Abstract
Currently, the selective activation of C(sp3)–F bonds and C–C bonds constitute one of the most widely used procedures for the synthesis of high-value products that range from pharmaceuticals to agrochemical applications. While numerous examples of these two methods have been reported in their respective fields, the processes which merge the activation of both single C(sp3)-F bonds and C–C bonds in one step still remain elusive. Here, we demonstrate the controllable defluoroalkylation–distal functionalization of trifluoromethylarenes with unactivated alkenes via distal heteroaryl migration. This is proposed to proceed via tandem C(sp3)–F and C–C bond cleavage using visible-light photoredox catalysis combined with Lewis acid activation. This strategy provides facile and flexible access to multiply functionalized α,α-difluorobenzylic ketones in useful yields (up to 88%) under mild conditions. The products can be further transformed into other valuable compounds, demonstrating the method’s utility.
Highlights
The selective activation of C(sp3)–F bonds and C–C bonds constitute one of the most widely used procedures for the synthesis of high-value products that range from pharmaceuticals to agrochemical applications
Yoshida and coworkers demonstrated the cleavage of a single C(sp3)–F bond accompanied by the transformation of F atom into an orthosilylium cation, providing an aryldifluoromethyl cation that can react with various nucleophilic species[12]
Gschwind and König disclosed the photocatalytic single C(sp3)–F functionalization of ArCF3 with Naryl acrylamides via photocatalysis combined with Lewis acid activation[14]
Summary
The selective activation of C(sp3)–F bonds and C–C bonds constitute one of the most widely used procedures for the synthesis of high-value products that range from pharmaceuticals to agrochemical applications. Yield (%)b 84 N.D. 17 42 66 50 48 30 N.R. N.R. aStandard conditions: 1a (2.0 eq, 0.2 mmol), 2a (1.0 eq, 0.1 mmol), fac-Ir (ppy)[3] (1.0 mol%), TMP (3.0 eq, 0.3 mmol), B2Pin[2] (3.0 eq, 0.3 mmol), DCE 1.0 mL, 25 °C, N2, 455 nm, 24 h.
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