Photoinduced Site-Selective Aryl C-H Borylation with Electron-Donor-Acceptor Complex Derived from B 2 Pin 2 and Isoquinoline.

Publisher: MDPI Country of Publication: Switzerland NLM ID: 100964009 Publication Model: Electronic Cited Medium: Internet ISSN: 1420-3049 (Electronic) Linking ISSN: 14203049 NLM ISO Abbreviation: Molecules Subsets: PubMed not MEDLINE; MEDLINE

Original Publication: Basel, Switzerland : MDPI, c1995-

Due to boron's metalloid properties, aromatic boron reagents are prevalent synthetic intermediates. The direct borylation of aryl C-H bonds for producing aromatic boron compounds offers an appealing, one-step solution. Despite significant advances in this field, achieving regioselective aryl C-H bond borylation using simple and readily available starting materials still remains a challenge. In this work, we attempted to enhance the reactivity of the electron-donor-acceptor (EDA) complex by selecting different bases to replace the organic base (NEt 3 ) used in our previous research. To our delight, when using NH 4 HCO 3 as the base, we have achieved a mild visible-light-mediated aromatic C-H bond borylation reaction with exceptional regioselectivity (rr > 40:1 to single isomers). Compared with our previous borylation methodologies, this protocol provides a more efficient and broader scope for aryl C-H bond borylation through the use of N-Bromosuccinimide. The protocol's good functional-group tolerance and excellent regioselectivity enable the functionalization of a variety of biologically relevant compounds and novel cascade transformations. Mechanistic experiments and theoretical calculations conducted in this study have indicated that, for certain arenes, the aryl C-H bond borylation might proceed through a new reaction mechanism, which involves the formation of a novel transient EDA complex.

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22271316 the National Natural Science Foundation of China; 21933004 the National Natural Science Foundation of China; 2022A1515011994 the Guangdong Basic and Applied Basic Research Foundation; SZBH202103 the Technology & Innovation Commission of Shenzhen Municipality; 23ykbj010 the Fundamental Research Funds for the Central Universities; startup fund the Sun Yat-sen University Startup Fund; RCBS20210706092258097 Shenzhen Science and Technology Program

Keywords: B2Pin2; C-H bond; borylation; electron-donor-acceptor; isoquinoline; photocatalysis

Date Created: 20240427 Latest Revision: 20240429

20250114

PMC11052414

10.3390/molecules29081783

38675603