Palladium‐Catalyzed Suzuki–Miyaura Cross‐Coupling of Secondary α‐(Trifluoromethyl)benzyl Tosylates

Abstract

Ap alladium-catalyzed C(sp 3 ) À C(sp 2 )S uzuki-Miyaura cross-coupling of aryl boronic acids and a-(trifluoromethyl)benzyl tosylates is reported. Ar eadily available,a irstable palladium catalyst was employed to access awide range of functionalized1 ,1-diaryl-2,2,2-trifluoroethanes.E nantioenriched a-(trifluoromethyl)benzyl tosylates were found to undergo cross-coupling to give the corresponding enantioenriched cross-coupled products with an overall inversion in configuration. The crucial role of the CF 3 group in promoting this transformation is demonstrated by comparison with nonfluorinated derivatives. Conflict of interestTheauthors declare no conflict of interest.

Design and Synthesis of TY‐Phos and Application in Palladium‐Catalyzed Enantioselective Fluoroarylation ofgem‐Difluoroalkenes

“…[7a] Herein, we wish to report the first example of highly enantioselective fluoroarylation of gemdifluoroalkenes with aryl halides enabled by the palladium and a new type of chiral sulfonamide phosphine (Sadphos) ligand, so called TY-Phos (Scheme 1 d), providing an easy access to chiral 1,1,1-trifluoro-2-arylalkanes. [13] The incorporation of a fluoride or trifluoromethyl group in an organic molecule often significantly alters the physical, chemical, and biological properties compared to a nonfluorinated organic molecule. [14] (Bis)arylethanes, in particular, with a hydroxy group or alkoxyl or hydroxyl group at the ortho-positition of the aryl, are ubiquitous structural motifs found in an array of biologically active natural products and pharmaceuticals ( Figure 1).…”