3 research outputs found

    Rhodium(I)-Catalyzed C8-Alkylation of 1‑Naphthylamide Derivatives with Alkenes through a Bidentate Picolinamide Chelation System

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    The rhodium­(I)-catalyzed C–H alkylation of 1-naphthylamide derivatives with alkenes at the C8-position using a picolinamide directing group is reported. Various alkenes including styrene derivatives, α,β-unsaturated carbonyl compounds, and even unactivated alkene could also be used as coupling partners. The reaction mechanism was investigated in kinetic studies, deuterium labeling studies, and control experiments. The reaction appears to proceed through a rhodium carbene intermediate, which is generated from an alkene

    Organosilicon Reducing Reagents for Stereoselective Formations of Silyl Enol Ethers from α‑Halo Carbonyl Compounds

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    Salt-free stereoselective synthesis of silyl enol ethers was achieved by treating α-halo carbonyl compounds with 2,3,5,6-tetramethyl-1,4-bis­(trimethylsilyl)-1,4-dihydropyrazine. In this reaction, easily removable trimethylsilyl halides and 2,3,5,6-tetramethylpyrazine were generated as the reaction byproducts. Due to the inertness of the reaction byproducts, we found a one-pot transformation of the <i>in situ</i> generated silyl enol ethers into various α-functionalized carbonyls by reaction with Togni-II reagent or aldehydes

    Mixed Ligated Tris(amidinate)dimolybdenum Complexes as Catalysts for Radical Addition of CCl<sub>4</sub> to 1‑Hexene: Leaving Ligand Lability Controls Catalyst Activity

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    We synthesized a series of mixed ligated tris­(amidinate)­dimolybdenum complexes, namely, [Mo<sub>2</sub>(DAniF)<sub>3</sub>(L)] [DAniF = <i>N</i>,<i>N</i>′-di­(<i>p</i>-anisyl)­formamidinate; L = acetate (OAc; <b>1a</b>), <i>m</i>-diphenylphosphino benzoate (<i>m</i>-PPh<sub>2</sub>Bz; <b>1b</b>), nicotinate (Nico; <b>1c</b>), benzoate (Bz; <b>1d</b>), 3-furoate (3-Furo; <b>1e</b>), isonicotinate (IsoNico; <b>1f</b>), and trifluoromethanesulfonate (OTf; <b>1g</b>)], which served as catalysts for radical addition of CCl<sub>4</sub> to 1-hexene to give 1,1,1,3-tetrachloroheptane. These mixed ligated complexes <b>1a</b>–<b>g</b> afforded the higher yield of the radical addition product than a homoleptic DAniF complex, [Mo<sub>2</sub>(DAniF)<sub>4</sub>] (<b>2</b>). Among them, complexes <b>1a</b> and <b>1g</b> gave the radical addition product quantitatively after 9 h with a short induction period. When complexes <b>1a</b> and <b>1g</b> were treated with CCl<sub>4</sub>, we detected the mixed-valence Mo<sub>2</sub>(II/III) complex, [Mo<sub>2</sub>(DAniF)<sub>3</sub>Cl<sub>2</sub>] (<b>4</b>), in electrospray ionization mass spectrometry measurements, indicating that the leaving nature of the L ligands was a crucial factor for initiating the catalytic reaction: the catalytic activity of the carboxylate-bridged complex <b>1a</b> and the triflate-bridged complex <b>1g</b> in the initial 30 min highly depended on the ligand-exchange rate of L, as estimated by monitoring the reaction with CCl<sub>4</sub> in pyridine, giving the pyridine adduct complex, [Mo<sub>2</sub>(DAniF)<sub>3</sub>Cl­(py)] (<b>3</b>)