Pretorius René, Olguín Juan, Albrecht Martin
Departement für Chemie und Biochemie, Universität Bern , Freiestrasse 3, CH-3012 Bern, Switzerland.
School of Chemistry and Chemical Biology, University College Dublin , Belfield, Dublin 4, Ireland.
Inorg Chem. 2017 Oct 16;56(20):12410-12420. doi: 10.1021/acs.inorgchem.7b01899. Epub 2017 Oct 3.
Acetylglucose- and acetylgalactose-functionalized triazolylideneruthenium(II) and -iridium(III) complexes were synthesized and fully characterized. Subsequent carbohydrate deprotection yielded the first examples of glucose- and galactose-functionalized 1,2,3-triazolylideneiridium complexes. Base-free oxidation of alcohols and amines was used to probe the catalytic potential of the metal complexes and the influence of the carbohydrate wingtip group. Generally, the performance of these complexes is higher in amine oxidation than in alcohol oxidation. While the stereochemistry at the carbohydrate C4 position had no marked influence (galactose vs glucose), the ruthenium complexes typically exhibited higher substrate selectivity and product specificity compared to the analogous iridium species. Most noteworthy is the fact that the catalytic performance is significantly enhanced when the carbohydrate functionality is deprotected, suggesting an active role of the carbohydrate substituent in these transformations.
合成并全面表征了乙酰葡萄糖和乙酰半乳糖功能化的三唑亚基钌（II）和铱（III）配合物。随后的碳水化合物脱保护产生了葡萄糖和半乳糖功能化的1,2,3-三唑亚基铱配合物的首个实例。利用醇和胺的无碱氧化来探究金属配合物的催化潜力以及碳水化合物末端基团的影响。一般来说，这些配合物在胺氧化中的性能高于醇氧化。虽然碳水化合物C4位的立体化学没有显著影响（半乳糖与葡萄糖），但与类似的铱物种相比，钌配合物通常表现出更高的底物选择性和产物特异性。最值得注意的是，当碳水化合物官能团脱保护时，催化性能显著增强，这表明碳水化合物取代基在这些转化中起到了积极作用。
