Asymmetric Hydrogenation of Alkynyl Ketones with the η6-Arene/TsDPEN-Ruthenium(II) Catalyst
Asymmetric Hydrogenation of Alkynyl Ketones with the η6-Arene/TsDPEN-Ruthenium(II) Catalyst
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DOI：
10.1021/ol4012184
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发表时间：
2013-06-21
期刊：
影响因子：
5.2
通讯作者：
Ohkuma, Takeshi
中科院分区：
文献类型：
--
作者：
Arai, Noriyoshi;Satoh, Hironori;Ohkuma, Takeshi
Ru（OTf）（TsDPEN）（η（6）-p-cymene）（TsDPEN = N-（对甲苯磺酰基）-1，2-二苯基乙二胺）催化炔基酮的不对称氢化，可得到高达97%ee的炔丙醇。该反应可以在10 atm的H-2下以高达5000的底物与催化剂摩尔比进行。对映体选择的模式与过渡态模型的指导下的CH/π吸引相互作用的底物和催化物种。
Enantioselective hydrogenation of alkynyl ketones catalyzed by Ru(OTf)(TsDPEN)(eta(6)-p-cymene) (TsDPEN = N-(p-toluenesulfonyl)-1,2-diphenylethylenediamine) affords the propargylic alcohols in up to 97% ee. The alkynyl moieties are left intact In most cases. The reaction can be conducted with a substrate-to-catalyst molar ratio as high as 5000 under 10 atm of H-2. The mode of enantioselection is elucidated with the transition state models directed by the CH/pi attractive interaction between the substrate and the catalytic species.