Catalytic Intermolecular Tail‐to‐Tail Hydroalkenylation of Styrenes with α Olefins: Regioselective Migratory Insertion Controlled by a Nickel/N‐Heterocyclic Carbene

Chiral N‐Heterocyclic Carbene Ligands Enable Asymmetric C−H Bond Functionalization

“…[51] The use of chiral NHC ligand in asymmetric nickel-catalyzed cross-hydrovinylation was reported by Ho and co-workers in 2015 (Scheme 15). [52] The intermolecular tail-to-tail hydroalkenylation of vinylarenes 53 with terminal olefins 54 was catalyzed by in situ generated NiH [53] complexes bearing C 1 -symmetrical NHC L36 and afforded the chiral gem-disubstituted olefin products 55 with high enantioselectivity. While both N-aryl groups of the NHC were substituted with a bulky cyclohexyl substituent at position 2, a steric discrimination at the ortho-positions was beneficial to the enantioselectivity of the reaction.…”

NHC‐Ni(0) Catalyzed Diastereodivergent Hydroacylative Enyne Cyclization: Synthesis of Heterocycles bearing γ‐Enone

“…Ideally, the strategy should be diastereodivergent, and applicable to the synthesis of both 6-or 7-membered heterocycles from enynes with conformationally less restricted spacers. [6] As part of our continuing efforts on the use of NHC-Ni as a catalyst for the development of novel hydroalkenylation methods and gem-olefin synthesis, [7] we have recently developed a catalytic reductive hydroalkenylation for the generation of heterocycles, by using hetero-substituted enynes as substrates and 1phenylethanol as the terminal reductant. [8] By manipulating the N-substitution on enynes, both sets of diastereoisomers could be obtained with high selectivity on demand.…”

Non-Selective Dimerization of Vinyl Silanes by the Putative (Phenanthroline)PdMe Cation to 1,4-Bis(trialkoxysilyl)butenes

“…Of particular interest are the products of homocoupling reactions of unsaturated substances; such processes attract attention because they function as model systems for both oligomerization and polymerization reactions of alkenes [6,7]. A wide variety of homocoupling reactions of unsaturated substrates are known [8][9][10][11][12][13][14][15][16][17][18][19][20]; however, only a few exist that involve vinyl silanes [21][22][23][24][25][26][27][28][29].…”

“…Trialkoxyvinylsilanes are attractive substrates to target as they are used extensively in materials and surface science [30][31][32][33][34][35][36][37][38], nanotechnology [39,40] for various applications including modification of surfaces [31,37], formation of sol-gel [36,37], and organogelators [32,34,35], to obtain novel organic-inorganic hybrid materials [33], preparation of nanocomposites [39], and several hybrid [38] and supported catalysts. In most of these applications, the nature of the precursor trialkoxysilane has a profound effect on the properties of the final product [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19][20]. Therefore, the availability of a diverse pool of trialkoxysilane precursors would enable incorporation of unprecedented properties to those end products [30][31][32][33]…”