C(alkenyl)–H Activation via Six-Membered Palladacycles: Catalytic 1,3-Diene Synthesis

A catalytic method to prepare highly substituted 1,3-dienes from two different alkenes is described using a directed, palladium­(II)-mediated C­(alkenyl)–H activation strategy. The transformation exhibits broad scope across three synthetically useful substrate classes masked with suitable bidentate auxiliaries (4-pentenoic acids, allylic alcohols, and bishomoallylic amines) and tolerates internal nonconjugated alkenes, which have traditionally been a challenging class of substrates in this type of chemistry. Catalytic turnover is enabled by either MnO₂ as the stoichiometric oxidant or co-catalytic Co­(OAc)₂ and O₂ (1 atm). Experimental and computational studies were performed to elucidate the preference for C­(alkenyl)–H activation over other potential pathways. As part of this effort, a structurally unique alkenylpalladium­(II) dimer was isolated and characterized

C(alkenyl)–H Activation via Six-Membered Palladacycles: Catalytic 1,3-Diene Synthesis

A catalytic method to prepare highly substituted 1,3-dienes from two different alkenes is described using a directed, palladium­(II)-mediated C­(alkenyl)–H activation strategy. The transformation exhibits broad scope across three synthetically useful substrate classes masked with suitable bidentate auxiliaries (4-pentenoic acids, allylic alcohols, and bishomoallylic amines) and tolerates internal nonconjugated alkenes, which have traditionally been a challenging class of substrates in this type of chemistry. Catalytic turnover is enabled by either MnO₂ as the stoichiometric oxidant or co-catalytic Co­(OAc)₂ and O₂ (1 atm). Experimental and computational studies were performed to elucidate the preference for C­(alkenyl)–H activation over other potential pathways. As part of this effort, a structurally unique alkenylpalladium­(II) dimer was isolated and characterized

C(alkenyl)–H Activation via Six-Membered Palladacycles: Catalytic 1,3-Diene Synthesis

A catalytic method to prepare highly substituted 1,3-dienes from two different alkenes is described using a directed, palladium­(II)-mediated C­(alkenyl)–H activation strategy. The transformation exhibits broad scope across three synthetically useful substrate classes masked with suitable bidentate auxiliaries (4-pentenoic acids, allylic alcohols, and bishomoallylic amines) and tolerates internal nonconjugated alkenes, which have traditionally been a challenging class of substrates in this type of chemistry. Catalytic turnover is enabled by either MnO₂ as the stoichiometric oxidant or co-catalytic Co­(OAc)₂ and O₂ (1 atm). Experimental and computational studies were performed to elucidate the preference for C­(alkenyl)–H activation over other potential pathways. As part of this effort, a structurally unique alkenylpalladium­(II) dimer was isolated and characterized

C(alkenyl)–H Activation via Six-Membered Palladacycles: Catalytic 1,3-Diene Synthesis

A catalytic method to prepare highly substituted 1,3-dienes from two different alkenes is described using a directed, palladium­(II)-mediated C­(alkenyl)–H activation strategy. The transformation exhibits broad scope across three synthetically useful substrate classes masked with suitable bidentate auxiliaries (4-pentenoic acids, allylic alcohols, and bishomoallylic amines) and tolerates internal nonconjugated alkenes, which have traditionally been a challenging class of substrates in this type of chemistry. Catalytic turnover is enabled by either MnO₂ as the stoichiometric oxidant or co-catalytic Co­(OAc)₂ and O₂ (1 atm). Experimental and computational studies were performed to elucidate the preference for C­(alkenyl)–H activation over other potential pathways. As part of this effort, a structurally unique alkenylpalladium­(II) dimer was isolated and characterized

C(alkenyl)–H Activation via Six-Membered Palladacycles: Catalytic 1,3-Diene Synthesis

A catalytic method to prepare highly substituted 1,3-dienes from two different alkenes is described using a directed, palladium­(II)-mediated C­(alkenyl)–H activation strategy. The transformation exhibits broad scope across three synthetically useful substrate classes masked with suitable bidentate auxiliaries (4-pentenoic acids, allylic alcohols, and bishomoallylic amines) and tolerates internal nonconjugated alkenes, which have traditionally been a challenging class of substrates in this type of chemistry. Catalytic turnover is enabled by either MnO₂ as the stoichiometric oxidant or co-catalytic Co­(OAc)₂ and O₂ (1 atm). Experimental and computational studies were performed to elucidate the preference for C­(alkenyl)–H activation over other potential pathways. As part of this effort, a structurally unique alkenylpalladium­(II) dimer was isolated and characterized

Directed Nickel-Catalyzed 1,2-Dialkylation of Alkenes

A nickel-catalyzed conjunctive cross-coupling of non-conjugated alkenes, alkyl halides, and alkylzinc reagents is reported. Regioselectivity is controlled by chelation of a removable bidentate 8-aminoquinoline directing group. Under optimized conditions, a wide range of 1,2-dialkylated products can be accessed in moderate to excellent yields. To the best of our knowledge, this report represents the first example of three-component 1,2-dialkylation of non-conjugated alkenes to introduce differentiated alkyl fragments

Additional file 1: Table S1. of MCM6 promotes metastasis of hepatocellular carcinoma via MEK/ERK pathway and serves as a novel serum biomarker for early recurrence

The primers used in this study. Table S2. Correlation of serum MCM6 expression with clinical variables. (DOCX 19 kb

Catalytic, Enantioselective Synthesis of Allenyl Boronates

A method to achieve enantioselective 1,4-hydroboration of terminal and internal enynes to access allenyl boronates under CuH catalysis is described. The reaction typically proceeds in a highly stereoselective manner and tolerates an array of synthetically useful functional groups. The utility of the enantioenriched allenyl boronate products is demonstrated through several representative downstream derivatizations

Catalytic, Enantioselective Synthesis of Allenyl Boronates

A method to achieve enantioselective 1,4-hydroboration of terminal enynes to access allenyl boronates under CuH catalysis is described. The reaction typically proceeds in a highly stereoselective manner and tolerates an array of synthetically useful functional groups. The utility of the enantioenriched allenyl boronate products is demonstrated through several representative downstream derivatizations

Catalytic, Enantioselective Synthesis of Allenyl Boronates

A method to achieve enantioselective 1,4-hydroboration of terminal and internal enynes to access allenyl boronates under CuH catalysis is described. The reaction typically proceeds in a highly stereoselective manner and tolerates an array of synthetically useful functional groups. The utility of the enantioenriched allenyl boronate products is demonstrated through several representative downstream derivatizations