91230-07-8Relevant academic research and scientific papers
Quaternary Charge-Transfer Complex Enables Photoenzymatic Intermolecular Hydroalkylation of Olefins
Page, Claire G.,Cooper, Simon J.,Dehovitz, Jacob S.,Oblinsky, Daniel G.,Biegasiewicz, Kyle F.,Antropow, Alyssa H.,Armbrust, Kurt W.,Ellis, J. Michael,Hamann, Lawrence G.,Horn, Evan J.,Oberg, Kevin M.,Scholes, Gregory D.,Hyster, Todd K.
supporting information, p. 97 - 102 (2021/01/12)
Intermolecular C-C bond-forming reactions are underdeveloped transformations in the field of biocatalysis. Here we report a photoenzymatic intermolecular hydroalkylation of olefins catalyzed by flavin-dependent 'ene'-reductases. Radical initiation occurs via photoexcitation of a rare high-order enzyme-templated charge-transfer complex that forms between an alkene, α-chloroamide, and flavin hydroquinone. This unique mechanism ensures that radical formation only occurs when both substrates are present within the protein active site. This active site can control the radical terminating hydrogen atom transfer, enabling the synthesis of enantioenriched γ-stereogenic amides. This work highlights the potential for photoenzymatic catalysis to enable new biocatalytic transformations via previously unknown electron transfer mechanisms.
Ruthenium-catalyzed alkene-alkyne coupling of disubstituted olefins: Application to the stereoselective synthesis of trisubstituted enecarbamates
Trost, Barry M.,Cregg, James J.
supporting information, p. 620 - 623 (2015/01/30)
The Ru-catalyzed alkene-alkyne coupling reaction has been demonstrated to be an enabling methodology for the synthesis of complex molecules. However, to date, it has been limited to monosubstituted olefins. Herein we report the first general utilization o
Relay catalysis by a metal-complex/bronsted acid binary system in a tandem isomerization/carbon-carbon bond forming sequence
Sorimachi, Keiichi,Terada, Masahiro
supporting information; experimental part, p. 14452 - 14453 (2009/02/08)
A one-pot tandem isomerization/carbon-carbon bond forming sequence catalyzed by a ruthenium complex/Bronsted acid binary system is demonstrated. The method enables the use of readily available allylamides to deliver reactive imines under relay catalysis using a binary catalytic system. Subsequent Bronsted acid catalyzed carbon-carbon bond forming reactions of the generated imines with nucleophilic components afforded Friedel-Crafts and Mannich products in good yields. Copyright
Allylic Selenides in Organic Synthesis: New Methods for the Synthesis of Allylic Amines
Shea, Regan G.,Fitzner, Jeffrey N.,Fankhauser, John E.,Spaltenstein, Andreas,Carpino, Philip A.,et al.
, p. 5243 - 5252 (2007/10/02)
Oxidative rearrangement of allylic selenides in the presence of various amine nucleophiles provides synthetic access to a variety of allylic amine derivatives.The stereochemical outcome of these reactions has been investigated, and is consistent with a -sigmatropic rearrangement mechanism.Several D-α-amino acids and racemic β,γ-unsaturated α-amino acids were prepared in this manner.A variant of this process employing an achiral allylic selenide and chiral amide afforded protected allylic amines in low diastereoisomeric excess.
