Controlling Selectivity in Shuttle Hetero-difunctionalization Reactions: Electrochemical Transfer Halo-thiolation of Alkynes
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Date
2023-01-09
Publication Type
Journal Article
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Abstract
Shuttle hetero-difunctionalization reaction, in which two chemically distinct functional groups are transferred between two molecules, has long been an unmet goal due to the daunting challenges in controlling the chemo-, regio-, and stereoselectivity. Herein, we disclose an electrochemistry enabled shuttle reaction (e-shuttle) to selectively transfer one RS− and one X− group between β-halosulfides and unsaturated hydrocarbons via a consecutive paired electrolysis mechanism. The preferential anodic oxidation of one anion over the other, which is controlled by their distinct redox potentials, plays pivotal role in controlling the high chemoselectivity of the process. This easily scalable methodology enables the construction of a myriad of densely functionalized β-halo alkenyl sulfides in unprecedented chemo-, regio-, and stereoselectivity using benign surrogates, e.g., 2-bromoethyl sulfide, avoiding the handling of corrosive and oxidative RS–Br reagents. In a broader context, these results open up new strategies for selective shuttle difunctionalization reactions.
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published
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Journal / series
Volume
62 (2)
Pages / Article No.
Publisher
Wiley-VCH
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Subject
Bromothiolation; Hetero-Difunctionalization; Paired Electrolysis; Reversible Reactions; Shuttle Catalysis
Organisational unit
09634 - Morandi, Bill / Morandi, Bill
Notes
Funding
757608 - Shuttle Catalysis for Reversible Molecular Construction (EC)
886102 - Elemental Halogen-Free Reversible Construction and Deconstruction of 1,2- Dihalides via Shuttle Catalysis (EC)
886102 - Elemental Halogen-Free Reversible Construction and Deconstruction of 1,2- Dihalides via Shuttle Catalysis (EC)