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首页> 外文期刊>Chemistry: A European journal >Atom-Efficient Gold(I)-Chloride-Catalyzed Synthesis of a-Sulfenylated Carbonyl Compounds from Propargylic Alcohols and Aryl Thiols: Substrate Scope and Experimental and Theoretical Mechanistic Investigation
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Atom-Efficient Gold(I)-Chloride-Catalyzed Synthesis of a-Sulfenylated Carbonyl Compounds from Propargylic Alcohols and Aryl Thiols: Substrate Scope and Experimental and Theoretical Mechanistic Investigation

机译：炔丙醇和芳基硫醇的原子高效氯化金（I）-氯化物催化的α-亚磺酰化羰基化合物的合成：底物范围以及实验和理论机理研究

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摘要

Gold(I)-chloride-catalyzed synthesis of a-sulfenylated carbonyl compounds from propargylic alcohols and aryl thiols showed a wide substrate scope with respect to both propargylic alcohols and aryl thiols. Primary and secondary aromatic propargylic alcohols generated a-sulfenylated aldehydes and ketones in 60–97% yield. Secondary aliphatic propargylic alcohols generated a-sulfenylated ketones in yields of 47–71%. Different gold sources and ligand effects were studied, and it was shown that gold(I) chloride gave the highest product yields. Experimental and theoretical studies demonstrated that the reaction proceeds in two separate steps. A sulfenylated allylic alcohol, generated by initial regioselective attack of the aryl thiol on the triple bond of the propargylic alcohol, was isolated, evaluated, and found to be an intermediate in the reaction. Deuterium labeling experiments showed that the protons from the propargylic alcohol and aryl thiol were transferred to the 3-position, and that the hydride from the alcohol was transferred to the 2-position of the product. Density functional theory (DFT) calculations showed that the observed regioselectivity of the aryl thiol attack towards the 2-position of propargylic alcohol was determined by a low-energy, five-membered cyclic protodeauration transition state instead of the strained, four-membered cyclic transition state found for attack at the 3-position. Experimental data and DFT calculations supported that the second step of the reaction is initiated by protonation of the double bond of the sulfenylated allylic alcohol with a proton donor coordinated to gold(I) chloride. This in turn allows for a 1,2-hydride shift, generating the final product of the reaction.
机译：从炔丙醇和芳基硫醇中氯化金（I）催化合成α-亚磺酰基羰基化合物显示出相对于炔丙醇和芳基硫醇均较宽的底物范围。伯和仲芳族炔丙醇以60-97％的产率生成α-亚磺酰化的醛和酮。仲脂族炔丙醇可生成α-亚磺酰化的酮，产率为47-71％。研究了不同的金源和配体效应，结果表明氯化金（I）的产率最高。实验和理论研究表明，反应分两个步骤进行。分离，评估由芳基硫醇对炔丙醇的三键的初始区域选择性攻击而生成的亚磺酰化的烯丙醇，发现其为反应的中间体。氘标记实验表明，炔丙醇和芳基硫醇的质子转移到3位，醇的氢化物转移到产物的2位。密度泛函理论（DFT）计算表明，所观察到的芳基硫醇对炔丙醇2位的区域选择性是由低能的五元环原型脱氢过渡态决定的，而不是由应变的四元环化转变态决定的在3位置发现进攻状态。实验数据和DFT计算支持该反应的第二步是通过将亚磺酰化的烯丙醇的双键与一个与氯化金（I）配位的质子供体进行质子化而引发的。这进而允许1,2-氢化物移位，从而生成反应的最终产物。

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