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The mechanism behind enhanced reactivity of unsaturated phosphorus(v) electrophiles towards thiols

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Title
The mechanism behind enhanced reactivity of unsaturated phosphorus(v) electrophiles towards thiols
Author(s)
Yerin Park; Baumann, Alice L.; Hyejin Moon; Byrne, Stephen; Kasper, Marc-Andre; Hwang, Songhwan; Sun, Han; Mu-Hyun Baik; Hackenberger, Christian P. R.
Publication Date
2021-05
Journal
CHEMICAL SCIENCE, v.12, no.23, pp.8141 - 8148
Publisher
ROYAL SOC CHEMISTRY
Abstract
Vinyl- and ethynyl phosphorus(v) electrophiles are a versatile class of thiol-reactive reagents suitable for cysteine-selective peptide and protein modifications, especially for the generation of antibody conjugates. Herein we investigated the reactivity of various P(v) reagents towards thiol addition. Complementing previous studies, we observed that the heteroatoms X (X = S, O, NH) as well as the vinyl- vs. ethynyl-substituent bound to phosphorus greatly influence the overall reactivity. These experimentally observed trends, as well as the high Z-selectivity for thiol additions to ethynyl derivatives, were further elucidated using DFT calculations. Hyperconjugation was a key means of stabilizing the intermediate generated upon the thiol addition, thus determining both the reactivity and stereoselectivity of unsaturated P(v) electrophiles. Specifically, the energetically low-lying sigma antibonding orbital of the P-S bond more readily stabilizes the electron density from the lone pair (LP) of the generated carbanion, rendering the phosphonothiolates more reactive compared to the derivatives bearing oxygen and nitrogen. Our studies provide a detailed mechanistic picture for designing P(v)-based electrophiles with fine-tuned reactivity profiles.
URI
https://pr.ibs.re.kr/handle/8788114/9834
DOI
10.1039/d1sc01730f
ISSN
2041-6520
Appears in Collections:
Center for Catalytic Hydrocarbon Functionalizations(분자활성 촉매반응 연구단) > 1. Journal Papers (저널논문)
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