A β‐Diketiminate‐Stabilized Sila‐Acyl Chloride: Systematic Access to Base‐Stabilized Silicon Analogues of Classical Carbonyl Compounds. Issue 42 (21st September 2018)

• Record Type: Journal Article
• Authors: Do, Dinh Cao Huan; Protchenko, Andrey V.; Ángeles Fuentes, M.; Hicks, Jamie; Kolychev, Eugene L.; Vasko, Petra; Aldridge, Simon
• Is Part Of: Angewandte Chemie international edition. Volume 57:Issue 42(2018)
• Page Start: 13907
• Page End: 13911
• Publication Date: 2018-09-21
• Subjects: carbonyl compounds -- ligand effects -- nucleophilic substitution -- silicon -- structure elucidation; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201807543
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: 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 Si IV 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 Si II 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. Abstract : 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.