Pd- and Ni-Catalyzed Cross-Coupling Reactions of Functionalized Organozinc Reagents with Unsaturated Thioethers
Pd- and Ni-Catalyzed Cross-Coupling Reactions of Functionalized Organozinc Reagents with Unsaturated Thioethers
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DOI：
10.1002/chem.201002850
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发表时间：
2011-03-01
影响因子：
4.3
通讯作者：
Knochel, Paul
中科院分区：
文献类型：
--
作者：
Melzig, Laurin;Metzger, Albrecht;Knochel, Paul
在过渡金属催化剂存在下，各种不饱和硫醚与官能化锌试剂进行了交叉偶联反应。以Pd（OAc）（2）或[Ni（acac）（2）]为催化剂，配体为S-Phos或DPE-Phos的三种催化体系的催化效果最好。基于吡啶、嘧啶、吡嗪、哒嗪、三嗪、苯并噻唑、苯并恶唑、吡咯或喹唑啉环的N-杂环硫醚以及硫代甲基乙炔在该交叉偶联反应中充当亲电试剂。具有敏感官能团（如酯、腈或酮基团）的芳基、杂芳基、苄基和烷基卤化锌在环境温度下使用Ni催化剂与不饱和硫醚反应。相应的Pd催化反应需要稍高的温度。还报道了与N-杂环的大规模交叉偶联实验（10-20 mmol）。
A variety of unsaturated thioethers have been subjected to cross-coupling reactions with functionalized zinc reagents in the presence of a transition-metal catalyst. Three different catalytic systems based on Pd(OAc)(2) or [Ni(acac)(2)] and the ligands S-Phos or DPE-Phos gave the best results. N-Heterocyclic thioethers based on a pyridine, pyrimidine, pyrazine, pyridazine, triazine, benzothiazole, benzoxazole, pyrrole, or quinazoline ring, as well as thiomethylacetylenes, serve as electrophiles in this cross-coupling reaction. Aryl-, heteroaryl-, benzylic, and alkyl-zinc halides with sensitive functionalities, such as ester, nitrile, or ketone groups react at ambient temperature with unsaturated thioethers using a Ni catalyst. The corresponding Pd-catalyzed reactions require slightly higher temperatures. Large-scale cross-coupling experiments (10-20 mmol) with N-heterocycles are also reported.