13197-81-4Relevant articles and documents
Aluminium-Catalyzed C(sp)?H Borylation of Alkynes
Willcox, Dominic R.,De Rosa, Daniel M.,Howley, Jack,Levy, Abigail,Steven, Alan,Nichol, Gary S.,Morrison, Carole A.,Cowley, Michael J.,Thomas, Stephen P.
, p. 20672 - 20677 (2021)
Historically used in stoichiometric hydroalumination chemistry, recent advances have transformed aluminium hydrides into versatile catalysts for the hydroboration of unsaturated multiple bonds. This catalytic ability is founded on the defining reactivity of aluminium hydrides with alkynes and alkenes: 1,2-hydroalumination of the unsaturated π-system. This manuscript reports the aluminium hydride catalyzed dehydroborylation of terminal alkynes. A tethered intramolecular amine ligand controls reactivity at the aluminium hydride centre, switching off hydroalumination and instead enabling selective reactions at the alkyne C?H σ-bond. Chemoselective C?H borylation was observed across a series of aryl- and alkyl-substituted alkynes (21 examples). On the basis of kinetic and density functional theory studies, a mechanism in which C?H borylation proceeds by σ-bond metathesis between pinacolborane (HBpin) and alkynyl aluminium intermediates is proposed.
Nickel-Catalyzed Allylmethylation of Alkynes with Allylic Alcohols and AlMe3: Facile Access to Skipped Dienes and Trienes
Li, Jincan,Li, Wanfang,Yu, Shun,Zhao, Yu
supporting information, p. 14404 - 14408 (2020/07/04)
We present herein an unprecedented allylative dicarbofunctionalization of alkynes with allylic alcohols. This simple catalytic procedure utilizes commercially available Ni(COD)2, triphenylphosphine, and inexpensive reagents, and delivers valuable skipped dienes and trienes with an all-carbon tetrasubstituted alkene unit in a highly stereoselective fashion. Preliminary mechanistic studies support the reaction pathway of allylnickelation followed by transmetalation in this dicarbofunctionalization of alkynes.
Rhodium-catalyzed enantioselective addition of organoaluminum reagents to N -tosyl ketimines
Hirner, Sebastian,Kolb, Andreas,Westmeier, Johannes,Gebhardt, Sandra,Middel, Stephen,Harms, Klaus,Von Zezschwitz, Paultheo
supporting information, p. 3162 - 3165 (2014/06/23)
Rhodium(I)/Binap complexes catalyze highly enantioselective additions of methyl- and arylaluminum reagents to cyclic α,β-unsaturated N-tosyl ketimines. Depending on the solvent and substituents at the ring, the reaction occurs either in a 1,2-manner to de
