Nickel-catalyzed addition of C-H bonds of terminal alkynes to 1,3-dienes and styrenes.
Nickel-catalyzed addition of C-H bonds of terminal alkynes to 1,3-dienes and styrenes.
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DOI：
10.1021/ja800997j
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发表时间：
2008-04
影响因子：
15
通讯作者：
Masamichi Shirakura;M. Suginome
中科院分区：
文献类型：
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作者：
Masamichi Shirakura;M. Suginome
在室温下，在镍催化剂存在下，末端炔烃的 C-H 键以区域和立体选择性方式加成到 1,3-二烯、苯乙烯和降冰片烯的碳-碳双键上。三异丙基甲硅烷基乙炔与1-取代的1,3-丁二烯衍生物的反应通过分别在二烯的4-位和3-位引入氢原子和三异丙基甲硅烷基乙炔基得到加氢炔化产物。同样，1-三异丙基硅氧基-1,3-丁二烯、1,3-戊二烯、1-环己烯-1-基-1,3-丁二烯和1,3-环己二烯进行加氢炔基化反应，在室温下以良好的收率得到相应的1,4-烯炔衍生物。对取代苯乙烯与三异丙基甲硅烷基乙炔的反应也在镍催化剂存在下进行，以良好的收率得到支链加氢炔化产物。降冰片烯在相同的反应条件下以良好的收率得到外加成产物。
The C-H bond of a terminal alkyne adds to a carbon-carbon double bond of 1,3-dienes, styrenes, and norbornene at room temperature in the presence of a nickel catalyst in regio- and stereoselective manners. Reaction of triisopropylsilylacetylene with 1-substituted 1,3-butadiene derivatives afforded hydroalkynylation products via introduction of a hydrogen atom and a triisopropylsilylethynyl group to 4- and 3-positions of the dienes, respectively. Likewise, 1-triisopropylsiloxy-1,3-butadiene, 1,3-pentadiene, 1-cyclohexen-1-yl-1,3-butadiene, and 1,3-cyclohexadiene underwent the hydroalkynylation reaction, giving the corresponding 1,4-enyne derivatives in good yields at room temperature. Reaction of p-substituted styrene with triisopropylsilylacetylene also proceeded in the presence of the nickel catalyst, giving the branched hydroalkynylation products in good yields. Norbornene gave a exo-addition product in good yield under the same reaction conditions.