Palladium-Catalyzed Oxidative Cross-Coupling of α-Cyanoketene Dithioacetals with Olefins.
Palladium-Catalyzed Oxidative Cross-Coupling of α-Cyanoketene Dithioacetals with Olefins.
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DOI：
10.1002/chem.201502280
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发表时间：
2015-09
期刊：
影响因子：
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通讯作者：
Xiaogen Yang;Zhuqing Liu;Chenglin Sun;Jiping Chen;Zhengkun Yu
中科院分区：
文献类型：
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作者：
Xiaogen Yang;Zhuqing Liu;Chenglin Sun;Jiping Chen;Zhengkun Yu
在二氧六烷/HOAc/DMSO （9:3:1 v/v/v）气氛下，或以AgOAc作为末端氧化剂，钯催化α-氰烯二硫缩醛与多种烯烃进行了高效的交叉偶联反应。缺电子末端烯烃与空气作氧化剂反应生成线性二烯衍生物。以AgOAc为氧化剂时，苯乙烯发生了交偶联反应，得到了直链和支链二烯。未活化的环状和线性内烯烃底物在空气中苯醌的催化量存在下均反应产生跳过二烯。用x射线晶体学对典型产物进行了结构验证。
Efficient palladium-catalyzed cross-coupling reactions of the internal olefins α-cyanoketene dithioacetals with a variety of olefins were achieved in dioxane/HOAc/DMSO (9:3:1 v/v/v) under air atmosphere or by means of AgOAc as the terminal oxidant. Electron-deficient terminal olefins reacted to form the linear diene derivatives with air as the oxidant. Styrenes underwent the cross-coupling to give both the linear and branched dienes when using AgOAc as the oxidant. Unactivated cyclic and linear internal olefin substrates both reacted in the presence of a catalytic amount of benzoquinone in air to produce skipped dienes. The typical products were structurally confirmed by X-ray crystallography.