54530-05-1Relevant academic research and scientific papers
Modular Photocatalytic Synthesis of α-Trialkyl-α-Tertiary Amines
Gaunt, Matthew J.,Harris, Georgia R.,Henry Blackwell, J.,Smith, Milo A.
supporting information, p. 15946 - 15959 (2021/10/12)
Molecules displaying an α-trialkyl-α-tertiary amine motif provide access to an important and versatile area of biologically relevant chemical space but are challenging to access through existing synthetic methods. Here, we report an operationally straightforward, multicomponent protocol for the synthesis of a range of functionally and structurally diverse α-trialkyl-α-tertiary amines, which makes use of three readily available components: dialkyl ketones, benzylamines, and alkenes. The strategy relies on the of use visible-light-mediated photocatalysis with readily available Ir(III) complexes to bring about single-electron reduction of an all-alkyl ketimine species to an α-amino radical intermediate; the α-amino radical undergoes Giese-type addition with a variety of alkenes to forge the α-trialkyl-α-tertiary amine center. The mechanism of this process is believed to proceed through an overall redox neutral pathway that involves photocatalytic redox-relay of the imine, generated from the starting amine-ketone condensation, through to an imine-derived product. This is possible because the presence of a benzylic amine component in the intermediate scaffold drives a 1,5-hydrogen atom transfer step after the Giese addition to form a stable benzylic α-amino radical, which is able to close the photocatalytic cycle. These studies detail the evolution of the reaction platform, an extensive investigation of the substrate scope, and preliminary investigation of some of the mechanistic features of this distinct photocatalytic process. We believe this transformation will provide convenient access to previously unexplored α-trialkyl-α-tertiary amine scaffolds that should be of considerable interest to practitioners of synthetic and medicinal chemistry in academic and industrial institutions.
BF3-mediated additions of organolithiums to ketimines: X-ray crystal structures of BF3-ketimine complexes
Ma, Yun,Lobkovsky, Emil,Collum, David B.
, p. 2335 - 2337 (2007/10/03)
(Chemical Equation Presented) Additions of lithium acetylides and n-BuLi to N-alkyl ketimines mediated by BF3-Et2O in THF afford hindered tert-alkylamines in moderate to good yields. Stereochemical results and crystal structures of t
Sulfur centered 1,3-dipoles. An efficient trapping of adamantanethione-S-sulfide generated in the reaction of adamantanethione with organic azides
Mloston,Romanski,Heimgartner
, p. 437 - 445 (2007/10/03)
The reaction of adamantanethione (1) and an organic azide at 80°C ("two-component reaction") yields the symmetrical 1,2,4-trithiolane 9 and the corresponding adamantylidene imine 10 in nearly equal amounts. Under the same conditions, the "three-component reaction" with 1, phenyl azide and an aromatic thioketone gives the unsymmetrical 1,2,4-trithiolane 12 as the major product, and 9 and imine 13 as by-products. A 1,3-dipolar cycloaddition of an intermediate thiocarbonyl-S-sulfide and a thioketone is proposed as the mechanism for the formation of the trithiolanes. The structure of trithiolane 12a has been established by X-ray crystallography.
SYNTHESIS AND TRANSFORMATIONS OF OXAZIRIDINES. ADAMANTANE-2-SPIRO-3'-OXAZIRIDINE AND ITS N-ALKYL DERIVATIVES
Novoselov, E. F.,Isaev, S. D.,Yurchenko, A. G.
, p. 97 - 103 (2007/10/02)
Unsubstituted and N-substituted adamantane-2-spiro-3'-oxaziridine were synthesized by the oxidation of Schiff bases, obtained from adamantanone and alkyl(aryl)amines, with peroxyacetic acid.The thermal rearrangement of the N-substituted derivatives leads to N-substituted 5-azahomoadamantan-4-ones, while fragmentation under the influence of Fe(II) ions leads to derivatives of bicyclononane in the form of N-substituted amides.Adamantane-2-spiro-3'-oxaziridine gives different transformation products, i.e., adamantanone in the first case and 5-azahomoadamantan-4-one in the second.
Photolyse d'oxaziridines. 9. Structures d'oxaziridines a jonction spirannique par etude en rmn du carbone-13
Oliveros, Esther,Riviere, Monique,Lattes, Armand
, p. 107 - 112 (2007/10/02)
Several spirooxaziridines derived from cyclohexanones have been studied by 13Carbon nmr spectroscopy.This method allows us to put forward unambiguous configurations for these heterocycles.
