van Putten Robbert, Filonenko Georgy A, Krieger Annika M, Lutz Martin, Pidko Evgeny A
Inorganic Systems Engineering, Department of Chemical Engineering, Faculty of Applied Sciences, Delft University of Technology, Van der Maasweg 9, 2629 HZ Delft, The Netherlands.
Crystal and Structural Chemistry, Bijvoet Centre for Biomolecular Research, Utrecht University, Padualaan 8, 3584 CH Utrecht, The Netherlands.
Organometallics. 2021 Mar 22;40(6):674-681. doi: 10.1021/acs.organomet.0c00781. Epub 2021 Mar 2.
Alkoxycarbonylations are important and versatile reactions that result in the formation of a new C-C bond. Herein, we report on a new and halide-free alkoxycarbonylation reaction that does not require the application of an external carbon monoxide atmosphere. Instead, manganese carbonyl complexes and organo(alkoxy)borate salts react to form an ester product containing the target C-C bond. The required organo(alkoxy)borate salts are conveniently generated from the stoichiometric reaction of an organoborane and an alkoxide salt and can be telescoped without purification. The protocol leads to the formation of both aromatic and aliphatic esters and gives complete control over the ester's substitution (e.g., OMe, O Bu, OPh). A reaction mechanism was proposed on the basis of stoichiometric reactivity studies, spectroscopy, and DFT calculations. The new chemistry is particularly relevant for the field of Mn(I) catalysis and clearly points to a potential pathway toward irreversible catalyst deactivation.
烷氧基羰基化反应是重要且用途广泛的反应，可形成新的碳 - 碳键。在此，我们报道了一种新型的无卤烷氧基羰基化反应，该反应无需外部一氧化碳气氛。相反，羰基锰配合物与有机（烷氧基）硼酸盐反应形成含有目标碳 - 碳键的酯产物。所需的有机（烷氧基）硼酸盐可通过有机硼烷与醇盐的化学计量反应方便地生成，并且无需纯化即可直接进行后续反应。该方法可生成芳香族和脂肪族酯，并能完全控制酯的取代基（如甲氧基、丁氧基、苯氧基）。基于化学计量反应性研究、光谱学和密度泛函理论计算提出了反应机理。这种新化学对于锰（I）催化领域尤为重要，并且明确指出了一条导致催化剂不可逆失活的潜在途径。
