1011-57-0Relevant articles and documents
Synthesis, structures and stereodynamic behavior of novel pentacoordinate (O→Si)-Chelate Difluoro(methyl)silylmethyl derivatives of amides and imides
Negrebetsky, Vadim V.,Kramarova, Eugeniya P.,Shipov, Aleksander G.,Baukov, Yuri I.,Korlyukov, Alexander A.,Arkhipov, Dmitry E.,Bassindale, Alan R.,Taylor, Peter G.,Bylikin, Sergey Yu
, p. 31 - 39 (2018)
The structures and stereodynamic behavior of (O→Si)-chelate methyldifluorosilanes in solutions were studied by multinuclear (1H, 13C, 19F, 29Si) and 2D (COSY, HETCOR 1H, 13C) NMR spectrosco
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.
Efficient metal-free hydrosilylation of tertiary, secondary and primary amides to amines
Blondiaux, Enguerrand,Cantat, Thibault
supporting information, p. 9349 - 9352 (2014/08/05)
Hydrosilylation of secondary and tertiary amides to amines is described using catalytic amounts of B(C6F5)3. The organic catalyst enables the reduction of amides with cost-efficient, non-toxic and air stable PMHS and TMDS hydrosilanes. The methodology was successfully extended to the more challenging reduction of primary amides.
Regio- and stereoselective methods for the conversion of (2S,3R)-β-phenylglycidic acid esters to taxoids and other enantiopure (2R,3S)-phenylisoserine esters
Afon'Kin,Kostrikin,Shumeiko,Popov,Matveev,Matvienko,Zabudkin
, p. 2149 - 2162 (2013/10/01)
A novel efficient method was proposed for the synthesis of enantiopure precursors of taxane-containing cytostatics, i.e., methyl esters of (2R,3S)- and (2S,3R)-N-benzoylphenylisoserine and similar taxoid esters. The method is based on the regio- and stereoselective hydrobromolysis of the corresponding trans-β-phenyl glycidate enatiomers, consecutive reactions of O-acylcarbamoylation of the obtained 3-bromohydrins, intramolecular cyclization to 4-phenyloxazolidin-2-one-5-carboxylic acid derivatives, and oxazolidinone ring opening.
Three-component synthesis of amine derivatives using benzylic and allylic alcohols as N-alkylating agents in the absence of external catalysts and additives
Li, Hai-Hua,Dong, De-Jun,Tian, Shi-Kai
experimental part, p. 3623 - 3626 (2009/05/07)
The direct employment of benzylic and allylic alcohols as N-alkylating agents provides a useful synthetic route for amine derivatives by avoiding the preactivation of the hydroxy groups of alcohols. Herein we report a novel by-product-catalyzed three-comp
REACTIONS OF 2-AMINO-4,5-BENZO-1,3,2-DIOXAPHOSPHOLANE WITH CARBOXYLIC AND PHOSPHOROUS ACIDS AND ACETIC ANHYDRIDE
Pudovik, M. A.,Kibardina, L. K.,Pudovik, A. N.
, p. 214 - 216 (2007/10/02)
The reactions of 2-amino-4,5-benzo-1,3,2-dioxaphospholane with acetic acid, benzoic acid, and acetic anhydride yield 2-trimethylsiloxy-4,5-benzo-1,3,2-dioxaphospholane.Upon reaction with dialkyl phosphites, the silylamidophosphite acts as a silylating agent.
An E.S.R. Investigation of Ethoxy and Trimethylsilyloxy Iminyl Radicals
Glover, Stephen A.,Beckwith, Athelstan L. J.
, p. 701 - 709 (2007/10/02)
Trimethylsilyloxy and ethoxy iminyls (4a-i) have been generated by photolysis of solutions of the corresponding trimethylsilyl and ethyl N-chloro imidates, in the cavity of an e.s.r. spectrometer.The unpaired electron resides in a 2py orbital o
