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

• Published in: Angewandte Chemie Vol. 130; no. 42; pp. 14103 - 14107
• Main Authors: Do, Dinh Cao Huan, Protchenko, Andrey V., Ángeles Fuentes, M., Hicks, Jamie, Kolychev, Eugene L., Vasko, Petra, Aldridge, Simon
• Format: Journal Article
• Language: English
• Published: Weinheim Wiley Subscription Services, Inc 15.10.2018
• Subjects: Acetyl chloride; Aldehydes; Carbonyl compounds; Carbonyls; Carbonylverbindungen; Chemistry; Chlorides; Lewis acid; Ligandeneffekte; Nukleophile Substitutionen; Organic chemistry; Oxidation; Silicium; Silicon; Strukturaufklärung; Substitutes; Synthesis
• ISSN: 0044-8249; 1521-3757
• DOI: 10.1002/ange.201807543

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. Ein einfaches Silicium‐Analogon eines Acylchlorids ist durch milde Oxidation eines N‐nacnac‐stabilisierten Chlorsilylens zugänglich (N‐nacnac=aminofunktionalisiertes β‐Diketiminat). Von diesem Silaacylchlorid aus sind Silaester und Silaaldehyde zugänglich, wobei analoge Methoden wie in der klassischen Carbonylchemie eingesetzt werden – ein Durchbruch bei der Übertragung organischer Reaktionspfade auf die schwereren Gruppe‐14‐Elemente.