51721-29-0Relevant academic research and scientific papers
Atom-Economical Cross-Coupling of Internal and Terminal Alkynes to Access 1,3-Enynes
Liu, Mingyu,Tang, Tianhua,Apolinar, Omar,Matsuura, Rei,Busacca, Carl A.,Qu, Bo,Fandrick, Daniel R.,Zatolochnaya, Olga V.,Senanayake, Chris H.,Song, Jinhua J.,Engle, Keary M.
supporting information, p. 3881 - 3888 (2021/04/06)
Selective carbon-carbon (C-C) bond formation in chemical synthesis generally requires prefunctionalized building blocks. However, the requisite prefunctionalization steps undermine the overall efficiency of synthetic sequences that rely on such reactions, which is particularly problematic in large-scale applications, such as in the commercial production of pharmaceuticals. Herein, we describe a selective and catalytic method for synthesizing 1,3-enynes without prefunctionalized building blocks. In this transformation several classes of unactivated internal acceptor alkynes can be coupled with terminal donor alkynes to deliver 1,3-enynes in a highly regio- and stereoselective manner. The scope of compatible acceptor alkynes includes propargyl alcohols, (homo)propargyl amine derivatives, and (homo)propargyl carboxamides. This method is facilitated by a tailored P,N-ligand that enables regioselective addition and suppresses secondary E/Z-isomerization of the product. The reaction is scalable and can operate effectively with as low as 0.5 mol % catalyst loading. The products are versatile intermediates that can participate in various downstream transformations. We also present preliminary mechanistic experiments that are consistent with a redox-neutral Pd(II) catalytic cycle.
Platinum-catalyzed hydrosilylations of internal alkynes: Harnessing substituent effects to achieve high regioselectivity
Rooke, Douglas A.,Ferreira, Eric M.
supporting information; experimental part, p. 3225 - 3230 (2012/05/31)
Rule of thumb: The high yielding title reaction is described with a focus on understanding the factors that govern the regioselectivity of the process (see scheme). Electronic, steric, and functional group properties all influence the selectivity, an understanding of which allows the selective formation of trisubstituted vinylsilanes, which are synthetically useful compounds for accessing stereodefined alkenes. Copyright
Directing group-controlled hydrosilylation: Regioselective functionalization of alkyne
Kawasaki, Yuuya,Ishikawa, Youhei,Igawa, Kazunobu,Tomooka, Katsuhiko
, p. 20712 - 20715 (2012/02/15)
Pt(0)-catalyzed hydrosilylation of unsymmetric alkynes proceeds in a highly regioselective manner with a dimethylvinylsilyl (DMVS) group as the directing group. This hydrosilylation affords a single regioisomer of silylalkenes from propargylic and homopro
Amide-directed catalytic asymmetric hydroboration of trisubstituted alkenes
Smith, Sean M.,Takacs, James M.
supporting information; experimental part, p. 1740 - 1741 (2010/04/25)
(Chemical Equation Presented) Rhodium-catalyzed hydroborations of trisubstituted alkenes are generally slow and often suffer from competing alkene isomerization. In contrast, the trisubstituted alkene moieties contained within the framework of a β,γ-unsat
