閉環炔基元合成反應 (RCAM)

Dr. Josephine Nakhla

自 Schrock 及其同事發現結構明確的金屬烷基炔以來，炔元合成一直是 C-C 鍵形成的有用工具。³ 這些複合物已在複雜天然產品的合成和材料科學中找到了用途。⁴ 這些催化劑的限制包括對空氣和濕氣的敏感性，以及與含有供體位點的底物不相容。Fürstner 及其合作者最近開發了一種空氣穩定的鉬催化劑，用於炔烴的偏析反應，該催化劑用途廣泛，並且與含有供體位點的基質相容。⁴ 作者還考察了這種催化劑在多種炔烃的閉環交輝合成 (RCAM) 中的應用，以良好的收率生成了多種大環 (Scheme 1)。

方案 1. 用於炔烴偏析的空氣穩定型鉬催化劑。

參考資料

1. Romero PE, Piers WE, McDonald R. 2004. Rapidly Initiating Ruthenium Olefin-Metathesis Catalysts. Angew. Chem. Int. Ed.. 43(45):6161-6165. https://doi.org/10.1002/anie.200461374

2. Romero PE, Piers WE. 2005. Direct Observation of a 14-Electron Ruthenacyclobutane Relevant to Olefin Metathesis. J. Am. Chem. Soc.. 127(14):5032-5033. https://doi.org/10.1021/ja042259d

3. Schrock RR. 2002. High Oxidation State Multiple Metal?Carbon Bonds. Chem. Rev.. 102(1):145-180. https://doi.org/10.1021/cr0103726

4. Fürstner A, Davies PW. 2005. Alkyne metathesis. Chem. Commun..(18):2307. https://doi.org/10.1039/b419143a

5. Schrock R, Czekelius C. 2007. Recent Advances in the Syntheses and Applications of Molybdenum and Tungsten Alkylidene and Alkylidyne Catalysts for the Metathesis of Alkenes and Alkynes. Adv. Synth. Catal.. 349(1-2):55-77. https://doi.org/10.1002/adsc.200600459

6. Bindl M, Stade R, Heilmann EK, Picot A, Goddard R, Fu?rstner A. 2009. Molybdenum Nitride Complexes with Ph3SiO Ligands Are Exceedingly Practical and Tolerant Precatalysts for Alkyne Metathesis and Efficient Nitrogen Transfer Agents. J. Am. Chem. Soc.. 131(27):9468-9470. https://doi.org/10.1021/ja903259g