Palladium(II)-Catalyzed Synthesis of Sulfinates from Boronic Acids and DABSO: A Redox-Neutral, Phosphine-Free Transformation

• Published in: Angewandte Chemie International Edition Vol. 55; no. 2; pp. 747 - 750
• Main Authors: Deeming, Alex S., Russell, Claire J., Willis, Michael C.
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 11.01.2016; WILEY‐VCH Verlag; Wiley; Wiley Subscription Services, Inc
• Edition: International ed. in English
• Subjects: Acids; Aromatic compounds; Catalysts; Chemical synthesis; Chemistry; Chemistry, Multidisciplinary; Communication; Communications; Conversion; electrophiles; Intermediates; oxidation; Palladium; Phosphine; Physical Sciences; Science & Technology; Sulfonamides; Sulfones; Sulfur; Sulfur dioxide; synthetic methods; SULFONE SYNTHESIS; ONE-POT; oxidation; DIARYLIODONIUM SALTS; SULFONAMIDES; ARYLBORONIC ACIDS; ALKYL-HALIDES; ARYL HALIDES; SULFUR-DIOXIDE SURROGATE; palladium; sulfur; PALLADIUM-CATALYZED AMINOSULFONYLATION; 3-COMPONENT; synthetic methods; electrophiles
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.201508370

A redox‐neutral palladium(II)‐catalyzed conversion of aryl, heteroaryl, and alkenyl boronic acids into sulfinate intermediates, and onwards to sulfones and sulfonamides, has been realized. A simple Pd(OAc)2 catalyst, in combination with the sulfur dioxide surrogate 1,4‐diazabicyclo[2.2.2]octane bis(sulfur dioxide) (DABSO), is sufficient to achieve rapid and high‐yielding conversion of the boronic acids into the corresponding sulfinates. Addition of C‐ or N‐based electrophiles then allows conversion into sulfones and sulfonamides, respectively, in a one‐pot, two‐step process. Staying neutral: Pd(OAc)2 promotes the addition of aryl and heteroaryl boronic acids to the sulfur dioxide surrogate 1,4‐diazabicyclo[2.2.2]octane bis(sulfur dioxide) (DABSO) thus delivering the corresponding sulfinates. When combined with an electrophilic trap, this redox‐neutral system provides a straightforward route for the one‐pot preparation of a broad range of sulfones and sulfonamides.