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Guo et al. Chem Synth 2023;3:34 Chemical Synthesis
DOI: 10.20517/cs.2023.04

Short Communication Open Access

Direct construction of d -methylated all-carbon
3
quaternary stereocenters through carbene-catalyzed
desymmetrization

2,#
3
2,#
Jingcheng Guo , Ye Zhang , Xiaoxiang Zhang , Zhenqian Fu 1,2,*
1
Ningbo Institute, Chongqing Technology Innovation Center, Frontiers Science Center for Flexible Electronics (FSCFE),
Northwestern Polytechnical University, Xi'an 710072, Shaanxi, China.
2
Institute of Advanced Materials, Nanjing Tech University, Nanjing 211816, Jiangsu, China.
3
Jiangsu Co-Innovation Center of Efficient Processing and Utilization of Forest Resources, College of Chemical Engineering,
Nanjing Forestry University, Nanjing 210037, Jiangsu, China.
#
All authors contributed equally.
*
Correspondence to: Prof. Zhenqian Fu, Institute of Advanced Materials, Nanjing Tech University, 30 South Puzhu Road, Nanjing
211816, Jiangsu, China. E-mail: iamzqfu@njtech.edu.cn
How to cite this article: Guo J, Zhang Y, Zhang X, Fu Z. Direct construction of d -methylated all-carbon quaternary stereocenters
3
through carbene-catalyzed desymmetrization. Chem Synth 2023;3:34. https://dx.doi.org/10.20517/cs.2023.04
Received: 28 Jan 2023 First Decision: 4 Apr 2023 Revised: 23 Apr 2023 Accepted: 30 May 2023 Published: 19 Jul 2023
Academic Editors: Bao-Lian Su, Feng Shi Copy Editor: Dan Zhang Production Editor: Dan Zhang

Abstract
The construction of d -methylated all-carbon quaternary stereocenters has been successfully developed via
3
carbene-catalyzed desymmetrization of prochiral d -methylated oxindolyl 1,3-diketones. Three new stereogenic
3
centers were efficiently constructed with satisfactory outcomes. Diverse spiro-polycyclic molecules with a d -
3
methylated all-carbon quaternary stereocenter were generated in good to excellent yields with good to excellent
diastereoselectivities and excellent enantioselectivities. This reaction features a broad substrate scope, good
functional-group tolerance, and easy scale-up.

Keywords: d -Methylated, all-carbon quaternary stereocenters, N-Heterocyclic carbene, organocatalysis,
3
desymmetrization

As a result of the unique nature of deuterium, deuterium-labeled organic compounds have been widely used
[3-5]
in organic chemistry , pharmaceuticals , and materials [6-10] . In the field of medicinal chemistry, replacing
[1,2]
a hydrogen atom of a bioactive molecule with a deuterium atom can significantly improve the

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