Co2(CO)8-Catalyzed Reactions of Acetals or Lactones with Hydrosilanes and Carbon Monoxide. A New Access to the Preparation of 1,2-Diol Derivatives through Siloxymethylation

The Co-2(CO)(8)-catalyzed reaction of acetals with hydrosilanes and CO under mild reaction conditions (an ambient temperature under an ambient CO pressure), leading to the production of vicinal diols is reported. A siloxymethyl group can be introduced via the cleavage of one of two alkoxy groups in the acetal. The effects of the types of hydrosilanes, acetals, solvents, and reaction temperatures on the yield of siloxymethylation products were examined in detail. The reactivity for hydrosilanes is as follows; HSiMe3 > HSiEtMe2 > HSiEt2Me > HSiEt3. Hemiacetal esters are more reactive than dimethyl acetals. The polarity of the solvent used also has a significant effect on both the course of the reaction as well as the reaction rate. The site-selective siloxymethylation can be achieved in the case of cyclic acetals such as tetrahydrofuran (THF) and tetrahydropyrane (THP) derivatives, depending on the nature of the oxygen substituent attached adjacent to the oxygen atom in the ring. When 2-alkoxy THF or THP derivatives are used as substrates, the siloxymethylation takes place with cleavage of the ring C-O bond. In contrast, the reaction of 2-acetoxy THF or THP derivatives results in siloxymethylation with the cleavage of C-OAc bond. The ring-opening siloxymethylation of lactones was also examined.

Automated summary

The study reports a Co-2(CO)(8)-catalyzed reaction of acetals with hydrosilanes and CO, leading to the production of vicinal diols under mild reaction conditions. The effects of different hydrosilanes, acetals, solvents, and reaction temperatures on the yield of siloxymethylation products were examined. Site-selective siloxymethylation can be achieved with cyclic acetals, depending on the nature of the oxygen substituent attached adjacent to the oxygen atom in the ring.