Chen, Mengyuan; Liang, Yuchen; Dong, Taotao; Liang, Weijian; Liu, Yanping; Zhang, Yage; Huang, Xin; Kong, Lichun; Wang, Zhi-Xiang; Peng, Bo published their research in Angewandte Chemie, International Edition in 2021. The article was titled 《Z-Selective α-Arylation of α,β-Unsaturated Nitriles via [3,3]-Sigmatropic Rearrangement》.Category: iodides-buliding-blocks The article contains the following contents:
The Morita-Baylis-Hillman (MBH) reaction and [3, 3]-sigmatropic rearrangement are two paradigms in organic synthesis. We have merged the two types of reactions to achieve [3,3]-rearrangement of aryl sulfoxides with α,β-unsaturated nitriles. The reaction was achieved by sequentially treating both coupling partners with electrophilic activator (Tf2O) and base, offering an effective approach to prepare synthetically versatile α-aryl α,β-unsaturated nitriles with Z-selectivity through direct α-C-H arylation of unmodified α,β-unsaturated nitriles. The control experiments and DFT calculations support a four-stage reaction sequence, including the assembly of Tf2O activated aryl sulfoxide with α,β-unsaturated nitrile, MBH-like Lewis base addition, [3,3]-rearrangement, and E1cB-elimination. Among these stages, the Lewis base addition is diastereoselective and E1cB-elimination is cis-selective, which could account for the remarkable Z-selectivity of the reaction. In the experiment, the researchers used many compounds, for example, Trimethylsulfoxonium iodide(cas: 1774-47-6Category: iodides-buliding-blocks)
Trimethylsulfoxonium iodide(cas: 1774-47-6) is a sulfoxonium salt. It is used to generate dimethyloxosulfonium methylide by reaction with sodium hydride. The latter compound is used as a methylene-transfer reagent, and is used to prepare epoxides.Category: iodides-buliding-blocks
Referemce:
Iodide – Wikipedia,
Iodide – an overview | ScienceDirect Topics – ScienceDirect.com