可见光诱导喹啉-N-氧化物与亚磺酸的脱氧C2-磺酰化通过自由基反应合成2-磺酰喹啉（英文）

喹啉类衍生物在有机合成、药物化学以及材料化学等领域一直具有重要作用,通过喹啉-N-氧化物合成喹啉类衍生物目前已有许多报道,其中采用金属催化剂实现反应占有很大比例,但这些方法存在催化剂对空气敏感及环境不友好等问题.因此,发展无金属催化反应受到越来越多的重视.近年来,光催化反应在有机合成中得到广泛应用.基于我们在光催化相关反应方面的研究,本文报道了一种可见光诱导喹啉-N-氧化物与亚磺酸脱氧C2-磺酰化合成2-磺酰喹啉衍生物的合成方法.我们选用喹啉-N-氧化物与苯亚磺酸为底物进行条件筛选实验,发现Na2?eosinY(2mol%)为催化剂,二氯乙烷为溶剂,TBHP(0.4mmol)为氧化剂,在蓝光照射下为最优化的实验条件,目标产物2-磺酰喹啉最高产率为88%.在该优化反应条件下,带有供电子或吸电子基团的喹啉-N-氧化物都能与苯亚磺酸反应得到中等至以上产率的目标物,另外带有不同官能团(F,Cl,Br,CH3和t-Bu等)的亚磺酸与喹啉-N-氧化物也都能得到中等以上产率.当使用萘亚磺酸作为反应底物时也能以较高产率得到相应目标产物.对照实验显示,在反应体系中加入自由基捕获剂TEMPO或BHT时反应不能发生,表明自由基中间体可能参与本反应的转化.另外在黑暗条件、无氧化剂或者无催化剂下反应也不能发生,证明这些反应条件是必须的.基于上述实验结果,提出了可能的反应机理.首先光催化剂在可见光照射下形成激发态,然后与TBHP反应生成叔丁氧基自由基,再作用于苯亚磺酸使其生成磺酰基并与喹啉氮氧化物反应,其中通过两步的磺酰基反应,最后通过芳构化得到目标产物,光催化剂可以通过TBHP氧化再生完成催化循环.在此,我们发展了一种简单高效的合成2-磺酰喹啉衍生物的反应方法,该方法无需金属催化剂,可在温和条件下通过可见光诱导实现反应发生.

Visible light induced four component reaction of styrene for the access of thiodifluoroesters

The visible light induced multicomponent reaction of styrene,carbon disulfide,amine and ethyl difluorobromoacetate for the synthesis of thiodifluoroesters is disclosed.This developed protocol offers a facile and general route to access various valuable thiodifluoroesters in moderate to good yields.Preliminary mechanistic studies revealed that a radical process might be involved in this transformation.

C(sp^(3))-H bond functionalization of oximes derivatives via 1,5-hydrogen atom transfer induced by iminyl radical

Oximes derivatives have been vastly used in organic synthesis. In this review, C(sp^(3))-H bond functionalization of oximes derivatives via iminyl radical induced 1,5-hydrogen atom transfer was discussed. According to the different type of products, this review was divided into three parts: (1) C(sp^(3))-H bond functionalization for C-C bond formation. (2) C(sp^(3))-H bond functionalization for C-N bond formation. (3) C(sp^(3))-H bond functionalization for C-S, C-F bond formation.

Hypervalent iodine mediated C-H amination of quinoxalinones with heteroaromatic amines under metal-free conditions

An efficient and facile method for C-H amination of quinoxalinones with heteroaromatic amines under metal-free conditions has been described.In the presence of hypervalent PIDA reagent,the desired products with various groups were obtained with moderate to high yields.

Alumina-supported heteropoly acid:An efficient catalyst for the synthesis of azaarene substituted 3-hydroxy-2-oxindole derivatives via C(sp^3)-H bond functionalization

A method of C（sp^3）-H bond functionalization of methyl azaarenes catalyzed by alumina-supported heteropoly acid and addition to isatins was developed. This transformation could be used for the synthesis of biologically important 3-hydroxy-2-oxindole derivatives in good to excellent yields and the catalyst could be reused for six times without significant decrease in activity.

Transformation of aldehydes or alcohols to amides at room temperature under aqueous conditions

A novel and efficient method for the synthesis of amide has been developed. The reactions proceeded smoothly under aqueous conditions at room temperature and generated the corresponding products in good to excellent yields. It is worth noting that alkyl amines which did not react in known approaches are well tolerated in our system.