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Elucidating the origin of selectivity of [3 + 2]-cycloaddition reactions between thioketone and carbohydrate-derived nitrones by the DFT

  • Junxia Yang
  • Yan Zhang
  • Yongsheng Yang
  • Ying XueEmail author
Original Paper
  • 46 Downloads

Abstract

The mechanism and origin of selectivity for [3 + 2]-cycloaddition (32CA) reactions between thioketone and carbohydrate-derived nitrones in THF were investigated by using the density functional theory (DFT) at the M06-2X/6-311+G(d,p)//M06-2X/6-31+G(d,p) level of theory combined with the solvation SMD model. The calculated results revealed that the 32CA reactions proceed through the asynchronous one-step manner. For the chemoselectivity in thioketone, the C=S bond as a dipolarophile attacking three-atom-component (TAC) nitrone in reactivity was more preferential than the C=O bond. The theoretical results also confirmed the stereoselectivity of two 32CA reactions of thioketone with carbohydrate-derived nitrones with the anti-form product being more favored than the syn-form product, and the predicted anti/syn product ratios are in agreement with the experimental ones in literature. Furthermore, the analysis of the conceptual density functional theory reactivity indices showed that the 32CA reactions have polar character. Weak noncovalent interaction and Parr function analyses are used to reveal the origin of the stereoselectivity.

Graphical abstract

[3 + 2]-cycloaddition reactions between thioketone and carbohydrate-derived nitrones

Keywords

Thioketone Carbohydrate-derived nitrones [3 + 2]-cycloaddition reactions Selectivity DFT calculation 

Notes

Acknowledgments

This project has been supported by the National Natural Science Foundation of China (Grant No. 21573153).

Supplementary material

894_2019_4104_MOESM1_ESM.docx (217 kb)
ESM 1 (DOCX 217 kb)

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Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2019

Authors and Affiliations

  1. 1.College of Chemistry, Key Lab of Green Chemistry and Technology in Ministry of EducationSichuan UniversityChengduPeople’s Republic of China

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