Photochromic Oxime Directing Groups for Spatially Controlled Pd-Catalyzed C–H Difunctionalization with Tandem Electrophiles

IF 13.1 1区化学 Q1 CHEMISTRY, PHYSICAL

ACS Catalysis Pub Date : 2025-09-23 DOI:10.1021/acscatal.5c05469

Mahmoud R. Saleh, , , Mahmoud Afrasi, , , Ajay H. Bansode, , , Poulami Ghosh, , , Dan E. Wise, , and , Marvin Parasram*,

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Abstract

Herein, we report the employment of oxime ethers as photochromic directing groups for the controlled functionalization of spatially and inherently distinct C(sp²)–H/C(sp³)–H bonds. Our approach features a semi-two-pot protocol for Pd-catalyzed C(sp²)–H oxygenation, photoisomerization, and Pd-catalyzed C(sp³)–H arylation for the synthesis of difunctionalized oxime derivatives in a highly selective and controlled manner. Notably, we illustrate the rare utilization of hypervalent iodine reagents as tandem electrophiles for C–H difunctionalization. The reverse sequence of functionalization events can be achieved thermally, thereby providing a platform for full directing group-controlled C–H difunctionalization. Overall, this work highlights that photochromic directing groups can provide an avenue for positionally controlled C–H difunctionalization.

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光致变色肟导向基团与串联亲电试剂的空间控制pd催化的C-H双官能化

在这里，我们报道了肟醚作为光致变色导向基团的应用，用于控制空间上和本质上不同的C(sp2) -H /C(sp3) -H键的功能化。我们的方法具有半双锅方案，pd催化C(sp2) -H氧化，光异构化和pd催化C(sp3) -H基化，以高度选择性和可控的方式合成双功能化肟衍生物。值得注意的是，我们说明了高价碘试剂作为C-H双官能化的串联亲电试剂的罕见利用。功能化事件的反向顺序可以通过热来实现，从而为完全定向基团控制的C-H双功能化提供了一个平台。总的来说，这项工作强调了光致变色导向基团可以为位置控制的碳氢化合物双功能化提供途径。

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来源期刊

ACS Catalysis CHEMISTRY, PHYSICAL-

CiteScore

20.80

自引率

6.20%

发文量

1253

审稿时长

1.5 months

期刊介绍： ACS Catalysis is an esteemed journal that publishes original research in the fields of heterogeneous catalysis, molecular catalysis, and biocatalysis. It offers broad coverage across diverse areas such as life sciences, organometallics and synthesis, photochemistry and electrochemistry, drug discovery and synthesis, materials science, environmental protection, polymer discovery and synthesis, and energy and fuels. The scope of the journal is to showcase innovative work in various aspects of catalysis. This includes new reactions and novel synthetic approaches utilizing known catalysts, the discovery or modification of new catalysts, elucidation of catalytic mechanisms through cutting-edge investigations, practical enhancements of existing processes, as well as conceptual advances in the field. Contributions to ACS Catalysis can encompass both experimental and theoretical research focused on catalytic molecules, macromolecules, and materials that exhibit catalytic turnover.