Nickel‐Catalyzed Dimerization and Alkylarylation of 1,3‐Dienes with Alkyl Fluorides and Aryl Grignard Reagents

Abstract

In the presence of a nickel catalyst, 1,3-butadiene undergoes selective dimerization and alkylarylation with alkyl fluorides and aryl Grignard reagents to give 1,6-octadienes with alkyl and aryl groups at the 3- and 8-positions, respectively, by the consecutive formation of three carbon-carbon bonds. The formation of an anionic nickel complex plays an important role in forming C-C bonds with alkyl fluorides.

Selective C−H Halogenation with a Highly Fluorinated Manganese Porphyrin

“…When Mn(TPFPP)Cl was used, we were pleased to observe that the conversion was significantly improved along with ahigh 3chloro selectivity ( Table 1, entry 6). [18] Inspired by these chlorination results,w ef urther investigated the ability of Mn(TPFPP)Cl to catalyze the direct CÀHf luorination of these electron-deficient and sterically hindered molecules.Only rare examples of C À Hfluorination addressing electron deficiencyh ave been reported. Higher yields were observed and the use of ap hase-transfer catalyst could be avoided when acetonitrile was used as the solvent (Table 1, entry 7).…”

Fe‐Catalyzed Cross‐Coupling Reaction of Vinylic Ethers with Aryl Grignard Reagents

“…Although the actual structure of the catalytic intermediates is not clear yet, FeCl 2 may undergo reduction by ArMgBr to form Fe I[22] or Fe 0[23] accompanied by the formation of biaryls . Thus formed low valent Fe species A react with aryl Grignard reagents to form anionic aryliron species B . The addition of thus formed Fe complex B toward C−C double bonds of vinyl ethers to afford C and subsequent anti ‐β‐oxygen elimination assisted by Mg cation gives the coupling products.…”

Transition‐Metal‐Catalyzed Three‐Component Difunctionalizations of Alkenes

“…The corresponding allylsilanes were generated in good yields under the reaction conditions. Recently, the same group extended the electrophiles from chlorosilanes to alkyl halides and perfluoroarenes …”

“…[41] The corresponding allylsilanes were generated in good yields under the reactionc onditions. Recently,t he same group extended the electrophiles from chlorosilanes to alkyl halides [42,43] and perfluoroarenes. [44] The directing strategy was also applied in the nickel-mediated three-component difunctionalizationo ft erminala lkenes.…”