Catalyst-Free C(sp 2 )-H Borylation through Aryl Radical Generation from Thiophenium Salts via Electron Donor–Acceptor Complex Formation

Organic Letters, vol. 24, pp. 7434–7439

Abstract

Aryl borates lie at the heart of carbon-carbon bond couplings, and they are widely applied to the synthesis of functional materials, pharmaceutical compounds, and natural products. Currently, synthetic methods for aryl borates are mostly limited to metal-catalyzed routes, and nonmetallic strategies remain comparatively underdeveloped. Herein, we report a mild, scalable, visible-light-induced cross-coupling between aryl dibenzothiophenium triflate salts and bis(catecholato)-diboron for the construction of C-B bonds in the absence of base, transition metal-ligand complex, or photoredox catalyst. Mechanistic studies reveal that this transformation is achieved through an electron donor-acceptor (EDA) complex activation in the absence of a catalyst. The mild reaction conditions allow the preparation of aromatic borates in good yields with excellent functional group tolerance. This photochemical protocol was also successfully applied to the late-stage modification of natural products and the synthesis of a drug intermediate, greatly demonstrating broadened utility.

Authors 7

1. Bo Li Aachen Institute of Organic Chemistry

   RWTH Aachen University · King Abdullah University of Science and Technology

   Affiliation as printed

   Institute of Organic Chemistry, RWTH Aachen University, Landoltweg 1, 52074Aachen, Germany

   King Abdullah University of Science and Technology (KAUST), KAUST Catalysis Center (KCC), Thuwal23955-6900, Saudi Arabia

2. Ke Wang Aachen Institute of Organic Chemistry

   RWTH Aachen University

   Affiliation as printed

   Institute of Organic Chemistry, RWTH Aachen University, Landoltweg 1, 52074Aachen, Germany

3. Huifeng Yue

   King Abdullah University of Science and Technology

   Affiliation as printed

   King Abdullah University of Science and Technology (KAUST), KAUST Catalysis Center (KCC), Thuwal23955-6900, Saudi Arabia

4. Alwin Drichel Aachen Institute of Organic Chemistry

   RWTH Aachen University

   Affiliation as printed

   Institute of Organic Chemistry, RWTH Aachen University, Landoltweg 1, 52074Aachen, Germany

5. Jingjing Lin Aachen Institute of Organic Chemistry

   RWTH Aachen University

   Affiliation as printed

   Institute of Organic Chemistry, RWTH Aachen University, Landoltweg 1, 52074Aachen, Germany

6. Zhenying Su Aachen Institute of Organic Chemistry

   RWTH Aachen University

   Affiliation as printed

   Institute of Organic Chemistry, RWTH Aachen University, Landoltweg 1, 52074Aachen, Germany

7. Magnus Rueping corresponding

   King Abdullah University of Science and Technology

   Affiliation as printed

   King Abdullah University of Science and Technology (KAUST), KAUST Catalysis Center (KCC), Thuwal23955-6900, Saudi Arabia