Experimental and density functional theory studies on hydroxymethylation of phenylboronic acids with paraformaldehyde over a Rh?PPh3 catalyst,Applied Organometallic Chemistry

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Experimental and density functional theory studies on hydroxymethylation of phenylboronic acids with paraformaldehyde over a Rh?PPh3 catalyst
Applied Organometallic Chemistry ( IF 3.7 ) Pub Date : 2020-11-17 , DOI: 10.1002/aoc.6104
Kuan Wang ₁ , Jie Lan ₁ , Zhen‐Hong He ₁ , Zhe Cao ₁ , Weitao Wang ₁ , Yang Yang ₁ , Zhao‐Tie Liu _{1,

2}

Affiliation

The synthesis of benzyl alcohols (BAs) is highly vital for their wide applications in organic synthesis and pharmaceuticals. Herein, BAs was efficiently synthesized via hydroxymethylation of phenylboronic acids (PBAs) and paraformaldehyde over a simple RhPPh₃ catalyst combined with an inorganic base (NaOH). A variety of BAs with the groups of CH₃⁻, CH₃O⁻, Cl⁻, Br⁻, and so on were obtained with moderate to good yields, indicating that the protocol had a good universality. Density functional theory (DFT) calculations proposed the Hayashi‐type arylation mechanism involved the arylation step of PBA and Rh(OH)(PPh₃)₂ catalyst to form Rh(I)‐bound aryl intermediates and the hydrolysis step of Rh(I)‐bound aryl intermediates and HCHO to generate BA product (the rate‐determining step). The present route provides a valuable and direct method for the synthesis of BAs and expands the application range of paraformaldehyde.

中文翻译：

实验和对苯酸与多聚甲醛在铑羟甲基化密度泛函理论研究？PPh3催化剂

苄醇（BAs）的合成对其在有机合成和药物中的广泛应用至关重要。在此，的BA被有效通过的苯基硼酸（PBA的）和多聚甲醛羟甲基化通过简单的Rh合成 PPH ₃催化剂与无机碱（NaOH）混合。各种用CH的基团的BA的₃^-，CH ₃ ö ^-，氯^-，溴^-，等等，用中等至良好的产率获得，表明该协议有一个很好的通用性。密度泛函理论（DFT）计算提出了Hayashi型芳构化机理涉及PBA和Rh（OH）（PPh ₃）的芳构化步骤₂催化剂形成Rh（I）结合的芳基中间体，Rh（I）结合的芳基中间体和HCHO的水解步骤生成BA产物（速率确定步骤）。本路线为合成BAs提供了有价值的直接方法，并扩展了多聚甲醛的应用范围。

更新日期：2020-11-17

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