Defluorinative Alkylation of Trifluoromethyl Alkenes with Soft Carbon Nucleophiles Enabled by a Catalytic Amount of Base

Abstract

Direct manipulation of readily accessible trifluoromethyl alkenes (TAs) represents an attractive approach to the preparation of diversified fluorine‐containing compounds. In this study, defluorinative alkylation reactions of TAs with a broad array of soft carbon nucleophiles have been documented. Nucleophilic substitutions occur enabled by a catalytic amount of base, providing access to tertiary alkyl substituted gem‐difluoroalkenes and 2‐fluoro‐4H‐pyrans. By extending the nucleophiles to silyl enol ethers, defluorination can be achieved in the absence of base to give gem‐difluoroalkenes. This process, which eliminates the requirement of organometallic reagents, transition metals, or strong bases for the C−F bond cleavage, is applicable to late‐stage modification of complex molecules.

Photocatalytic Synthesis of γ,γ-Difluoroallylic Ketones and δ,δ-Difluoroallylic Ketones via a Desulfurative/Defluorinative Alkylation Process

“…Hence, based on the above experimental observations and previous studies, − a plausible mechanism was proposed (Figure ). Upon photoirradiation, PPh 3 is oxidized by the photocatalyst and generates radical cation I , which then forms a complex with ethyl 2-mercaptoacetate.…”

Solvent- and catalyst-dependent palladium-catalyzed switchable chemodivergent cascade cyclizations of trimethylenemethanes with ortho-formyl cinnamates

“…2a). 14 It is well known from the hard–soft acid–base (HSAB) theory that a soft nucleophile preferentially attacks the soft electrophilic site, generating a more charged separated center; 15 thus soft C3 favors the interaction with a soft electrophile C2 . This was the primary reason why ortho -formyl styrene 5a afforded only the CC-selective [3 + 2] cycloadduct.…”

Visible‐Light Photoredox Catalyzed Regioselective 1,4‐Hydroalkylation of 1,3‐Enyne

“…Additional references cited within the Supporting Information. [17][18][19][20][21][22][23][24][25][26][27][28][29][30]…”