Ethenolysis Reactions Catalyzed by Imido Alkylidene Monoaryloxide Monopyrrolide (MAP) Complexes of Molybdenum
Ethenolysis Reactions Catalyzed by Imido Alkylidene Monoaryloxide Monopyrrolide (MAP) Complexes of Molybdenum
复制标题
DOI：
10.1021/ja904786y
复制
发表时间：
2009-08-12
影响因子：
15
通讯作者：
Hoveyda, Amir H.
中科院分区：
文献类型：
--
作者：
Marinescu, Smaranda C.;Schrock, Richard R.;Hoveyda, Amir H.
单芳氧基吡咯烷酮(MAP)钼的烯烃歧化反应催化剂中含有手性二氢呋喃基芳氧基配体，对油酸甲酯、环辛烯和环戊烯的乙烯裂解反应具有较高的催化活性。用5000当量的油酸甲酯进行乙烯裂解制得1-癸烯(1D)和9-癸烯酸甲酯(M9D)，其选择性为~gt；99%，产率可达95%，在15h内可达4750吨(周转数)。在室温或50℃时，钨环丁烷催化剂的产率约为钼催化剂的一半，尽管选择性仍为>；99%。30000当量的环辛烯在20atm下可用22500t进行乙烯裂解生成1，9-十二烯(产率75%)，而10000当量的环戊烯在20atm下可用5800当量的乙烯裂解成1，6-庚二烯(产率58%)。没有理由认为，用这里报道的最成功的催化剂可以最大限度地提高乙烯分解的效率。
Monoaryloxide-pyrrolide (MAP) olefin metathesis catalysts of molybdenum that contain a chiral bitetralin-based aryloxide ligand are efficient for ethenolysis of methyl oleate, cyclooctene, and cyclopentene. Ethenolysis of 5000 equiv of methyl oleate produced 1-decene (1D) and methyl-9-decenoate (M9D) with a selectivity of > 99%, yields up to 95%, and a TON (turnover number) of 4750 in 15 h. Tungstacyclobutane catalysts gave yields approximately half those of molybdenum catalysts, either at room temperature or at 50 degrees C, although selectivity was still > 99%. Ethenolysis of 30000 equiv of cyclooctene to 1,9-decadiene could be carried out with a TON of 22 500 at 20 atm (75% yield), while ethenolysis of 10000 equiv of cyclopentene to 1,6-heptadiene could be carried out with a TON of 5800 at 20 atm (58% yield). There is no reason to propose that the efficiency of ethenolysis has been maximized with the most successful catalyst reported here.