Rh/Ag-Mediated Peri-Selective Heteroarylation/Single Electron Transfer Annulation Cascade of 1-(Methylthio)naphthalenes and Analogues: Road Less Traveled to Benzo[de]thioacenes,ACS Catalysis

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Rh/Ag-Mediated Peri-Selective Heteroarylation/Single Electron Transfer Annulation Cascade of 1-(Methylthio)naphthalenes and Analogues: Road Less Traveled to Benzo[de]thioacenes
ACS Catalysis ( IF 11.3 ) Pub Date : 2019-05-31 00:00:00 , DOI: 10.1021/acscatal.9b01426
Shiping Yang ₁ , Rui Cheng ₁ , Min Zhang ₁ , Zhengyang Bin ₁ , Jingsong You ₁

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Reported herein is a one-shot synthesis of benzo[de]thioacenes via a Rh-catalyzed peri-selective heteroarylation/Ag-mediated SET intramolecular cyclization sequence of 1-(methylthio)naphthalenes and heteroatom-embedded analogues in HFIP. Moreover, the different alcohols enable an exquisite switch in the reaction process. t-BuOH instead of HFIP delivers biaryl sulfides rather than cyclized products. By separation of rhodacycle species, control experiments, EPR experiments, and especially capture and isolation of thiophene radical adduct with BHT, the mechanistic pathway has been illustrated clearly. The formation of a sulfur-bridged six-membered ring via SET cyclization of the cation-radical to the methylthio group presented herein is intrinsically different from the conventional acid-mediated cyclization of sulfoxides. The annulative π-extension developed herein exemplifies the high compatibility of oxidative C–H activation and radical chemistry.

中文翻译：

的Rh /银介导的围路移动到苯并[：1-（甲硫基）萘和类似物-选择性杂芳基化/单电子转移环级联德] thioacenes

本文报道的是苯并一步法合成[ DE ] thioacenes经由Rh的催化围-选择性的1-（甲硫基）萘杂芳基化/银介导的SET分子内环化序列和在HFIP中的杂原子嵌入的类似物。此外，不同的醇可在反应过程中实现出色的转换。Ť-BuOH代替HFIP传递联芳基硫醚而不是环化产物。通过罗丹环物种的分离，对照实验，EPR实验，尤其是用BHT捕获和分离噻吩自由基加合物，已清楚地说明了其机理途径。经由本文所述的阳离子自由基至甲硫基的SET环化形成的硫桥联的六元环本质上不同于常规的酸介导的亚砜环化。本文开发的环形π延伸物例证了氧化C–H活化和自由基化学的高度相容性。

更新日期：2019-05-31

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