Low catalyst loading in ring-closing metathesis reactions.

Low catalyst loading in ring-closing metathesis reactions.
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闭环复分解反应中催化剂负载量低。

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发表时间:
2013
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影响因子:
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通讯作者:
R. Kadyrov
R. Kadyrov
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作者:
R. Kadyrov

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描述了一种有效的闭环复分解反应过程。在稀溶液中,二烯丙基丙二酸二乙酯的转化率可在几分钟内达到95%,TOF=4173NHCmin(-1),并且含有不饱和 配体的商用Ru催化剂的负载量很低。一般来说,只需要50到250 ppm的催化剂就可以实现近乎定量的转化为各种5-16元杂环化合物。合成了5-8元N-叔丁氧基酮(N-Boc)和N-对甲苯磺酸(N-ts)保护的环胺和9-16元内酯,证明了该方法的实用性。合成大环脯氨酸内酰胺类化合物需要稍高的催化剂负载量。除单环产物外,还分离和鉴定了低聚副产物,主要是环二聚体。
An efficient procedure is described for ring-closing metathesis reactions. A conversion of 95% for diethyl diallylmalonate in dilute solution could be achieved within a few minutes, reaching TOF = 4173 min(-1), with very low loading of commercially available Ru catalysts that contained unsaturated NHC ligands. In general, only 50 to 250 ppm of the catalyst is required to achieve near-quantitative conversion into a broad variety of 5-16-membered heterocyclic compounds. The practicality of this procedure was illustrated in the synthesis of 5-8-membered N-tert-butoxycarbonyl (N-Boc)- and N-para-toluenesulfonyl (N-Ts)-protected cyclic amines and 9-16-membered lactones. The synthesis of macrocyclic proline-based lactams required slightly higher catalyst loadings. Along with monocyclic products, oligomeric byproducts, mostly cyclodimers, were isolated and characterized.
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