Yadagiri Dongari, Anbarasan Pazhamalai
Department of Chemistry , Indian Institute of Technology Madras , Chennai 600036 , India . Email:
Chem Sci. 2015 Oct 1;6(10):5847-5852. doi: 10.1039/c5sc02379c. Epub 2015 Jul 10.
Rhodium catalyzed synthesis of substituted tetrahydropyridines was accomplished from readily accessible thio-tethered -sulfonyl-1,2,3-triazoles. The reaction involves tandem rhodium catalyzed 1,2-sulfur migration in β-thio-α-diazoimines, generated from thio-tethered -sulfonyl-1,2,3-triazoles, to thio-substituted 1-azadiene and subsequent self aza-Diels-Alder reaction. Interestingly, the methodology was effectively extended to the synthesis of fused tetrahydropyridines, dihydropyridines and cyclohexenes through the trapping of the intermediate, 1-azadiene, with various dienophiles such as enol ether, enamine, ketene ,-acetal, alkyne, alkene and diene. Furthermore, the direct conversion of propargyl sulfides to (fused)-tetrahydropyridines was also achieved through the successful integration of copper and rhodium catalysts in one-pot.
铑催化的取代四氢吡啶的合成是通过易于获得的硫连接的 - 磺酰基 - 1,2,3 - 三唑完成的。该反应涉及铑催化硫连接的 - 磺酰基 - 1,2,3 - 三唑生成的β - 硫代 - α - 重氮亚胺中的1,2 - 硫迁移至硫取代的1 - 氮杂二烯，随后进行自身的氮杂 - Diels - Alder反应。有趣的是，该方法通过用各种亲双烯体（如烯醇醚、烯胺、乙烯酮、缩醛、炔烃、烯烃和二烯烃）捕获中间体1 - 氮杂二烯，有效地扩展到稠合四氢吡啶、二氢吡啶和环己烯的合成。此外，通过在一锅法中成功整合铜和铑催化剂，也实现了炔丙基硫醚直接转化为（稠合） - 四氢吡啶。
