Please use this identifier to cite or link to this item: https://hdl.handle.net/10356/155057
Title: Catalytic atroposelective synthesis of axially chiral benzonitriles via chirality control during bond dissociation and CN group formation
Authors: Lv, Ya
Luo, Guoyong
Liu, Qian
Jin, Zhichao
Zhang, Xinglong
Chi, Robin Yonggui
Keywords: Science::Chemistry
Issue Date: 2022
Source: Lv, Y., Luo, G., Liu, Q., Jin, Z., Zhang, X. & Chi, R. Y. (2022). Catalytic atroposelective synthesis of axially chiral benzonitriles via chirality control during bond dissociation and CN group formation. Nature Communications, 13(1), 36-. https://dx.doi.org/10.1038/s41467-021-27813-4
Project: NRFNRFI2016-06
NRF-CRP22-2019-0002
RG7/20
RG5/19
MOE2019-T2-2-117
MOE2018-T3-1- 003
Journal: Nature Communications
Abstract: The applications of axially chiral benzonitriles and their derivatives remain mostly unexplored due to their synthetic difficulties. Here we disclose an unusual strategy for atroposelective access to benzonitriles via formation of the nitrile unit on biaryl scaffolds pre-installed with stereogenic axes in racemic forms. Our method starts with racemic 2-arylbenzaldehydes and sulfonamides as the substrates and N-heterocyclic carbenes as the organocatalysts to afford axially chiral benzonitriles in good to excellent yields and enantioselectivities. DFT calculations suggest that the loss of p-toluenesulfinate group is both the rate-determining and stereo-determining step. The axial chirality is controlled during the bond dissociation and CN group formation. The reaction features a dynamic kinetic resolution process modulated by both covalent and non-covalent catalytic interactions. The axially chiral benzonitriles from our method can be easily converted to a large set of functional molecules that show promising catalytic activities for chemical syntheses and anti-bacterial activities for plant protections.
URI: https://hdl.handle.net/10356/155057
ISSN: 2041-1723
DOI: 10.1038/s41467-021-27813-4
Schools: School of Physical and Mathematical Sciences 
Rights: © 2022 The Author(s). This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons license and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this license, visit http://creativecommons.org/ licenses/by/4.0/.
Fulltext Permission: open
Fulltext Availability: With Fulltext
Appears in Collections:SPMS Journal Articles

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