170751-24-3Relevant academic research and scientific papers
Selective Alkynylallylation of the C?C σ Bond of Cyclopropenes
Chen, Ying-Chun,Jiang, Zeqi,Niu, Sheng-Li,Ouyang, Qin,Xiao, Qing,Zeng, Qiang
, p. 297 - 303 (2020/11/30)
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.
Azide Radical Initiated Ring Opening of Cyclopropenes Leading to Alkenyl Nitriles and Polycyclic Aromatic Compounds
Muriel, Bastian,Waser, Jerome
, p. 4075 - 4079 (2021/01/18)
We report herein a radical-mediated amination of cyclopropenes. The transformation proceeds through a cleavage of the three-membered ring after the addition of an azide radical on the strained double bond and leads to tetrasubstituted alkenyl nitrile derivatives upon loss of N2. With 1,2-diaryl substituted cyclopropenes, this methodology could be extended to a one-pot synthesis of highly functionalized polycyclic aromatic compounds (PACs). This transformation allows the synthesis of nitrile-substituted alkenes and aromatic compounds from rapidly accessed cyclopropenes using only commercially available reagents.
Regioselective oxidative ring-opening of cyclopropenyl carboxylates by visible light photoredox catalysis
Ye, Qianwen,Ye, Hongqiang,Cheng, Dongping,Li, Xiaonian,Xu, Xiaoliang
, p. 2546 - 2549 (2018/05/28)
Catalyzed by Ir(dFCF3ppy)2(dtbbpy)PF6, several aroyl methylidenemalonates were synthesized in good to excellent yields via visible light photoredox-catalyzed the oxidative ring-opening of cyclopropenyl carboxylate derivatives. The possible mechanism of oxidative quenching cycle was proposed.
Design, preparation, X-ray crystal structure, and reactivity of o-alkoxyphenyliodonium bis(methoxycarbonyl)methanide, a highly soluble carbene precursor
Zhu, Chenjie,Yoshimura, Akira,Ji, Lei,Wei, Yunyang,Nemykin, Victor N.,Zhdankin, Viktor V.
supporting information; experimental part, p. 3170 - 3173 (2012/08/07)
The preparation, X-ray structure, and reactivity of new, highly soluble, and reactive iodonium ylides derived from malonate methyl ester and bearing an ortho substituent on the phenyl ring are reported. These new reagents show higher reactivity than common phenyliodonium ylides in the Rh-catalyzed cyclopropanation, C-H insertion, and transylidation reactions under homogeneous conditions.
An efficient and general method for resolving cyclopropene carboxylic acids
Liao, Lian-An,Zhang, Fan,Yan, Ni,Golen, James A.,Fox, Joseph M.
, p. 1803 - 1816 (2007/10/03)
A general method is described for the resolution of cycloprop-2-ene carboxylic acids via diastereomeric N-acyloxazolidines prepared from enantiomerically pure oxazolidinones. Although a number of oxazolidinones were shown to resolve cyclopropene carboxylic acids, the oxazolidinones of S-phenylalaninol, S-phenylglycine and (1S,2R)-cis-1-amino-2-indanol are optimal in terms of resolving power and cost effectiveness. Separations were performed using simple flash chromatography, and because there is typically a large difference in Rf values it is possible to separate gram quantities of pure diastereomers in a single chromatogram. The cycloprop-2-ene carboxylic acids that can be resolved include those that are substituted at the 1-position by H, Ph, α-naphthyl, CO2Me, CH2OMOM, and trans-styryl; alkene substituents include Me, n-alkyl, Ph and tethered alkynes. Remarkably, 2-methyl-3-propylcycloprop-2-ene carboxylic acid can also be resolved with ease. The relative configurations of four diastereomerically pure oxazolidines were determined by X-ray crystallography. Reduction of the N-acyloxazolidinones with LiBH4 give enantiomerically pure derivatives of 3-hydroxymethylcyclopropene that react with either MeMgCl or vinylMgCl and catalytic CuI to give enantiomerically pure products of syn-addition.
RhII-catalyzed cycloadditions of carbomethoxy iodonium ylides
Batsila, Christina,Kostakis, George,Hadjiarapoglou, Lazaros P
, p. 5997 - 6000 (2007/10/03)
Carbomethoxy iodonium ylides, generated from methyl acetoacetate and methyl malonate, respectively, are exploited in synthesis of cyclopropanes, cyclopropenes as well as various heterocycles.
77. Carbenoid Reactions in Rhodium(II)-Catalyzed Decomposition of Iodonium Ylides
Mueller, Paul,Fernandez, Daniel
, p. 947 - 958 (2007/10/02)
The intermediacy of metallocarbenes in decomposition reactions of iodonium ylides with was established by comparison with reactions of the corresponding diazo compounds.The sensitivity of the RhII-catalyzed intermolecular cyclopropa
