46037-61-0Relevant academic research and scientific papers
Synthesis of Fulvene Vinyl Ethers by Gold Catalysis
Ahrens, Alexander,Dreuw, Andreas,Hashmi, A. Stephen K.,Hoffmann, Marvin,Lustosa, Danilo M.,Pourkaveh, Raheleh,Rominger, Frank,Rudolph, Matthias,Schwarz, Julia
supporting information, (2020/04/20)
Gold-catalyzed cyclization of 1,5-diynes with ketones as reagents and solvent provides diversely substituted vinyl ethers under mild conditions. The regioselectivity of such gold-catalyzed cyclizations is usually controlled by the scaffold of the diyne. H
CO extrusion in homogeneous gold catalysis: Reactivity of gold acyl species generated through water addition to gold vinylidenes
Bucher, Janina,St?sser, Tim,Rudolph, Matthias,Rominger, Frank,Hashmi, A. Stephen K.
supporting information, p. 1666 - 1670 (2015/01/30)
Herein, we describe a new gold-catalyzed decarbonylative indene synthesis. Synergistic σ,π-activation of diyne substrates leads to gold vinylidene intermediates, which upon addition of water are transformed into gold acyl species, a type of organogold compound hitherto only scarcely reported. The latter are shown to undergo extrusion of CO, an elementary step completely unknown for homogeneous gold catalysis. By tuning the electronic and steric properties of the starting diyne systems, this new reactivity could be exploited for the synthesis of indene derivatives in high yields.
Gold-catalyzed hydroarylating cyclization of 1,2-Bis(2-iodoethynyl)benzenes
N?sel, Pascal,Müller, Vanessa,Mader, Steffen,Moghimi, Setareh,Rudolph, Matthias,Braun, Ingo,Rominger, Frank,Hashmi, A. Stephen K.
supporting information, p. 500 - 506 (2015/03/05)
1,5-Diynes bearing halogen-substituted alkynes were synthesized and converted in the presence of a gold catalyst. In contrast to the corresponding hydroarylating aromatization reaction with terminal alkynes, a totally different reaction mode was observed.
Dibenzopentalenes from B(C6F5)3-induced cyclization reactions of 1,2-bis(phenylethynyl)benzenes
Chen, Chao,Harhausen, Marcel,Liedtke, Rene,Bussmann, Kathrin,Fukazawa, Aiko,Yamaguchi, Shigehiro,Petersen, Jeffrey L.,Daniliuc, Constantin G.,Froehlich, Roland,Kehr, Gerald,Erker, Gerhard
supporting information, p. 5992 - 5996 (2013/07/19)
'Lene' and mean: The strong Lewis acid B(C6F5) 3 efficiently converts some bis(arylethynyl)benzenes into dibenzopentalenes through a series of Lewis acid induced cyclization reactions at room temperature. Thus the reaction has the potential to be useful in the synthesis of substituted dibenzopentalene derivatives which are difficult to make by conventional means. Copyright
Tetranuclear copper(I) iodide complexes of chelating bis(1 -benzyl-1 H-1,2,3triazole) ligands: Structural characterization and solid state photoluminescence
Manbeck, Gerald F.,Brennessel, William W.,Evans, Christopher M.,Eisenberg, Richard
experimental part, p. 2834 - 2843 (2010/05/15)
A series of tetranuclear Cu4l4(Ln)2 clusters (1-3) supported by the chelating 4,4'-(4,5-diX-1,2-phenylene)bls(1 -benzyl-1 H-1,2,3-triazole) ligands (L1, X = H; L2, X = CH3; L3, X = F) have been prepared. Crystal
Synthetic and mechanistic investigations on the rearrangement of 2,3-unsaturated 1,4-bis(alkylidene)carbenes to enediynes
Sahu, Bichismita,Muruganantham, Rajendran,Namboothiri, Irishi N. N.
, p. 2477 - 2489 (2008/03/13)
The synthesis of 3,4-ene-1,5-diynes, the key structural moiety present in several naturally occurring antitumor antibiotics, from 1,2-enedialdehydes under two different experimental conditions is reported. One method involves the dibromomethylenation of dialdehydes under Corey-Fuchs conditions (CBr 4, Ph3P, and Zn) and treatment of the resulting tetrabromides with nBuLi or LDA to afford enediynes. The second method involves a base-mediated reaction of enedialdehydes with diethyl (1-diazo-2-oxopropyl) phosphonate (Bestmann-Ohira reagent) and subsequent transformation of the bis(diazo) compounds generated in situ to enediynes. While the transformation of bis(diazo) compounds to enediynes could take place exclusively through alkylidene-carbenes, generated in situ by geminal elimination of N2, an alternative pathway, involving the vicinal elimination of HBr to afford an intermediate bromoalkyne and its subsequent metal-halogen exchange and protonation during workup, exists for the bis(dibromoalkylidenes). However, our deuterium-labeling experiments with a model substrate, deuterated p-methoxybenzylidene dibromide, established the predominance of the alkylidenecarbenes, generated in situ by metal-halogen exchange and elimination, for this substrate and, by analogy, for the tetrabromides as well. The scope of this novel methodology was extended to the synthesis of various heteroatom-based (S, Se, and P) enediynes by quenching the acetylides with suitable electrophiles. Wiley-VCH Verlag GmbH & Co. KGaA, 2007.
Synthesis of arenediynes via the vinylidenecarbene-acetylene rearrangement
Sahu, Bichismita,Namboothiri, Irishi N.N.,Persky, Rachel
, p. 2593 - 2597 (2007/10/03)
A convenient method for the two-step synthesis of arenediynes from 1,2-arenedialdehydes is reported. Dibromomethylenation of dialdehydes under Corey-Fuchs conditions (CBr4, Ph3P, Zn) provides the tetrabromides in excellent yields. Treatment of the tetrabromides with n-BuLi or LDA affords 3,4-unsaturated 1,5-diynes, the key structural moiety present in several naturally occurring antitumour antibiotics, in varying yields. The key intermediates in these transformations appear to be vinylidenecarbenes or carbenoids, generated in situ via metal-halogen exchange and elimination.
Intramolecular Reaction Of Nitroxide Radicals With Biradical Intermediates Generated From Aromatic Enediynes
Grissom, Janet Wisniewski,Gunawardena, Gamini U.
, p. 4951 - 4954 (2007/10/02)
1,4-Dehydronaphthalene biradicals generated by thermolysis of aromatic enediynes can be trapped with the nitroxide radical TEMPO.The isolated products, however, are not the direct trapping products but 1,4-naphthoquinones resulting from the homolysis of N-O bonds of trapping products.
