- Selective Alkynylallylation of the C?C σ Bond of Cyclopropenes
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A Pd-catalyzed regio- and stereoselective alkynylallylation of a specific C?C σ bond in cyclopropenes, using allyl propiolates as both allylation and alkynylation reagents, has been achieved for the first time. By merging selective C(sp2)-C(sp3) bond scission with conjunctive cross-couplings, this decarboxylative reorganization reaction features fascinating atom and step economy and provides an efficient approach to highly functionalized dienynes from readily available substrates. Without further optimization, gram-scale products can be easily obtained by such a simple, neutral, and low-cost catalytic system with high TONs. DFT calculations afford a rationale toward the formation of the products and indicate that the selective insertion of the double bond of cyclopropenes into the C-Pd bond of ambidentate Pd complex and the subsequent nonclassical β-C elimination promoted by 1,4-palladium migration are critical for the success of the reaction.
- Chen, Ying-Chun,Jiang, Zeqi,Niu, Sheng-Li,Ouyang, Qin,Xiao, Qing,Zeng, Qiang
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supporting information
p. 297 - 303
(2020/11/30)
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- Isolable Copper(I) ?2-Cyclopropene Complexes
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Treatment of bis(pyrazolyl)borate ligand supported [(CF3)2Bp]Cu(NCMe) with 1,2,3-trisubstituted cyclopropenes produced thermally stable copper(I) ?2-cyclopropene complexes amenable to detailed solution and solid-state analysis. The [(CF3)2Bp]Cu(NCMe) also catalyzed [2 + 1]-cycloaddition chemistry of terminal and internal alkynes with ethyl diazoacetate affording cyclopropenes, including those used as ligands in this work. The tris(pyrazolyl)borate [(CF3)2Tp]Cu(NCMe) is a competent catalyst for this process as well. The treatment of [(CF3)2Tp]Cu with ethyl 2,3-diethylcycloprop-2-enecarboxylate substrate gave an O-bonded rather than a ?2-cyclopropene copper complex.
- Noonikara-Poyil, Anurag,Ridlen, Shawn G.,Dias, H.V.Rasika
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supporting information
p. 17860 - 17865
(2020/11/30)
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- Cu(I)-Catalyzed Intramolecular Tandem Cyclization of N-Indole-Tethered Cyclopropenes: Synthesis of Functionalized Hydrogenated Diazabenzo[ a]cyclopenta[ cd]azulene Derivatives
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A Cu(I)-catalyzed [3 + 2] intramolecular cycloaddition reaction of N-indole-tethered cyclopropenes is presented in this paper. This reaction starts from the formation of ?-allyl cationic intermediate or its resonance-stabilized metal carbenoid intermediate upon activation of cyclopropene with Cu(I) catalyst and a Friedel-Crafts-type cyclization to give functionalized hydrogenated diazabenzo[a]cyclopenta[cd]azulenes in good to excellent yields along with moderate to good dr values. The asymmetric variant of this cycloaddition reaction can be realized, giving the desired products with moderate ee values.
- Li, Peng-Hua,Yang, Song,Hao, Tong-Gang,Xu, Qin,Shi, Min
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supporting information
(2019/05/07)
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- ORGANIC ELECTROLUMINESCENT MATERIALS AND DEVICES
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An organic light emitting device (OLED) that includes an anode, a cathode, and an organic layer disposed between the anode and the cathode. The organic layer includes a metal compound that comprises a ligand LA of Formula I, wherein the dashed
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Paragraph 0150; 0151
(2019/10/29)
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- RhI-Catalyzed Carbonylative [3+1] Construction of Cyclobutenones via C?C σ-Bond Activation of Cyclopropenes
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With a catalytic amount of Rh(cod)2BF4 and dppm, cyclopropenes undergo a direct carbonylative [3+1] cycloaddition reaction under an atmosphere of CO to produce the cyclobutenones in excellent yields, in which the regio- and diastereoselectivities can be controlled in certain cases with the help of chelating groups. Cyclobutenone with a chiral 4-position was prepared by diastereoselective induction. Rhodacyclopentenone has been determined as the key intermediate, as it was synthesized and applied to the reductive elimination step.
- Xu, Wen-Bin,Li, Changkun,Wang, Jianbo
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supporting information
p. 15786 - 15790
(2018/10/15)
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- Carboxylates as Nucleophiles in the Enantioselective Ring-Opening of Formylcyclopropanes under Iminium Ion Catalysis
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In this work, carboxylic acids, which are typically regarded as poor nucleophiles, are demonstrated to be competent reagents to promote the ring-opening of formylcyclopropanes after activation of the latter through iminium ion formation. Under optimized r
- Díaz, Estibaliz,Reyes, Efraim,Uria, Uxue,Carrillo, Luisa,Tejero, Tomas,Merino, Pedro,Vicario, Jose L.
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supporting information
p. 8764 - 8768
(2018/05/30)
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- Gold(i)-catalysed synthesis of conjugated trienes
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Gold(i)-catalysed reaction between cyclopropenes and furans produces functionalised conjugated trienes. The reaction is mild, facile and proceeds with very low catalyst loadings.
- Hadfield, Maximillian S.,Lee, Ai-Lan
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supporting information; scheme or table
p. 1333 - 1335
(2011/03/22)
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- Rh(I)-catalyzed carbonylative carbocyclization of tethered ene- and yne-cyclopropenes
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Rh(I)-catalyzed carbonylative carbocyclization of ene- and yne-cyclopropene systems provides cyclohexenones and phenols with high efficiency, respectively.
- Li, Changkun,Zhang, Hang,Feng, Jiajie,Zhang, Yan,Wang, Jianbo
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supporting information; experimental part
p. 3082 - 3085
(2010/08/20)
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- Gold(I)-catalyzed cycloisomerization of enynes containing cyclopropenes
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Goldenyne: Gold-catalyzed cycloisomerization reactions of propargyl cyclopropenes afford benzene derivatives in a highly efficient manner. The reaction either proceeds through a mechanism with or without double and triple bond cleavage, depending on the substituents (see scheme). Copyright
- Li, Changkun,Zeng, Yi,Zhang, Hang,Feng, Jiajie,Zhang, Yan,Wang, Jianbo
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supporting information; experimental part
p. 6413 - 6417
(2010/11/19)
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- 1,3,5-Tris(thiocyanatomethyl)mesitylene as a Ligand. Pseudooctahedral molybdenum, manganese, and rhenium carbonyl complexes and copper and silver dimers. Copper-catalyzed carbene- and nitrene-transfer reactions
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New molybdenum(0), molybdenum(II), manganese(I), rhenium(I), silver(I), and copper(I) complexes with the 1,3,5-tris(thiocyanatomethyl)mesitylene [Ms(CH2SCN)3] ligand have been synthesized and characterized by IR, NMR, and by X-ray diffraction (except for the rhenium complex). The Ms(CH2SCN)3 ligand coordinated with the molybdenum, manganese, and rhenium carbonyl fragments as a tripodal chelate. With copper and silver, dimeric dicationic species were obtained instead, with the Ms(CH2SCN)3 ligand acting simultaneously as a bidentate chelate and bridge. The [{Cu(Ms(CH2SCN)3)} 2][BAr′4]2 (BAr′4 = tetra(3,5-bis(trifluoromethyl)phenyl)borate) product is an excellent catalyst for cyclopropanation and aziridination of alkenes and cyclopropenation of alkynes by means of carbene- and nitrene-transfer reactions.
- Martinez-Garcia, Hector,Morales, Dolores,Perez, Julio,Puerto, Marcos,Miguel, Daniel
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experimental part
p. 6974 - 6985
(2010/09/06)
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- Synthesis of new copper(i) complexes with tris(2-pyridyl) ligands. Applications to carbene and nitrene transfer reactions
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New copper(i) complexes with tris(2-pyridyl)methane (TPC), tris(2-pyridyl)methoxymethane (TPM) and tris(2-pyridyl)amine (TPN) ligands have been synthesized and characterized, including structural determinations by X-ray diffraction of some examples. Their activity as catalysts in carbene and nitrene transfer reactions was studied.
- Perez, Julio,Morales, Dolores,Garcia-Escudero, Luis A.,Martinez-Garcia, Hector,Miguel, Daniel,Bernad, Pablo
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experimental part
p. 375 - 382
(2009/04/14)
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- Diphenyl-cyclopropenes as selective K-agonists
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The diphenyl-cyclopropene derivatives of the instant invention are kappa opioids useful in the treatment of pain, inflammation, Parkinsonism, dystonia, cerebral ischemia, diuresis, asthma, psoriasis, irritable bowel syndrome, and stroke. The compounds are
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- Trapping of Cyclopropenyl Radicals by 5,5-Dimethyl-1-pyrroline-N-oxide
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The possible generation of cyclopropenyl radicals by ultraviolet irradiation of different cyclopropenyl derivatives in fluid solution and in the presence of 5,5-dimethyl-1-pyrroline-N-oxide (DMPO) as spin trap has been detected by electron paramagnetic re
- Cano, Montserrat,Quintana, Jordi,Julia, Luis,Camps, Francisco,Joglar, Jesus
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p. 5096 - 5099
(2007/10/03)
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- Trans N-Methyl-N-[2-(1-pyrrolidinyl)cyclohexyl] cycloprop-2-ene-1-carboxamides: Novel lipophilic kappa opioid agonists
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The synthesis and kappa opioid agonist activities of some lipophilic analogues of the kappa opioid agonist U-50488 incorporating motifs bearing two aromatic rings in place of the 3,4-dichlorophenyl group are described. Trans 2,3-diphenyl-N-methyl-N[2-(1-pyrrolidinyl)cyclohexyl]-2-cyclopropene-1 -carboxamide, 7, is a potent kappa opioid agonist. A diphenylcyclopropene analogue of CI-977, trans 2,3-diphenyl-N-methyl-N-[7-(1-pyrrolidinyl)-1-oxaspiro[4.5]dec-8-yl]-2 -cyclopropene-1-carboxamide, 13, is a highly lipophilic chemically novel potent selective kappa opioid agonist.
- Sabin,Horwell,McKnight,Broqua
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p. 291 - 296
(2007/10/03)
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- 1,2,3-Triazines, IV. - Synthesis of 1,2,3-Triazinecarboxylates
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1,2,3-Triazinecarboxylates 5 have been prepared by rearrangement of the cyclopropenyl azides 6 as well as by oxidation of the 1-aminopyrazoles 9, 10.Reaction of 1-aminopyrazole-5-carboxylates 10 with triethyl orthoformate (19) and ammonia affords pyrazolotriazin-4-ones 18 Key Words: 1,2,3-Triazines / Cyclopropenyl azides / Pyrazoles / Pyrazolotriazines
- Neunhoeffer, Hans,Bopp, Ralf,Diehl, Werner
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p. 367 - 374
(2007/10/02)
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- The Attempted Generation of a Methylene-Bridged Trimethylenemethane Biradical (1,3-Diphenyl-2-methylenecyclobutane-1,3-diyl) by Oxidation of endo-1,3-Diphenyl-2-(phenylselenomethyl)bicyclobutane.
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Copper-catalysed addition of ethyl diazoacetate to diphenylacetylene and hydrolysis gives 1,2-diphenylcyclopropane-3-carboxylic acid (18b).Conversion to the acid chloride (18c) and reduction with lithium aluminium tri-tert-butoxy hydride gives 1,2-dipheny
- Bushby, Richard J.,Jesudason, Malini V.
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p. 1144 - 1170
(2007/10/02)
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- Small Rings, 33. Attempts to Synthesize Diphenyltetrahedrane
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Carbene 7, formed on photochemical or thermal excitation of (2,3-diphenyl-2-cyclopropen-1-yl)diazomethane (6i), splits mostly into two acetylenes 8 and 9 instead of undergoing an intramolecular cycloaddition.Photolysis of the Masamune ketone 16 depending on the reaction conditions gives either p-terphenyl or a mixture of the two cyclooctatetraens 18 and 19.The intermediate formation of tetrahedrane 10 would fit into the mechanistic picture of this fragmentation.
- White, Emil H.,Winter, Rudolph E. K.,Graeve, Rolf,Zirngibl, Ulrich,Friend, Earl W.,et al.
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p. 3906 - 3915
(2007/10/02)
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