35449-05-9Relevant articles and documents
Nitrogen Atom Transfer Catalysis by Metallonitrene C?H Insertion: Photocatalytic Amidation of Aldehydes
Schmidt-R?ntsch, Till,Verplancke, Hendrik,Lienert, Jonas N.,Demeshko, Serhiy,Otte, Matthias,Van Trieste, Gerard P.,Reid, Kaleb A.,Reibenspies, Joseph H.,Powers, David C.,Holthausen, Max C.,Schneider, Sven
supporting information, (2022/01/20)
C?H amination and amidation by catalytic nitrene transfer are well-established and typically proceed via electrophilic attack of nitrenoid intermediates. In contrast, the insertion of (formal) terminal nitride ligands into C?H bonds is much less developed and catalytic nitrogen atom transfer remains unknown. We here report the synthesis of a formal terminal nitride complex of palladium. Photocrystallographic, magnetic, and computational characterization support the assignment as an authentic metallonitrene (Pd?N) with a diradical nitrogen ligand that is singly bonded to PdII. Despite the subvalent nitrene character, selective C?H insertion with aldehydes follows nucleophilic selectivity. Transamidation of the benzamide product is enabled by reaction with N3SiMe3. Based on these results, a photocatalytic protocol for aldehyde C?H trimethylsilylamidation was developed that exhibits inverted, nucleophilic selectivity as compared to typical nitrene transfer catalysis. This first example of catalytic C?H nitrogen atom transfer offers facile access to primary amides after deprotection.
Lewis acid catalyzed enlargement of cyclic β-alkoxyenals and one-pot synthesis of polyfunctional enoxysilanes derived from aucubin with trimethylsilyldiazomethane
Lemus, Christelle,Poleschak, Marko,Gailly, Sophie,Desage-El Murr, Marine,Koch, Michel,Deguin, Brigitte
supporting information, p. 4686 - 4690 (2013/05/22)
Pyrane to oxepane in one step: Highly regio- and stereoselective homologations dependent on the nature of carbonyl function and catalysts have been observed during the formation of enoxysilanes (see scheme). Trimethylsilyl trifluoromethanesulfonate (TMSOT
A new method for the preparation of silyl enol ethers from carbonyl compounds and (trimenthylsily)diazomethane in a regiospecific and highly stereoselective manner
Aggarwal, Varinder K.,Sheldon, Chris G.,Macdonald, Gregor J.,Martin, William P.
, p. 10300 - 10301 (2007/10/03)
The reaction of lithium (trimethylsilyl)diazomethane with aldehydes and ketones has been investigated, and it has been found that quenching at low temperature with MeOH followed by addition of Rh2(OAc)4 gave silyl enol ethers in high yields. Quenching with other electrophiles (e.g., deuterium, MeI) gave terminal and substituted silyl enol ethers with complete control over regio- and stereochemistry. The mechanism of this novel process has been mapped out through a combination of deuterium labeling, ReactIR, and isolation of reaction intermediates. Copyright
STEREO- AND REGIOSELECTIVE FORMATION OF SILYL ENOL ETHERS VIA OXIDATION OF VINYL ANIONS
Davis, Franklin A.,Lal, Sankar G.,Wei, Jia
, p. 4269 - 4272 (2007/10/02)
Oxidation of E- and Z-vinyl lithiums with silyl peroxides 5 affords silyl enol ethers 3 in good to excellent yield with retention of configuration.This methodology represents a useful new procedure for the stereo and regioselective synthesis of ketone eno
