503595-76-4Relevant academic research and scientific papers
Enantioselective Rh(II)-Catalyzed Desymmetric Cycloisomerization of Diynes: Constructing Furan-Fused Dihydropiperidines with an Alkyne-Substituted Aza-Quaternary Stereocenter
Cao, Tongxiang,Chen, Kai,Lu, Jiajun,Ma, Jun,Wu, Rui,Zhu, Shifa
supporting information, p. 14916 - 14925 (2021/09/18)
Described herein is an enantioselective dirhodium(II)-catalyzed cycloisomerization of diynes achieved by the strategy of desymmetrization, which not only represents a new cycloisomerization reaction of diynes but also constitutes the first Rh(II)-catalyzed asymmetric intramolecular cycloisomerization of 1,6-diynes. This protocol provides a range of valuable furan-fused dihydropiperidine derivatives with an enantiomerically enriched alkynyl-substituted aza-quaternary stereocenter in high efficiency, complete atom economy, and excellent enantioselectivity (up to 98% ee). Besides, the highly functionalized products could be easily transformed into various synthetically useful building blocks and conjugated with a series of pharmaceutical molecules. The mechanism involving a concerted [3+2] cycloaddition/[1,2]-H shift of the Rh(II) carbenoid intermediate was elucidated by DFT calculations and mechanistic studies. More importantly, the first single crystal of alkyne-dirhodium(II) was obtained to show that a η2-coordinating activation of alkynal by dirhodium(II) was involved. Weak hydrogen bondings between the carboxylate ligands and alkynal were found, which probably made the well-defined paddlewheel-like dirhodium(II) distinctive from other metal complexes in catalyzing this transformation. Furthermore, the origin of the enantioselectivity was elucidated by a Rh2(R-PTAD)4-alkyne complex and additional calculational studies.
Ynonylation of Acyl Radicals by Electroinduced Homolysis of 4-Acyl-1,4-dihydropyridines
Luo, Xiaosheng,Wang, Ping
supporting information, p. 4960 - 4965 (2021/07/20)
Herein we report the conversion of 4-Acyl-1,4-dihydropyridines (DHPs) into ynones under electrochemical conditions. The reaction proceeds via the homolysis of acyl-DHP under electron activation. The resulting acyl radicals react with hypervalent iodine(III) reagents to form the target ynones or ynamides in acceptable yields. This mild reaction condition allows wider functionality tolerance that includes halides, carboxylates, or alkenes. The synthetic utility of this methodology is further demonstrated by the late-stage modification of complex molecules.
Alkyne derivative as well as preparation method and application thereof (by machine translation)
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Paragraph 0067-0072, (2020/06/05)
The invention belongs to the technical field of organic synthesis, and discloses an acetylenic ketone derivative and a preparation method and application thereof. The formula (I) is shown in the structural formula of the alkyne derivative. R1 And R2 Heterocyclyl groups of C1 - C20, halogen, ester, carbonyl, nitro, substituted amino, C5 - C30, or C5 - C30, respectively. To the strategy of nickel catalytic reduction coupling, a carboxylic acid derivative which is widely used in nature is used as a substrate, an alkyne halide is combined as an active alkynylation reagent, and under the condition of room temperature, the universality and the high efficiency method for rapidly constructing various substituted alkynes are obtained. The alkyne compound disclosed by the invention not only can be used as a practical synthesis, but also can be used as a precursor of heterocyclic compounds such as furan, pyrazole, quinoline, pyrimidine and the like. (by machine translation)
Acyl Radicals from Benzothiazolines: Synthons for Alkylation, Alkenylation, and Alkynylation Reactions
Li, Lei,Guo, Shan,Wang, Qi,Zhu, Jin
, p. 5462 - 5466 (2019/08/01)
We describe herein a fundamentally new visible light-driven homolytic C-C bond breaking mode for the generation of acyl radicals from C2-acyl-substituted benzothiazolines. The reactive species can be used as versatile synthons for formal radical alkylatio
Alkynylation of Csp2 (O)–H Bonds Enabled by Photoredox-Mediated Hydrogen-Atom Transfer
Mukherjee, Satobhisha,Garza-Sanchez, R. Aleyda,Tlahuext-Aca, Adrian,Glorius, Frank
, p. 14723 - 14726 (2017/10/18)
The development of new hydrogen-atom transfer (HAT) strategies within the framework of photoredox catalysis is highly appealing for its power to activate a desired C?H bond in the substrate leading to its selective functionalization. Reported here is the first photoredox-mediated hydrogen-atom transfer method for the efficient synthesis of ynones, ynamides, and ynoates with high regio- and chemoselectivity by direct functionalization of Csp2 (O)?H bonds. The broad synthetic application of this method has been demonstrated by the selective functionalization of C(O)?H bonds within complex molecular scaffolds.
PHOSPHINE COMPOUND HAVING PERFLUORO GROUP, AND COMPLEX BETWEEN METAL AND PHOSPHINE HAVING PERFLUORO GROUP
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Paragraph 0275; 0280-0282; 0285, (2018/10/16)
PROBLEM TO BE SOLVED: To provide a perfluoroalkylphosphine compound, and a complex between a metal and the perfluoroalkylphosphine. SOLUTION: A perfluoroalkylphosphine compound is a phosphine compound represented by the general formula Rf-PR1R2. In the formula, R1 and R2 are each independently a substituted or unsubstituted hydrocarbon group; Rf is a perfluorinated hydrocarbon group. Also provided is a complex between the perfluoroalkylphosphine and a phosphine coordination metal. SELECTED DRAWING: None COPYRIGHT: (C)2016,JPOandINPIT
METHODS OF PRODUCING PHOSPHINE COMPOUND HAVING PERFLUORO GROUP AND COMPLEX BETWEEN METAL AND PHOSPHINE HAVING PERFLUORO GROUP
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Paragraph 0233-0234; 0238, (2018/10/19)
PROBLEM TO BE SOLVED: To provide methods of producing a perfluoroalkylphosphine compound improved in a phosphorus element yield and a chemical yield. SOLUTION: A method of producing a perfluoroalkylphosphine compound comprises either reacting a perfluoroalkyl iodide with, e.g., 2,4,6-trimethylbenzoyldiphenylphosphine oxide (TMDPO) or a triarylphosphine such as triphenylphosphine, which are easily available, in the presence of a radical generator such as azobis(isobutyronitrile) or light irradiation, or reacting TMDPO or the like with perfluoroalkyl iodide in the presence of diphenylphosphine, diethylphosphine, dicyclohexylphosphine or the like. SELECTED DRAWING: None COPYRIGHT: (C)2016,JPOandINPIT
Photoinduced Synthesis of P-Perfluoroalkylated Phosphines from Triarylphosphines and Their Application in the Copper-Free Cross-Coupling of Acid Chlorides and Terminal Alkynes
Kawaguchi, Shin-Ichi,Minamida, Yoshiaki,Okuda, Takumi,Sato, Yuki,Saeki, Tomokazu,Yoshimura, Aya,Nomoto, Akihiro,Ogawa, Akiya
, p. 2509 - 2519 (2015/08/18)
A practical synthesis yielding P-perfluoroalkylated phosphines from triarylphosphines and perfluoroalkyl iodides has been developed. The photoinduced reaction involves the substitution of aryl groups on the phosphorus atom with perfluoroalkyl groups to successfully afford P-perfluoroalkylated phosphines. In addition, the P-perfluoroalkylated phosphines were found to promote the Cu-free cross-coupling reaction of acid chlorides with terminal alkynes.
Metal-free synthesis of ynones via direct C-H alkynylation of aldehydes with ethynylbenziodoxolones
Zhang, Ruo-Yi,Xi, Long-Yi,Zhang, Lei,Chen, Shan-Yong,Yu, Xiao-Qi
supporting information, p. 6176 - 6182 (2015/08/03)
Abstract A metal-free synthesis of ynones via direct alkynlyation of C-H bonds in aldehydes with ethynylbenziodoxolones is described. A variety of unactivated aldehydes undergo this transformation, affording ynones in good yields. These ynones could be fu
Radical-induced metal-free alkynylation of aldehydes by direct C-H activation
Liu, Xuesong,Yu, Linqian,Luo, Mupeng,Zhu, Jidong,Wei, Wanguo
supporting information, p. 8745 - 8749 (2015/06/08)
A direct C(sp2)-H alkynylation of aldehyde C(O)-H bonds with hypervalent iodine alkynylation reagents provides ynones under metal-free conditions. In this method, 1-[(triisopropylsilyl)ethynyl]-1,2-benziodoxol-3(1H)-one (TIPS-EBX) constitutes a
