Ligand-Enabled C–H Hydroxylation with Aqueous H2O2 at Room Temperature,Journal of the American Chemical Society

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Ligand-Enabled C–H Hydroxylation with Aqueous H2O2 at Room Temperature
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2022-09-22 , DOI: 10.1021/jacs.2c08332
Zhen Li ₁ , Han Seul Park ₁ , Jennifer X Qiao ₂ , Kap-Sun Yeung ₃ , Jin-Quan Yu ₁

Affiliation

With the large number of Pd(II)-catalyzed C–H activation reactions of native substrates developed in the past decade, the development of catalysts to enable the use of green oxidants under safe and practical conditions has become an increasingly important challenge. Notably, the compatibility of Pd(II) catalysts with sustainable aqueous H₂O₂ has been a long-standing challenge in catalysis including Wacker-type oxidations. We report herein a bifunctional bidentate carboxyl-pyridone (CarboxPyridone) ligand that enables room-temperature Pd-catalyzed C–H hydroxylation of a broad range of benzoic and phenylacetic acids with an industry-compatible oxidant, aqueous hydrogen peroxide (35% H₂O₂). The scalability of this methodology is demonstrated by a 1000 mmol scale reaction of ibuprofen (206 g) using only a 1 mol % Pd catalyst loading. The utility of this protocol is further illustrated through derivatization of the products and synthesis of polyfluorinated natural product coumestan and pterocarpene from phenol intermediates prepared using this methodology.

中文翻译：

室温下用 H2O2 水溶液进行配体驱动的 C–H 羟基化

随着过去十年中大量Pd(II)催化的天然底物C-H活化反应的发展，开发能够在安全实用的条件下使用绿色氧化剂的催化剂已成为一个日益重要的挑战。_{值得注意的是，Pd(II) 催化剂与可持续含水 H 2} O ₂的相容性一直是包括瓦克型氧化在内的催化领域的长期挑战。_{我们在此报道了一种双功能双齿羧基吡啶酮 (CarboxPyridone) 配体，该配体能够使用工业兼容的氧化剂过氧化氢水溶液 (35% H 2} O)在室温下 Pd 催化的各种苯甲酸和苯乙酸的 C-H 羟基化反应。₂）。仅使用 1 mol% Pd 催化剂负载的布洛芬 (206 g) 的 1000 mmol 规模反应证明了该方法的可扩展性。通过产品的衍生化以及从使用该方法制备的苯酚中间体合成多氟天然产物古美斯坦和紫檀烯，进一步说明了该协议的实用性。

更新日期：2022-09-22

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