Synthesis of monoalkoxide monopyrrolyl complexes Mo(NR)(CHR')(OR")(pyrroly1):: enyne metathesis with high oxidation state catalysts
Synthesis of monoalkoxide monopyrrolyl complexes Mo(NR)(CHR')(OR")(pyrroly1):: enyne metathesis with high oxidation state catalysts
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DOI：
10.1021/ja075569f
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发表时间：
2007-10-24
影响因子：
15
通讯作者：
Hoveyda, Amir H.
中科院分区：
文献类型：
--
作者：
Singh, Rojendra;Schrock, Richard R.;Hoveyda, Amir H.
将 1 当量的 ROH 添加到二乙醚或 THF 中的 Mo(NAr)(CHCMe2Ph)(Me(2)Pyr)(2) (Ar 2,6-i -Pr2C6H3, Me(2)Pyr = 2,5-二甲基吡咯基)中，得到 Mo(NAr)(CHCMe2Ph)(OR)(Me(2)Pyr) 物质，其中 R (CH3)(3)C (1, 22% 分离收率)、(CH3)(2)CH (2, 83%)、Ar (3, 81%)、(CF3)(2)CH (4, 45%) 或 (CF3)(2)(CH3)C (5, 80%)。通过各种催化剂进行的闭环烯炔复分解会产生环状产物，该环状产物是通过最初将三键加成到亚甲基（最初是新亚甲基）上而产生的，从而产生α-或β-取代的金属环丁烯中间体。
Addition of 1 equiv of ROH to Mo(NAr)(CHCMe2Ph)(Me(2)Pyr)(2) (Ar 2,6-i -Pr2C6H3, Me(2)Pyr = 2,5-dimethylpyrrolyl) in diethyl ether or THF yields Mo(NAr)(CHCMe2Ph)(OR)(Me(2)Pyr) species where R (CH3)(3)C (1, 22% isolated yield), (CH3)(2)CH (2, 83%), Ar (3, 81%), (CF3)(2)CH (4, 45%), or (CF3)(2)(CH3)C (5, 80%). Ring-closing enyne metathesis by various catalysts leads to cyclic products that arise through initial addition of the triple bond to a methylene species (initially neophylidene) to yield an alpha- or a beta-substituted metallacyclobutene intermediate.