScore
32.40
自引率
1.30%
发文量
281
期刊介绍: Chem, affiliated with Cell as its sister journal, serves as a platform for groundbreaking research and illustrates how fundamental inquiries in chemistry and its related fields can contribute to addressing future global challenges. It was established in 2016, and is currently edited by Robert Eagling.
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