Skip navigation
Please use this identifier to cite or link to this item: http://repository.iitr.ac.in/handle/123456789/3056
Title: Tuning the Reactivity of Ketones through Unsaturation: Construction of Cyclic and Acyclic Quaternary Stereocenters via Zn-ProPhenol Catalyzed Mannich Reactions
Authors: Trost B.M.
Hung C.-I.J.
Gnanamani, Elumalai
Published in: ACS Catalysis
Abstract: Introduction of unsaturation adjacent to the carbonyl drastically improves the reactivity of the Zn-ProPhenol catalyzed Mannich reactions between N-carbamoyl imines and a-branched ketones. Despite only a small change in the substrate acidity, the bimetallic catalyst can preferentially recognize and activate unsaturated ketones over their fully saturated counterparts, providing a chemo-, diastereo-, and enantioselective route to valuable ?-aminoketones bearing both cyclic and acyclic quaternary stereocenters, which are common motifs in numerous biologically active alkaloids. Unsaturated ketones and imines with various substitution patterns are viable substrates, and the reaction can be performed on multi-millimole scale at low catalyst loading without impacting its efficiency. More importantly, the unsaturation introduced via the nucleophile provides a useful platform for structural diversification. © Copyright 2019 American Chemical Society.
Citation: ACS Catalysis (2019), 9(2): 1549-1557
URI: https://doi.org/10.1021/acscatal.8b04685
http://repository.iitr.ac.in/handle/123456789/3056
Issue Date: 2019
Publisher: American Chemical Society
Keywords: asymmetric catalysis
catalysis
Mannich reactions
ProPhenol
quaternary stereocenters
zinc
ISSN: 21555435
Author Scopus IDs: 57217139833
56768679500
35319775800
Author Affiliations: Trost, B.M., Department of Chemistry, Stanford University, Stanford, CA 94305-5080, United States
Hung, C.-I.J., Department of Chemistry, Stanford University, Stanford, CA 94305-5080, United States
Gnanamani, E., Department of Chemistry, Stanford University, Stanford, CA 94305-5080, United States
Funding Details: We thank Dr. Jana Maclaren (Stanford University) for X-ray crystallographic analysis and Dr. Stephen Lynch (Stanford University) for conducting NOE experiments. We also thank Christopher Kalnmals (Stanford University) for technical assistance. Finally, C.-I.H. acknowledges support from the William S. Johnson Fellowship.
Corresponding Author: Trost, B.M.; Department of Chemistry, Stanford UniversityUnited States; email: bmtrost@stanford.edu
Appears in Collections:Journal Publications [CY]

Files in This Item:
There are no files associated with this item.
Show full item record


Items in Repository are protected by copyright, with all rights reserved, unless otherwise indicated.