Citation: Meng-Meng Zheng, Hao-Dong Tan, Yueqian Sang, Xiao-Song Xue, Jin-Pei Cheng. Computational insights into the effects of reagent structure and bases on nucleophilic monofluoromethylation of aldehydes[J]. Chinese Chemical Letters, ;2022, 33(5): 2387-2390. doi: 10.1016/j.cclet.2021.11.045 shu

Computational insights into the effects of reagent structure and bases on nucleophilic monofluoromethylation of aldehydes

Meng-Meng Zheng ^a ,
Hao-Dong Tan ^a ,
Yueqian Sang ^b ,
Xiao-Song Xue ^{a, b, *,} ,
Jin-Pei Cheng ^{a, c}

a.
State Key Laboratory of Elemento-Organic Chemistry, College of Chemistry, Nankai University, Tianjin 300071, China
b.
Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, Shanghai 200032, China
c.
Center of Basic Molecular Science, Department of Chemistry, Tsinghua University, Beijing 100084, China

xuexs@sioc.ac.cn

xuexs@nankai.edu.cn

Received Date: 18 September 2021
Revised Date: 13 November 2021
Accepted Date: 15 November 2021
Available Online: 19 November 2021

Figures(5)

Although fluorobis(phenylsulfonyl)methane (FBSM) and its cyclic analog 2-fluoro-1, 3-benzodithiole-1, 1, 3, 3-tetraoxide (FBDT) possess similar physicochemical properties, Shibata et al. found that FBSM failed to undergo nucleophilic monofluoromethylation of aldehydes regardless of the reaction conditions attempted (using various organic and inorganic bases). However, it was later discovered by Hu et al. that the nucleophilic monofluoromethylation could be accomplished by employing lithium hexamethyldisilazide (LiHMDS) as a base. Herein, we present an in-depth computational investigation into the intriguing effects of reagent structure and bases on the nucleophilic monofluoromethylation of aldehydes. The computations reveal the 1, 4-diazabicyclo[2.2.2]octane (DABCO) catalyzed nucleophilic monofluoromethylation of benzaldehyde with acyclic FBSM is a thermodynamically unfavorable process mainly due to the destabilizing O···O lone pair repulsions in FBSM product, whereas such repulsion could be largely avoided in FBDT product because of its constrained five-membered ring structure. Employing LiHMDS as a base can not only facilitate the nucleophilic monofluoromethylation via Li–O interactions but also render the monofluoromethylation of benzaldehyde with FBSM thermodynamically favored.
- Nucleophilic monofluoromethylation,
- Fluoroalkylation reagent,
- DFT calculations,
- Thermodynamic effect,
- Lone pair repulsion
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