Grzesiński Łukasz, Milewski Mariusz, Nadirova Maryana, Kajetanowicz Anna, Grela Karol
Biological and Chemical Research Centre, Faculty of Chemistry, University of Warsaw, Żwirki i Wigury Street 101, 02-089 Warsaw, Poland.
Organometallics. 2022 Nov 2;42(18):2453-2459. doi: 10.1021/acs.organomet.2c00428. eCollection 2023 Sep 25.
A set of ruthenium complexes bearing a CAAC or uNHC ligand and a dithiocatechol fragment have been obtained and characterized spectroscopically. The activity and -selectivity of the newly obtained catalysts were studied in selected model CM, self-CM, and RCM olefin metathesis reactions. Intriguingly, and in contrast to structurally related NHC-bearing catalysts and , the CAAC and uNHC analogues showed no or only very little activity in olefin metathesis. Interestingly, despite being not productive in metathesis reactions conducted in solution, enabled the synthesis of a model 16-membered macrocyclic lactone of valuable musk smell with excellent chemoselectivity (no C-C double-bond migration was observed) at a concentration 40 times higher than that typically used by organic chemists in similar macrocyclizations (200 mM instead of 5 mM) with excellent -selectivity. Unfortunately, also here the conversion was low.
已获得一组带有环戊二烯基氨基甲酸盐（CAAC）或非经典氮杂环卡宾（uNHC）配体以及二硫代邻苯二酚片段的钌配合物，并通过光谱对其进行了表征。在选定的模型交叉复分解反应（CM）、自复分解反应（self-CM）和关环复分解反应（RCM）烯烃复分解反应中研究了新制得催化剂的活性和选择性。有趣的是，与结构相关的含氮杂环卡宾催化剂不同，CAAC和uNHC类似物在烯烃复分解反应中没有活性或只有极低的活性。有意思的是，尽管在溶液中进行的复分解反应中没有效果，但它能够以比有机化学家在类似大环化反应中通常使用的浓度高40倍（200 mM而非5 mM）的浓度，以优异的化学选择性（未观察到碳 - 碳双键迁移）合成具有珍贵麝香气味的模型16元大环内酯，且具有优异的选择性。遗憾的是，此处的转化率也很低。
