Version 1
: Received: 9 July 2018 / Approved: 10 July 2018 / Online: 10 July 2018 (11:54:41 CEST)
How to cite:
Li, H.; Luo, M.; Tao, G.; Qin, S. Computational Investigation on the Enantioselective Copper(I)-Catalyzed Addition of Enynes to Ketones. Preprints2018, 2018070175. https://doi.org/10.20944/preprints201807.0175.v1
Li, H.; Luo, M.; Tao, G.; Qin, S. Computational Investigation on the Enantioselective Copper(I)-Catalyzed Addition of Enynes to Ketones. Preprints 2018, 2018070175. https://doi.org/10.20944/preprints201807.0175.v1
Li, H.; Luo, M.; Tao, G.; Qin, S. Computational Investigation on the Enantioselective Copper(I)-Catalyzed Addition of Enynes to Ketones. Preprints2018, 2018070175. https://doi.org/10.20944/preprints201807.0175.v1
APA Style
Li, H., Luo, M., Tao, G., & Qin, S. (2018). Computational Investigation on the Enantioselective Copper(I)-Catalyzed Addition of Enynes to Ketones. Preprints. https://doi.org/10.20944/preprints201807.0175.v1
Chicago/Turabian Style
Li, H., Guohong Tao and Song Qin. 2018 "Computational Investigation on the Enantioselective Copper(I)-Catalyzed Addition of Enynes to Ketones" Preprints. https://doi.org/10.20944/preprints201807.0175.v1
Abstract
Computational investigations on the BPE-ligated Cu-catalysed enantioselective addition of enynes to ketones were performed with DFT method. Two BPE-CuMes catalysts, BPE-CuMes and (S,S)-Ph-BPE–CuMes, were employed to probe the reaction mechanism with the emphasis on stereoselectivity. The calculations on the BPE-CuMes system indicate that the actvie metallized enyne intermediate acts as the catalyst for the catalytic cycle. The catalytic cycle involves two steps: 1) the ketone addition to the alkene moiety of the metallized enyne; 2) the metallization of enyne followed by the release of product with the recovery of the active metallized enyne intermediate. The first step accounts for the distribution of the products, and therefore is the stereo-controlling step in chiral systems. In the chiral (S,S)-Ph-BPE–CuMes system, the steric hindrance is vital for the distribution of products and responsible for the stereoselectivity of this reaction. The steric hindrance between the phenyl ring of the two substrates and groups at the chiral centers in the ligand skeleton is identified as the original of the stereoselectivity for the titled reaction.
Keywords
copper-catalysed; enantioselective; DFT
Subject
Chemistry and Materials Science, Organic Chemistry
Copyright:
This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.
