Silylation of Alcohols, Phenols, and Silanols with Alkynylsilanes – an Efficient Route to Silyl Ethers and Unsymmetrical Siloxanes

The formation of several silyl ethers (alkoxysilanes, R3Si‐OR') and unsymmetrical siloxanes (R3Si‐O‐SiR'3) can be catalyzed by the commercially available potassium bis(trimethylsilyl)amide (KHMDS). The reaction proceeds via direct dealkynative coupling between various alcohols or silanols...

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Bibliographic Details
Published in:European journal of organic chemistry 2020-07, Vol.2020 (26), p.4042-4049
Main Authors: Kuciński, Krzysztof, Stachowiak, Hanna, Hreczycho, Grzegorz
Format: Article
Language:English
Subjects:
Acetylene
Alcohol
Alcohols
Alkoxysilanes
Alkynylsilanes
Base‐catalysis
Coupling
Dehydrogenation
Ethers
Organosilicon compounds
Phenols
Siloxanes
Silyl ethers
Solvent‐free
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Summary:The formation of several silyl ethers (alkoxysilanes, R3Si‐OR') and unsymmetrical siloxanes (R3Si‐O‐SiR'3) can be catalyzed by the commercially available potassium bis(trimethylsilyl)amide (KHMDS). The reaction proceeds via direct dealkynative coupling between various alcohols or silanols and alkynylsilanes, with a simultaneous formation of gaseous acetylene as the sole by‐product. The dehydrogenative and dealkenative coupling of alcohols or silanols are well‐investigated, whilst the utilization of alkynylsilanes as silylating agents has never been comprehensively studied in this context. Overall, the presented system allows the synthesis of various attractive organosilicon compounds under mild conditions, making this approach an atom‐efficient, environmentally benign, and sustainable alternative to existing synthetic solutions. Alkynylsilanes – a missing piece of different silylation agents, can serve as valuable substrates in the O‐silylation through a dealkynative coupling with alcohols or silanols. The described approach displays a whole array of advantages in terms of green chemistry and is a promising alternative to existing methodologies.
ISSN:1434-193X
1099-0690
DOI:10.1002/ejoc.202000573