Enabling Site-Selective C–H Functionalization of Aliphatic Alcohols and Amines with exo-Directing Groups by Tether-Tunable Design of PdII/PdIV Catalysis

IF 11.3 1区化学 Q1 CHEMISTRY, PHYSICAL

ACS Catalysis Pub Date : 2024-11-05 DOI:10.1021/acscatal.4c05553

Kang Fu, Lei Shi

引用次数: 0

Abstract

We report herein a general platform for palladium catalysis using a library of cyclic diacyl peroxides, achieving site-selective C–H functionalization of aliphatic alcohols and amines. Experimental studies and theoretical calculations indicate that bystanding cyclic diacyl peroxides minimize unwanted reductive elimination events and enable controlled C–H cleavage. The protocol is simple and scalable and offers high selectivity and a broad range of substrates and nucleophiles, including complex molecules. The findings advance understanding of high-valent palladium chemistry, providing a tool for creating chemically diverse vicinal diols and amino alcohols and opening new possibilities in C–H functionalization.

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通过 PdII/PdIV 催化的系链可调设计实现脂肪醇和胺与外定向基的 C-H 功能化的位点选择性

我们在此报告了一个使用环二酰基过氧化物库进行钯催化的通用平台，可实现脂肪醇和胺的位点选择性 C-H 功能化。实验研究和理论计算表明，独立的环状二酰过氧化物可最大限度地减少不必要的还原消除事件，实现受控的 C-H 裂解。该方案简单且可扩展，具有高选择性和广泛的底物和亲核物范围，包括复杂分子。这些研究成果加深了人们对高价钯化学的理解，为创造化学性质多样的邻位二元醇和氨基醇提供了工具，并为 C-H 功能化开辟了新的可能性。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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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.