轉自：康龍化成

Nickel-Catalyzed Suzuki–Miyaura Cross-Coupling Reaction of Aliphatic Alcohol Derivatives

Chloe D. Wong, Lauren C. Bradford, Nadia Hirbawi, and Elizabeth R. Jarvo*

Department of Chemistry, University of California, Irvine, California 92617, USA

—Angew.Chem. Int. Ed. 2025, 10.1002/anie.202509657

Recommended by Rui Jin_MC5 and Shi Li_MOC

KEY WORDS: Suzuki–Miyauracoupling (XC), Ni catalysis, enantioselective (反應類型), C(sp2)-C(sp3) (成鍵類型), aliphatic sulfonates, alcohols, aryl boronic acids (原料), aryl alkane, enantioenriched α-aryl and heteroaryl glutarimides (產物), NaI, one-pot, NiBr2(dme), Dtbbpy, chiral bisoxazoline, CBN ligand, PROTAC (其他)

ABSTRACT:Reactions leveraging readily available starting materials are valuable for synthetic utility, especially for late-stage functionalization. Herein, we report a nickel-catalyzed Suzuki–Miyaura cross-coupling (XC) reaction of aliphatic sulfonates with aryl boronic acids. This reaction provides straightforward access to an array of arylated products in good yield. We have established a one-pot protocol allowing for the arylation of alcohols in a single reaction vessel. Additionally, an asymmetric reaction was developed to provide enantioenriched α-aryl and heteroaryl glutarimides in good yield and enantioselectivity.

Background and this work: Suzuki–Miyaura reaction progress toward development of C(sp3) coupling

Substrate scope for aliphatic mesylate and boronic acid

Enantioselective reaction scope of α‐aryl glutarimides

One‐pot arylation of alcohols

Proposed mechanism

In conclusion, Elizabeth R. Jarvo et al. report anickel-catalyzed Suzuki–Miyaura XC reaction of aliphatic sulfonates with aryl boronic acids for the installation of aryl groups. The reaction features a broad scope of aliphatic mesylates and boronic acids, including heteroaryl boronic acids. The reaction can be performed in a one-potmanner, allowing for the direct arylation of alcohols. Mechanistic studies confirmed the stereoablative nature of the reaction and the intermediacy of alkyl radicals. Finally, we rendered the transformation to be enantioselective with a chiral bisoxazoline ligandfor the synthesis of enantioenriched bioactive building blocks.

加利福尼亞大學歐文分校Elizabeth R. Jarvo課題組報道了一種鎳催化脂肪族磺酸酯與芳基硼酸的Suzuki-Miyaura交叉偶聯反應，可以良好的收率直接獲得多種芳基化產物。同時，該策略具有廣泛的底物范圍，多種脂肪族甲磺酸酯及硼酸類化合物（包括雜芳基硼酸）均與體系兼容。其次，通過一鍋法反應實現了醇類底物的原位芳基化反應。機理研究證實了該反應的立體消蝕性以及烷基自由基的中介性。此外，通過使用手性雙噁唑啉配體，還可實現相應的對映選擇性轉化，為合成高度對映體富集的生物活性砌塊提供了新策略。

（轉自：康龍化成）

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