15332-33-9Relevant academic research and scientific papers
A Highly Efficient Dimeric Manganese-Catalyzed Selective Hydroarylation of Internal Alkynes
Huang, Congcong,Li, Weipeng,Liu, Gengtu,Pang, Yubo,Xie, Jin,Yuan, Xiang-Ai
, p. 12789 - 12794 (2020)
We have developed a general and site-predictable manganese-catalyzed hydroarylation of internal alkynes in the presence of water, under an air atmosphere without the involvement of ligand. The unique catalytic feature of this reaction is highlighted by comparison with other widely used transition metal catalysts including palladium, rhodium, nickel, or copper. The simple operation, high efficiency and excellent functional group compatibility make this protocol practical for more than 90 structurally diverse internal alkynes, overcoming the influence of both electronic and steric effect of alkynes. Its exclusive regio- and chemoselectivity originates from the unique reactivity of the manganese-based catalyst towards an inherent double controlled strategy of sterically hindered propargyl alcohols without the installing of external directing groups. Its synthetic robustness and practicality have been illustrated by the concise synthesis of bervastatin, a hypolipidemic drug, and late-stage modification of complex alkynes with precise regioselectivity.
Iron-Catalyzed Cross-Coupling of Propargyl Ethers with Grignard Reagents for the Synthesis of Functionalized Allenes and Allenols
B?ckvall, Jan-E.,Bermejo-López, Aitor,Posevins, Daniels
supporting information, p. 22178 - 22183 (2021/09/06)
Herein we disclose an iron-catalyzed cross-coupling reaction of propargyl ethers with Grignard reagents. The reaction was demonstrated to be stereospecific and allows for a facile preparation of optically active allenes via efficient chirality transfer. Various tri- and tetrasubstituted fluoroalkyl allenes can be obtained in good to excellent yields. In addition, an iron-catalyzed cross-coupling of Grignard reagents with α-alkynyl oxetanes and tetrahydrofurans is disclosed herein, which constitutes a straightforward approach towards fully substituted β- or γ-allenols, respectively.
Synthesis of 4-Oxoisoxazoline N-Oxides via Pd-Catalyzed Cyclization of Propargylic Alcohols with tert-Butyl Nitrite
Feng, Kai-Wen,Ban, Yong-Liang,Yuan, Pan-Feng,Lei, Wen-Long,Liu, Qiang,Fang, Ran
supporting information, p. 3131 - 3135 (2019/05/10)
A cyclization of propargylic alcohols with tert-butyl nitrite at room temperature in air was achieved using Pd(OAc)2 as catalyst. The first reported 4-oxoisoxazoline N-oxides could be directly accessed from a range of multisubstituted propargylic alcohols in moderate to excellent yields under mild conditions. Density functional theory calculations indicated that the reaction proceeds through a palladium-catalyzed NO2 addition that efficiently generates a ketoxime radical, which eventually produces 4-oxoisoxazoline N-oxide.
Cadmium(II) Chloride-Catalyzed Dehydrative C?P Coupling of Propargyl Alcohols with Diarylphosphine Oxides to Afford Allenylphosphine Oxides
Yang, Jianlin,Zhang, Ming,Qiu, Kang,Wang, Lize,Yu, Jingjing,Xia, Zefeng,Shen, Ruwei,Han, Li-Biao
supporting information, p. 4417 - 4426 (2017/12/26)
The cadmium(II) chloride-catalyzed dehydrative C?P cross-coupling reaction of propargyl alcohols with diarylphosphine oxides is reported. Several propargyl alcohols including those bearing the sterically demanding tert-butyl group at the triple bond terminus can be used as good substrates in the reaction to produce the corresponding allenylphosphine oxides in good to high yields in acetonitrile at 100 °C. The reaction can also be easily scaled up to a gram-scale synthesis. A mechanism study indicates that the reaction may proceed through a process of propargylic substitution to generate phosphonite intermediates followed by [2,3] sigmatropic rearrangement to produce the allenyl products, rather than through a common allenylative substitution resulting from P-nucleophilicity. (Figure presented.).
Microwave-Assisted Organocatalyzed Rearrangement of Propargyl Vinyl Ethers to Salicylaldehyde Derivatives: An Experimental and Theoretical Study
Tejedor, David,Cotos, Leandro,Márquez-Arce, Daniel,Odriozola-Gimeno, Mikel,Torrent-Sucarrat, Miquel,Cossío, Fernando P.,García-Tellado, Fernando
supporting information, p. 18280 - 18289 (2015/12/24)
The microwave-assisted imidazole-catalyzed transformation of propargyl vinyl ethers (PVEs) into multisubstituted salicylaldehydes is described. The reaction is instrumentally simple, scalable, and tolerates a diverse degree of substitution at the propargylic position of the starting PVE. The generated salicylaldehyde motifs incorporate a broad range of topologies, spanning from simple aromatic monocycles to complex fused polycyclic systems. The reaction is highly regioselective and takes place under symmetry-breaking conditions. The preparative power of this reaction was demonstrated in the first total synthesis of morintrifolin B, a benzophenone metabolite isolated from the small tree Morinda citrifolia L. A DFT study of the reaction was performed with full agreement between calculated values and experimental results. The theoretically calculated values support a domino mechanism comprising a propargyl Claisen rearrangement, a [1,3]-H shift, a [1,7]-H shift (enolization), a 6π electrocyclization, and an aromatization reaction.
Borylation of propargylic substrates by bimetallic catalysis. Synthesis of allenyl, propargylic, and butadienyl bpin derivatives
Zhao, Tony S. N.,Yang, Yuzhu,Lessing, Timo,Szabó, Kálmán J.
supporting information, p. 7563 - 7566 (2014/06/10)
Bimetallic Pd/Cu and Pd/Ag catalytic systems were used for borylation of propargylic alcohol derivatives. The substrate scope includes even terminal alkynes. The reactions proceed stererospecifically with formal S N2′ pathways to give allenyl boronates. Opening of propargyl epoxides leads to 1,2-diborylated butadienes probably via en allenylboronate intermediate.
The vinyl moiety as a handle for regiocontrol in the preparation of unsymmetrical 2,3-aliphatic-substituted indoles and pyrroles
Huestis, Malcolm P.,Chan, Lina,Stuart, David R.,Fagnou, Keith
supporting information; scheme or table, p. 1338 - 1341 (2011/04/21)
Rho-Rho-Rho your boat: A rhodium catalyst effects the regioselective oxidative coupling of enynes with N-aryl ureas (X=NR2) and N-vinylacetamides (X=C(O)Me), affording the corresponding 2-alkenylindoles and 2-alkenylpyrroles in good yield. Simple hydrogenation delivers the C2/C3-aliphatic-substituted indole or pyrrole (see scheme).
Domino gold-catalyzed rearrangement and fluorination of propargyl acetates
De Haro, Teresa,Nevado, Cristina
supporting information; experimental part, p. 248 - 249 (2011/02/23)
A combination of IPrAuNTf2 as catalyst in the presence of Selectfluor has been successfully used for the high yielding synthesis of α-fluoroenones via 1,3-acyloxy rearrangement of propargyl acetates followed by Csp2-F bond formation,
Gold-catalyzed efficient preparation of linear α-haloenones from propargylic acetates
Yu, Meng,Zhang, Guozhu,Zhang, Liming
experimental part, p. 1846 - 1855 (2009/07/04)
Versatile linear α-iodo- and α-bromoenones are prepared efficiently from readily accessible propargylic acetates using 2 mol % of Au(PPh3)NTf2. This reaction is easy to execute and has broad substrate scope. Good to excellent Z-selectivities are observed in the cases of propargylic acetates derived from aliphatic aldehydes.
Silver(I)-catalyzed cascade: Direct access to furans from alkynyloxiranes
Blanc, Aurelien,Tenbrink, Katharina,Weibel, Jean-Marc,Pale, Patrick
supporting information; experimental part, p. 4360 - 4363 (2009/09/06)
(Chemical Equation Presented) Functionalized furans are conveniently formed by a new silver(I)-catalyzed reaction of alk-1-ynyl oxiranes in the presence of p-toluenesulfonic acid and methanol. Evidence supported a cascade mechanism.
