We report the total synthesis of (+)-eburnamonine using enantioselective alkene cyanoamidation to form the all-carbon quaternary stereocenter. Palladium, phosphoramidite ligand, and a Lewis acid combine to form a co-catalyst that promotes C-CN activation of a cyanoformamide, followed by intramolecular alkene cyanoamidation. Overall, the synthesis of (+)-eburnamonine is accomplished in 8 steps from 4-methylene hexanoic acid and tryptamine, providing an example of asymmetric aliphatic-tethered alkene cyanoamidation and its use in total synthesis.
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Total Synthesis of (+)-Eburnamonine Using Asymmetric Alkene Cyanoamidation through C-CN Bond Activation.
Org Lett
July 2024
Department of Chemistry, University of Minnesota─Twin Cities, Minneapolis, Minnesota 55455, United States.
We report the total synthesis of (+)-eburnamonine using enantioselective alkene cyanoamidation to form the all-carbon quaternary stereocenter. Palladium, phosphoramidite ligand, and a Lewis acid combine to form a co-catalyst that promotes C-CN activation of a cyanoformamide, followed by intramolecular alkene cyanoamidation. Overall, the synthesis of (+)-eburnamonine is accomplished in 8 steps from 4-methylene hexanoic acid and tryptamine, providing an example of asymmetric aliphatic-tethered alkene cyanoamidation and its use in total synthesis.
View Article and Find Full Text PDFDiastereoselective Intramolecular Cyanoamidation with Alkenes.
European J Org Chem
January 2017
Department of Chemistry, University of Minnesota-Twin Cities 207 Pleasant St. SE, Minneapolis, MN 55155, USA.
Reported herein is a diastereoselective intramolecular alkene cyanoamidation, wherein high d.r. values are imparted by chiral directing groups.
View Article and Find Full Text PDFMechanistic Model for Enantioselective Intramolecular Alkene Cyanoamidation via Palladium-Catalyzed C-CN Bond Activation.
J Org Chem
April 2017
Department of Chemistry, University of Minnesota-Twin Cities, 207 Pleasant Street SE, Minneapolis, Minnesota 55455, United States.
We studied key aspects of the mechanism of Pd-catalyzed C-CN bond activation and intramolecular enantioselective alkene cyanoamidation. An Abboud-Abraham-Kamlet-Taft (AAKT) linear solvation energy relationship (LSER) model for enantioselectivity was established. We investigated the impact of Lewis acid (BPh), Lewis base (DMPU), and no additives.
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Org Lett
March 2010
Department of Chemistry, 207 Pleasant Street, SE, University of Minnesota, Minneapolis, Minnesota 55455, USA.
The first asymmetric cyanoamidation with synthetically useful enantioselectivity (ee up to 99%) to produce 3,3-disubstituted oxindoles is reported. Palladium catalysts with chiral phosphoramidite ligands activate the cyanoformamide C-CN bond, which is subsequently functionalized with a tethered alkene to give all-carbon quaternary stereocenters. The use of the N,N-(i-Pr)(2) derivative of octahydro-MonoPhos allowed the production of oxindoles with high enantioselectivities.
View Article and Find Full Text PDFIntra- and intermolecular amidation of C-C unsaturated bonds through palladium-catalyzed reactions of carbamoyl derivatives.
Chem Rec
February 2009
Graduate School of Pharmaceutical Sciences, Kyoto University, Yoshida, Sakyo-ku, Kyoto 606-8501, Japan.
Toward concise access to functionalized amides and lactams, palladium-catalyzed amidations of alkynes and alkenes with formamide derivatives were developed. Cyanoformamides having an alkynyl group were found to undergo intermolecular cyanoamidation in the presence of palladium catalyst to afford alpha-alkylidene lactams. Whereas, when cyanoformamides that possess a 1,1-disubstituted alkenyl group were used as starting materials, alpha,alpha-disubstituted lactams were obtained.
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