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. 2024 Jul 19;15(33):13459-13465.
doi: 10.1039/d4sc02821j. eCollection 2024 Aug 22.

The merger of electro-reduction and hydrogen bonding activation for a radical Smiles rearrangement

Liyuan Lan  1 , Kun Xu  1 , Chengchu Zeng  1
Affiliations

The merger of electro-reduction and hydrogen bonding activation for a radical Smiles rearrangement

Liyuan Lan et al. Chem Sci. .

Abstract

The reductive activation of chemical bonds at less negative potentials provides a foundation for high functional group tolerance and selectivity, and it is one of the central topics in organic electrosynthesis. Along this line, we report the design of a dual-activation mode by merging electro-reduction with hydrogen bonding activation. As a proof of principle, the reduction potential of N-phenylpropiolamide was shifted positively by 218 mV. Enabled by this strategy, the radical Smiles rearrangement of N-arylpropiolamides without external radical precursors and prefunctionalization steps was accomplished. [DBU][HOAc], a readily accessible ionic liquid, was exploited for the first time both as a hydrogen bonding donor and as a supporting electrolyte.

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Conflict of interest statement

There are no conflicts to declare.

Figures

Scheme 1
Scheme 1. The collaboration between electro-reduction and hydrogen bonding and the reported strategies to radical Smiles rearrangement.
Scheme 2
Scheme 2. The substrate scope. aReaction conditions: 1a (0.3 mmol), 2 (0.3 mmol), DMSO (4 mL), graphite anode (1 cm × 1 cm × 0.2 cm), foamed nickel cathode (1 cm × 1 cm × 0.2 cm), J = 10 mA cm−2, N2, rt, 8 h; isolated yield. aJ = 8 mA cm−2. bJ = 5 mA cm−2.
Fig. 1
Fig. 1. CV experiments.
Fig. 2
Fig. 2. 1H NMR experiments.
Scheme 3
Scheme 3. The control experiments.
Scheme 4
Scheme 4. A plausible mechanism accounting for the generation of 3.
See this image and copyright information in PMC

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