848821-61-4Relevant articles and documents
Mechanism of the stereoselective α-alkylation of aldehydes driven by the photochemical activity of enamines
Bahamonde, Ana,Melchiorre, Paolo
supporting information, p. 8019 - 8030 (2016/07/11)
Herein we describe our efforts to elucidate the key mechanistic aspects of the previously reported enantioselective photochemical α-alkylation of aldehydes with electron-poor organic halides. The chemistry exploits the potential of chiral enamines, key organocatalytic intermediates in thermal asymmetric processes, to directly participate in the photoexcitation of substrates either by forming a photoactive electron donor-acceptor complex or by directly reaching an electronically excited state upon light absorption. These photochemical mechanisms generate radicals from closed-shell precursors under mild conditions. At the same time, the ground-state chiral enamines provide effective stereochemical control over the enantioselective radical-trapping process. We use a combination of conventional photophysical investigations, nuclear magnetic resonance spectroscopy, and kinetic studies to gain a better understanding of the factors governing these enantioselective photochemical catalytic processes. Measurements of the quantum yield reveal that a radical chain mechanism is operative, while reaction-profile analysis and rate-order assessment indicate the trapping of the carbon-centered radical by the enamine, to form the carbon-carbon bond, as rate-determining. Our kinetic studies unveil the existence of a delicate interplay between the light-triggered initiation step and the radical chain propagation manifold, both mediated by the chiral enamines.
Transfer of 1-alkenyl groups between secondary amines. Relative stability and reactivity of enamines from popular organocatalysts
Carneros, Hector,Sanchez, Dani,Vilarrasa, Jaume
, p. 2900 - 2903 (2014/06/23)
Enamines from 3-methylbutanal and several Pro- and Phe-derived secondary amines were prepared in DMSO-d6, CD3CN, and CDCl 3. For the first time, the relative thermodynamic stabilities of these and other enamines were compared, and rapid exchanges of 1-alkenyl groups were demonstrated. Competition experiments showed that the most favored enamines (without significant steric inhibition of resonance) react more rapidly with electrophiles.
CATALYTIC ASYMMETRIC SYNTHESIS OF OPTICALLY ACTIVE α-HALO-CARBONYL COMPOUNDS
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Page/Page column 31-32, (2010/02/13)
A process for the catalytic asymmetric synthesis of an optically active compound of the formula (la) or (lb): wherein R is an organic group; X is halogen; Rland R2which may the same or different represents H, or an organic group or R