A β‐Diketiminate‐Stabilized Sila‐Acyl Chloride: Systematic Access to Base‐Stabilized Silicon Analogues of Classical Carbonyl Compounds

An oxidation/substitution strategy for the synthesis of silicon analogues of classical organic carbonyl compounds is reported, by making use of a novel β‐diketiminate‐supported sila‐acyl chloride—the first example of such a compound isolated without the use of a stabilizing Lewis acid. Nucleophilic...

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Bibliographic Details
Published in:Angewandte Chemie International Edition 2018-10, Vol.57 (42), p.13907-13911
Main Authors: Do, Dinh Cao Huan, Protchenko, Andrey V., Ángeles Fuentes, M., Hicks, Jamie, Kolychev, Eugene L., Vasko, Petra, Aldridge, Simon
Format: Article
Language:English
Subjects:
Acetyl chloride
Aldehydes
Carbonyl compounds
Carbonyls
Chlorides
Lewis acid
ligand effects
nucleophilic substitution
Organic chemistry
Oxidation
Silicon
structure elucidation
Substitutes
Synthesis
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Summary:An oxidation/substitution strategy for the synthesis of silicon analogues of classical organic carbonyl compounds is reported, by making use of a novel β‐diketiminate‐supported sila‐acyl chloride—the first example of such a compound isolated without the use of a stabilizing Lewis acid. Nucleophilic substitution at the SiIV center allows direct access to the corresponding sila‐aldehyde and sila‐ester. An alternative approach utilizing the reverse order of synthetic steps is thwarted by the facile rearrangement of the corresponding SiII systems featuring either H or OR substituents. As such, the isolation of (N‐nacnac)Si(O)Cl represents a key step forward in enabling the synthesis of sila‐carbonyl compounds by a synthetic approach ubiquitous in organic chemistry. Nacnac. Who′s there? The first simple silicon analogue of an acyl chloride can be accessed by mild oxidation of an N‐nacnac‐stabilized chlorosilylene (N‐nacnac=amino‐functionalized β‐diketiminate). This sila‐acyl chloride undergoes facile functional‐group exchange to yield the corresponding sila‐ester and sila‐aldehyde in a manner analogous to that seen in classical carbonyl chemistry.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.201807543