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. 2025 Jul 21;64(30):e202506785.
doi: 10.1002/anie.202506785. Epub 2025 May 26.

Copper-Photoredox-Catalyzed C(sp3)-C(sp3) Reductive Cross-Coupling of Alkyl Bromides with BCP-Thianthrenium Reagents

Saikat Pandit  1   2 , Tobias Ritter  1   2
Affiliations

Copper-Photoredox-Catalyzed C(sp3)-C(sp3) Reductive Cross-Coupling of Alkyl Bromides with BCP-Thianthrenium Reagents

Saikat Pandit et al. Angew Chem Int Ed Engl. .

Abstract

Herein, we report a reductive cross-coupling reaction of bicyclo[1.1.1]pentyl (BCP)-thianthrenium reagents and alkyl bromides. The reaction is catalyzed by a copper/photoredox catalyst system. The approach is the first example of a cross-coupling between BCP-based reagents with alkyl electrophiles.

Keywords: Bicyclopentylation; Bioisosteres; Copper catalysis; Reductive coupling; Thianthrenium salt.

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Conflict of interest statement

The authors declare no conflict of interest.

Figures

Figure 1
Figure 1
Reductive coupling of alkyl bromides with BCP‐thianthrenium salts. X, halides; PC, photocatalyst.
Figure 2
Figure 2
Proposed mechanism.
Scheme 1
Scheme 1
Substrate scope of the reductive cross‐coupling between alkyl bromides and BCP‐thianthrenium salts. General reaction conditions: alkyl bromide (0.25 mmol, 1.0 equiv.), 1b–1d (2.0 equiv.), 4CzIPN (5.0 mol%), CuCl (20 mol%), TMS3SiOH (2.0 equiv.), K2HPO4 (4.0 equiv.), DMA (c = 0.1 M), blue LED (460 nm, 40 W), 12 hr, 30 °C. a )CuCl2 (20 mol%) was used as catalyst, Na2CO3 (4.0 equiv.) was used as base, and DMSO (c = 0.05 M) was used as solvent. d.r., diastereomeric ratio.
Scheme 2
Scheme 2
Synthesis of BCP analog of tesmilifene.
See this image and copyright information in PMC

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