LMCT-driven electron relay unlocks alcohols as tunable reductants for nickel-catalyzed cross-electrophilic couplings.

IF 14.7 1区 综合性期刊 Q1 MULTIDISCIPLINARY SCIENCES
Shun Wang, Weidi Zeng, Qing An, Lingfei Duan, Zhiwei Zuo
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引用次数: 0

Abstract

Photoinduced electron transfer is fundamental to both biological and synthetic processes; however, modulating back electron transfer (BET) remains a formidable challenge in achieving more efficient photocatalytic transformations. In this work, we present a strategy to regulate electron transfer dynamics via ligand-to-metal charge transfer (LMCT) catalysis, wherein the rapid β-scission of alkoxy radicals is harnessed to suppress BET, thereby facilitating the efficient transfer of reducing equivalents to drive transition metal-mediated reductive cross-coupling reactions. By strategically utilizing a diverse array of alcohol reductants, such as methanol and pinacol, we employ a cerium benzoate catalyst to enable reductive processes not through modulation of redox potentials, but by promoting synchronized electron transfer. Detailed mechanistic investigations reveal that the photoinduced electron relay process, governed by LMCT-BET, plays a pivotal role in effectively delivering reducing equivalents to catalytic sites, underscoring its significance in optimizing catalytic efficiency.

lmct驱动的电子继电器解锁醇作为镍催化的交叉亲电偶联的可调还原剂。
光致电子转移是生物和合成过程的基础;然而,在实现更有效的光催化转化过程中,调制反向电子转移(BET)仍然是一个艰巨的挑战。在这项工作中,我们提出了一种通过配体到金属电荷转移(LMCT)催化调节电子转移动力学的策略,其中利用烷氧基自由基的快速β断裂来抑制BET,从而促进还原性当量的有效转移,以驱动过渡金属介导的还原性交叉偶联反应。通过战略性地利用多种醇还原剂,如甲醇和品纳科尔,我们采用苯甲酸铈催化剂来实现还原过程,而不是通过调节氧化还原电位,而是通过促进同步电子转移。详细的机理研究表明,由LMCT-BET控制的光致电子接力过程在有效地向催化位点传递还原物方面起着关键作用,强调了其在优化催化效率方面的重要性。
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来源期刊
Nature Communications
Nature Communications Biological Science Disciplines-
CiteScore
24.90
自引率
2.40%
发文量
6928
审稿时长
3.7 months
期刊介绍: Nature Communications, an open-access journal, publishes high-quality research spanning all areas of the natural sciences. Papers featured in the journal showcase significant advances relevant to specialists in each respective field. With a 2-year impact factor of 16.6 (2022) and a median time of 8 days from submission to the first editorial decision, Nature Communications is committed to rapid dissemination of research findings. As a multidisciplinary journal, it welcomes contributions from biological, health, physical, chemical, Earth, social, mathematical, applied, and engineering sciences, aiming to highlight important breakthroughs within each domain.
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