16336-82-6Relevant articles and documents
Configurational Instability of α-Alkenyl and α-Alkynyl Vinyllithiums. Syntheses of Stereodefined 2-Alkyl-1-en-3-ynes
Miller, Joseph A.,Leong, William,Zweifel, George
, p. 1839 - 1840 (1988)
Metal-halogen exchange of either (Z)-enynyl bromides or (Z)-dienyl bromides by sec-BuLi produces vinyllithiums that are configurationally stable only at temperatures below -120 deg C and -78 deg C, respectively.Allylation of (Z)-enynylalanates with allyl bromide or methylation of (Z)-enynyl bromides with CH3MgI and Fe(acac)3 catalyst furnishes the corresponding 2-alkyl-1-en-3-ynes.
Rhodium(I)-NHC Complexes Bearing Bidentate Bis-Heteroatomic Acidato Ligands as gem-Selective Catalysts for Alkyne Dimerization
Galiana-Cameo, María,Borraz, Marina,Zelenkova, Yaroslava,Passarelli, Vincenzo,Lahoz, Fernando J.,Pérez-Torrente, Jesús J.,Oro, Luis A.,Di Giuseppe, Andrea,Castarlenas, Ricardo
supporting information, p. 9598 - 9608 (2020/07/13)
A series of Rh(κ2-BHetA)(η2-coe)(IPr) complexes bearing 1,3-bis-hetereoatomic acidato ligands (BHetA) including carboxylato (O,O), thioacetato (O,S), amidato (O,N), thioamidato (N,S), and amidinato (N,N), have been prepared by reacti
Pseudo-tetrahedral Rhodium and Iridium Complexes: Catalytic Synthesis of E-Enynes
Geer, Ana M.,Julián, Alejandro,López, José A.,Ciriano, Miguel A.,Tejel, Cristina
, p. 17545 - 17556 (2018/11/23)
The reactions of the rhodium(I) and iridium(I) complexes [M(PhBP3)(C2H4)(NCMe)] (PhBP3=PhB(CH2PPh2)3?) with alkynes have resulted in the synthesis of a new family of p
A copper (I or II)/diethylphosphite catalytic system for base-free additive dimerization of alkynes
Trostyanskaya, Inna G.,Beletskaya, Irina P.
supporting information, p. 148 - 153 (2016/12/23)
Copper (I) or copper (II) salts and oxides promote regioselective head-to-head additive dimerization of aromatic and aliphatic terminal alkynes in the presence a catalytic amount of diethylphosphite. The reaction proceeds under ambient conditions without
A series of pincer-ligated rhodium complexes as catalysts for the dimerization of terminal alkynes
Pell, Christopher J.,Ozerov, Oleg V.
, p. 3470 - 3480 (2015/02/19)
A series of pincer complexes of Rh has been prepared and tested as catalysts for the dimerization of terminal alkynes. The pincers included aryl/bis(phosphinite) POCOP, aryl/bis(phosphine) PCP, and diarylamido/bis(phosphine) PNP ligands. RhI co
Pyridine-enhanced head-to-tail dimerization of terminal alkynes by a rhodium-N-heterocyclic-carbene catalyst
Rubio-Perez, Laura,Azpiroz, Ramon,Di Giuseppe, Andrea,Polo, Victor,Castarlenas, Ricardo,Perez-Torrente, Jesus J.,Oro, Luis A.
supporting information, p. 15304 - 15314 (2013/11/06)
A general regioselective rhodium-catalyzed head-to-tail dimerization of terminal alkynes is presented. The presence of a pyridine ligand (py) in a Rh-N-heterocyclic-carbene (NHC) catalytic system not only dramatically switches the chemoselectivity from alkyne cyclotrimerization to dimerization but also enhances the catalytic activity. Several intermediates have been detected in the catalytic process, including the π-alkyne-coordinated RhI species [RhCl(NHC)(η2-HC ≡CCH2Ph)(py)] (3) and [RhCl(NHC){η2-C(tBu) ≡C(E)CH=CHtBu}(py)] (4) and the RhIII-hydride-alkynyl species [RhClH{-C ≡CSi(Me) 3}(IPr)(py)2] (5). Computational DFT studies reveal an operational mechanism consisting of sequential alkyne Ci￡ H oxidative addition, alkyne insertion, and reductive elimination. A 2,1-hydrometalation of the alkyne is the more favorable pathway in accordance with a head-to-tail selectivity. Control plan: Addition of pyridine to rhodium-N-heterocyclic- carbene catalysts not only switches the chemoselectivity from alkyne cyclotrimerization to dimerization, but also enhances the catalytic activity for the formation of 1,3-enynes (see figure). A 2,1-hydrometalation of the alkyne is the more favorable pathway calculated by DFT.
Silaborations of 1,3-enynes - Substrate controlled allene/1,3-diene selectivity
Lueken, Christian,Moberg, Christina
supporting information; experimental part, p. 2505 - 2508 (2009/05/26)
(Chemical Equation Presented) Silaboration of 1,3-enynes catalyzed by group 10 metal complexes affords 1,3-dienes with vinylborane and vinylsilane functions or 1,2-dienes with allylborane and vinylsilane functions. The type of product formed is determined
Skeletal change in the PNP pincer ligand leads to a highly regioselective alkyne dimerization catalyst
Weng, Wei,Guo, Chengyun,Celenligil-Cetin, Remle,Foxman, Bruce M.,Ozerov, Oleg V.
, p. 197 - 199 (2008/02/07)
A Rh complex of a bulky diarylamino-based PNP pincer ligand is a robust catalyst for the dimerization of terminal alkynes and highly selective for the trans-enyne product. The Royal Society of Chemistry 2006.
Regio- and stereoselective dimerization of terminal alkynes to enynes catalyzed by a palladium/imidazolium system
Yang, Chuluo,Nolan, Steven P.
, p. 591 - 593 (2007/10/03)
A Palladium/imidazolium chloride system has been used to mediate the dimerization of terminal alkynes to enynes. The combination of 1 mol % Pd(OAc)2 and 2 mol % IMes·HCl in the presence of Cs2CO3 as base shows high activit
Controlling the catalytic oligomerization of terminal alkynes promoted by organoactinides: A strategy to short oligomers
Haskel, Ariel,Wang, Ji Quan,Straub, Thomas,Neyroud, Tal Gueta,Eisen, Moris S.
, p. 3025 - 3034 (2007/10/03)
A novel strategy has been developed for the catalytic synthesis of short oligomers, dimers and/or trimers, of terminal alkynes. The method allows control of the extent of and, in some cases, the regiospecificity in the catalyzed oligomerization of terminal alkynes promoted by bis(pentamethylcyclopentadienyl)actinide dimethyl complexes (Cp*2AnMe2; Cp* = C5Me5, An = Th, U). These metallocene precursors are known to promote the simultaneous production of a large number of differently sized oligomers in the presence of terminal alkynes. However, the addition of specific amines ensures the selective synthesis of short oligomers. Catalytic 'tailoring' to dimers or a mixture of dimers and trimers can be achieved by using nonbulky or bulky amines, respectively. The kinetics in the catalytic oligomerization of 1-hexyne, in the presence of i-BuNH2, mediated by Cp*2ThMe2 are first order in [alkyne], first order in [Th], and inverse first order in [amine]. Kinetic, spectroscopic, and mechanistic data argue that the turnover-limiting step involves the formation of the mono(amido)thorium acetylide complex with rapid insertion of the alkyne and protonolysis by the amine.
