I_(2)O_(5)/KSCN介导的炔烃碘硫氰化反应  

An I_(2)O_(5)/KSCN-Mediated Iodothiocyanation of Alkynes

作　　者：黄涎廷 韩洪亮 肖婧 王帆 柳忠全 Huang Xianting;Han Hongliang;Xiao Jing;Wang Fan;Liu Zhong-Quan(College of Pharmacy,Nanjing University of Chinese Medicine,Nanjing 210023,China)

机构地区：[1]南京中医药大学药学院,南京210023

出　　处：《化学学报》2024年第1期5-8,共4页Acta Chimica Sinica

基　　金：国家自然科学基金(No.21971116)资助项目。

摘　　要：报道了一种通过炔烃与I_(2)O_(5)及KSCN的碘代硫氰化来获得(E)-β-碘代乙烯基硫氰酸酯的绿色途径.与以前的方法相比,本策略具有不含过渡金属、高度非对映选择性、放大到克级以及反应温和等优点.Thiocyanates are an important compound family that widely found in natural products and active pharmaceutical ingredients.In addition,their ability to function as versatile electrophiles either on sulfur or carbon centers enables them especially valuable intermediates in synthetic organic chemistry.In the past decades,considerable advances for synthesis of thiocyanates have been made.However,most of them rely on transition-metal promotion or suffer from harsh reaction conditions or limited substrate scope.Therefore,efficient and practical accesses to thiocyanates are highly desirable.Herein,we disclose herein a general and practical access to(E)-β-iodo vinylthiocyanates via iodothiocyanation of alkynes with I_(2)O_(5) and KSCN.In contrast to previous methods,the present strategy holds the advantages of transition-metal free,high diasteroselectivity,scaled-up to grams and mild conditions.By treatment of the alkynes with I_(2)O_(5) and KSCN at room temperature,we found that a wide variety of terminal and/or internal alkynes all gave the corresponding(E)-β-iodo vinylthiocyanates in high yields and excellent chemoselectivities.In addition,the desired(E)-β-iodo vinylthiocyanates were also obtained in good yields with both aryl and simple alkyl substituted alkynes.Interestingly,propargyl alcohol was also effective substrate.Furthermore,several propionates afforded the corresponding(E)-β-iodo vinylthiocyanates as a mixture of regio-isomers.Treatment of a herbicide clodinafop-propargyl with I_(2)O_(5) and KSCN resulted in high yield of the corresponding(E)-β-iodo vinylthiocyanates,which indicated that this strategy could be applied in direct modification of drugs.Finally,this iodothiocyanation reaction can be smoothly scaled-up to gram level,which indicates it could be applied in industrial synthesis of pharmaceuticals.

关 键 词：碘代硫氰化 炔烃 双官能团化 无金属 高度非对映选择性 

分 类 号：O621.256.22[理学—有机化学]