Tert‐Butyl Sulfoxides: Key Precursors for Palladium‐Catalyzed Arylation of Sulfenate Salts. Issue 9 (15th June 2015)

• Record Type: Journal Article
• Authors: Gelat, Fabien; Lohier, Jean‐François; Gaumont, Annie‐Claude; Perrio, Stéphane
• Is Part Of: Advanced synthesis & catalysis. Volume 357:Issue 9(2015)
• Page Start: 2011
• Page End: 2016
• Publication Date: 2015-06-15
• Subjects: Catalysis -- Periodicals; Organic compounds -- Synthesis -- Periodicals; Chemistry -- Periodicals; Chemistry, Technical -- Periodicals; Chemistry -- Periodicals; Catalysis -- Periodicals; Technology, Pharmaceutical -- Periodicals; 547.2
• DOI: 10.1002/adsc.201500368
• Languages: English
• ISSNs: 1615-4150

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>The present report describes an efficient and clean generation of sulfenate salts (R¹SO⁻) by pyrolysis of readily available <italic>tert</italic>‐butyl sulfoxides to give sulfenic acids (R¹SOH) and traceless isobutene, followed by hydrogen abstraction with a weak inorganic base (K₃PO₄). The relevance of this process was exemplified through an <italic>in situ</italic> palladium‐catalyzed cross‐coupling reaction with aryl halides/triflates leading to aryl sulfoxides. The operationally simple CS bond‐forming protocol developed uses Pd(dba)₂ as catalyst and Xantphos as ligand in toluene or a toluene/H₂O mixture. Further extensions include the use of di‐<italic>tert</italic>‐butyl sulfoxide as an equivalent for sulfur monoxide dianion (SO²⁻) and the development of diastereoselective versions in the [2.2]paracyclophane and biaryl series.</p> <p> <graphic position="anchor" mimetype="image" xlink:href="ark:/27927/pgj10cp1rj5" orientation="portrait" xlink:type="simple" xmlns:xlink="http://www.w3.org/1999/xlink" /> </p> </abstract>