- Mechanistic Studies on the Palladium-Catalyzed Cross Dehydrogenative Coupling of P(O)-H Compounds with Terminal Alkynes: Stereochemistry and Reactive Intermediates
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The mechanism of the palladium-catalyzed cross dehydrogenative coupling of P(O)-H compounds with terminal alkynes was studied. Successive ligand-exchange reactions of Pd(OAc)2 with a hydrogen phosphoryl compound and a terminal alkyne take place
- Yang, Jia,Chen, Tieqiao,Zhou, Yongbo,Yin, Shuang-Feng,Han, Li-Biao
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- Copper-Catalyzed Vicinal Cyano-, Thiocyano-, and Chlorophosphorylation of Alkynes: A Phosphinoyl Radical-Initiated Approach for Difunctionalized Alkenes
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A copper-catalyzed difunctional cyano-, thiocyano-, and chlorophosphorylation reaction of alkynes with P(O)-H compounds and coupling partners (TBACN, TMSNCS, TMSCl) is described. The reaction introduces versatile groups (-P(O)R2 and -CN, -SCN, or -Cl) to form tri- and tetrasubstituted alkenyl phosphine oxides/phosphonates regio- and stereoselectively.
- Li, Cheng-Kun,Li, Jian-An,Shoberu, Adedamola,Tao, Ze-Kun,Zhang, Wei,Zou, Jian-Ping
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supporting information
p. 4342 - 4347
(2021/06/28)
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- Visible-Light-Promoted Formation of C—C and C—P Bonds Derived from Evolution of Bromoalkynes under Additive-Free Conditions: Synthesis of 1,1-Dibromo-1-en-3-ynes and Alkynylphosphine Oxides
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The controllable achievement of C—C and C—P bond formations is developed via visible-light-promoted bromoalkyne dimerization or its further transformation with secondary phosphine oxides. The 1,1-dibromo-1-en-3-ynes are formed when bromoalkyne is exposed to visible-light. While alkynylphosphine oxides are generated when bromoalkynes are mixed with secondary phosphine oxides.
- Xu, Hailong,Chen, Rui,Ruan, Hongjie,Ye, Ruyi,Meng, Ling-Guo
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supporting information
p. 873 - 878
(2021/03/04)
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- Additive-free coupling of bromoalkynes with secondary phosphine oxides to generate alkynylphosphine oxides in acetic anhydride
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A coupling of bromoalkynes with secondary phosphine oxides was developed for the synthesis of alkynylphosphine oxides. This transformation was accomplished under additive-free conditions in acetic anhydride (Ac2O). The reaction could be carried out under mild conditions, and a wide range of secondary phosphine oxides were obtained in good yields.
- Ruan, Hongjie,Meng, Ling-Guo,Xu, Hailong,Liang, Yuqing,Wang, Lei
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p. 1087 - 1090
(2020/02/22)
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- Azobisisobutyronitrile-Initiated Oxidative C-H Functionalization of Simple Alcohols with Diaryl(arylethynyl)phosphine Oxides: A Metal-Free Approach toward Hydroxymethyl Benzo[ b]phosphole Oxides and 6 H-Indeno[2,1- b]phosphindole 5-Oxide Derivatives
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The first metal-free and facile radical addition/cyclization of simple alcohols with diaryl(arylethynyl)phosphine oxides has been described with azobisisobutyronitrile as a radical initiator, affording an efficient and one-pot procedure to access a new cl
- Guo, Jiami,Mao, Chenlu,Deng, Bin,Ye, Liyi,Yin, Yingwu,Gao, Yuxing,Tu, Song
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p. 6359 - 6371
(2020/07/14)
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- TiO2/Cu2O nanoparticle-catalyzed direct C(sp)-P bond formation: Via aerobic oxidative coupling in air and visible light
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The synthesis of organophosphorus compounds is one of the important goals in organic chemistry. Among these compounds, alkynylphosphonates are significantly utilized as the main precursors for the synthesis of biologically active molecules in medicinal chemistry and have attracted extensive interest in the past few decades. Although few efforts have been made towards the direct and atom-economical synthesis of alkynylphosphonates, efforts towards the utilization of visible light as a green and renewable energy source have not been made to date. Here, we have promoted a strategy to construct a type of nano metal oxide composite photocatalyst (Cu2O decorated on TiO2) for the synthesis of alkynylphosphonates via direct C-P bond formation between terminal alkyne and H-phosphonate under visible light irradiation. In this p-n heterojunction photocatalyst, Cu2O acted as a visible-light absorber; moreover, the CB (conduction band) of TiO2 was favorable for accepting a photogenerated electron, and the generated electron hole (e-/h+) pair could initiate the reaction. The present study can provide a new way for the synthesis of this important class of phosphorus organic compounds.
- Hosseini-Sarvari, Mona,Jafari, Fattaneh
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p. 3001 - 3006
(2020/03/13)
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- Selective P?C(sp3) Bond Cleavage and Radical Alkynylation of α-Phosphorus Alcohols by Photoredox Catalysis
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Herein the first P?C(sp3) bond cleavage and radical alkynylation of α-phosphorus alcohols to construct phosphonoalkynes is reported. The phosphorus radical is generated upon P?C bond cleavage reaction via the alkoxyl radical through photoredox catalysis with cyclic iodine(III) reagents. Various arylphosphinoyl-, alkylphosphinoyl-, phosphonate-, and phosphonic amide alcohols serve as radical phosphorus precursors to construct phosphonoalkynes for the first time.
- Jia, Kunfang,Li, Junzhao,Chen, Yiyun
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p. 3174 - 3177
(2018/02/09)
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- Asymmetric Covalent Triazine Framework for Enhanced Visible-Light Photoredox Catalysis via Energy Transfer Cascade
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Complex multiple-component semiconductor photocatalysts can be constructed that display enhanced catalytic efficiency via multiple charge and energy transfer, mimicking photosystems in nature. In contrast, the efficiency of single-component semiconductor photocatalysts is usually limited due to the fast recombination of the photogenerated excitons. Here, we report the design of an asymmetric covalent triazine framework as an efficient organic single-component semiconductor photocatalyst. Four different molecular donor–acceptor domains are obtained within the network, leading to enhanced photogenerated charge separation via an intramolecular energy transfer cascade. The photocatalytic efficiency of the asymmetric covalent triazine framework is superior to that of its symmetric counterparts; this was demonstrated by the visible-light-driven formation of benzophosphole oxides from diphenylphosphine oxide and diphenylacetylene.
- Huang, Wei,Byun, Jeehye,R?rich, Irina,Ramanan, Charusheela,Blom, Paul W. M.,Lu, Hao,Wang, Di,Caire da Silva, Lucas,Li, Run,Wang, Lei,Landfester, Katharina,Zhang, Kai A. I.
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p. 8316 - 8320
(2018/06/29)
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- Catalyst- and Oxidant-Free Desulfonative C?P Couplings for the Synthesis of Phosphine Oxides and Phosphonates
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An efficient and practical approach towards phosphine oxides and phosphonates has been successfully developed through the desulfonative coupling of various sulfones with secondary phosphine oxides and phosphites. This protocol features simple experimental
- Guo, Hong-Mei,Zhou, Quan-Quan,Jiang, Xuan,Shi, De-Qing,Xiao, Wen-Jing
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supporting information
p. 4141 - 4146
(2017/10/09)
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- Silver-Free Direct Synthesis of Alkynylphosphine Oxides via spC-H/P(O)-H Dehydrogenative Coupling Catalyzed by Palladium
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A silver-free palladium-catalyzed dehydrogenative phosphorylation of terminal alkynes with hydrogen phosphine oxides has been developed. Both aromatic and aliphatic terminal alkynes including those bearing functional groups coupled readily with hydrogen phosphine oxides, producing the corresponding value-added alkynylphosphine oxides in good to excellent yields. This reaction could be easily conducted at gram scales (10 mmol) without any decrease of the reaction efficiency, showing highly potential synthetic value in organic synthesis. A plausible Pd(0)/Pd(II) mechanism is proposed.
- Zhang, Jian-Qiu,Chen, Tieqiao,Zhang, Ji-Shu,Han, Li-Biao
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supporting information
p. 4692 - 4695
(2017/09/11)
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- Room-Temperature Alkynylation of Phosphine Oxides with Copper Acetylides: Practical Synthesis of Alkynylphosphine Oxides
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An efficient procedure for the synthesis of alkynylphosphine oxides based on the oxidative alkynylation of secondary phosphine oxides with copper acetylides was developed. Activation with molecular oxygen in the presence of either a mixture of 1,2-dimethylimidazole and triethylamine or N-methylimidazole alone enabled the formal umpolung of the poorly nucleophilic copper acetylides, which were coupled with phosphine oxides under remarkably mild conditions. Notable features of this procedure are the availability of the starting materials, its user-friendliness, and its mild conditions, which allow the synthesis of complex alkynylphosphine oxides.
- Gérard, Phidéline,Veillard, Romain,Alayrac, Carole,Gaumont, Annie-Claude,Evano, Gwilherm
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p. 633 - 638
(2017/01/18)
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- Palladium-catalyzed dehydrogenative coupling of terminal alkynes with secondary phosphine oxides
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The dehydrogenative coupling of terminal alkynes with secondary phosphine oxides is developed. In the presence of a silver additive, palladium acetate could efficiently catalyze the dehydrocoupling of secondary phosphine oxides with a variety of terminal alkynes to produce the corresponding alkynylphosphine oxides in high yields. A reaction mechanism is proposed. This journal is
- Yang, Jia,Chen, Tieqiao,Zhou, Yongbo,Yin, Shuangfeng,Han, Li-Biao
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supporting information
p. 3549 - 3551
(2015/03/30)
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- Silver-Mediated Selective Oxidative Cross-Coupling between C-H/P-H: A Strategy to Construct Alkynyl(diaryl)phosphine Oxide
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(Formula Presented) A direct oxidative cross-coupling between terminal alkynes and secondary phosphine oxides was developed. This approach provides an efficient way to construct alkynyl di(phenyl) phosphine oxides from basic materials, and in this process
- Wang, Tao,Chen, Songtao,Shao, Ailong,Gao, Meng,Huang, Yangfei,Lei, Aiwen
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supporting information
p. 118 - 121
(2015/07/28)
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- Cs2CO3-promoted one-pot synthesis of alkynylphosphonates, -phosphinates, and -phosphine oxides
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A novel and efficient Cs2CO3-promoted phosphorylation or phosphinylation of various 1,1-dibromo-1-alkenes with readily available trialkyl phosphites, ethyl diphenylphosphinite, or diethyl phenylphosphonite has been developed under metal-free conditions, providing a practical and powerful tool for one-pot synthesis of valuable alkynylphosphonates, -phosphinates, and -phosphine oxides in good to excellent yields.
- Wang, Yulei,Gan, Jiepeng,Liu, Liu Leo,Yuan, Hang,Gao, Yuxing,Liu, Yan,Zhao, Yufen
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p. 3678 - 3683
(2014/05/06)
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- Copper-Mediated oxidative decarboxylative coupling of arylpropiolic acids with dialkyl h-phosphonates in water
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An efficient, mild, and generally applicable protocol for copper-mediated oxidative decarboxylative coupling of arylpropiolic acids with dialkyl H-phosphonates in water has been developed. Note that the reaction could proceed smoothly under air at relativ
- Li, Xiang,Yang, Fan,Wu, Yangjie,Wu, Yusheng
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supporting information
p. 992 - 995
(2014/03/21)
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- Selective deprotection of Me3Si-/Ph2P(O)-protected arylalkynes: Methyl Grignard reagent-promoted dephosphorylation of Ph2P(O)-protected alkynes
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A Ph2P(O)-protected alkyne underwent dephosphorylation by treatment with MeMgBr in THF with Me3Si-protection untouched. The dephosphorylation followed by a transition-metal-catalyzed coupling of the resulting terminal a lkyne with aryl halides was carried out in a one-pot manner to afford the desired coupling product. Selective deprotection of Me3Si-/Ph2P(O)-protected alkynes enabled facile syntheses of expanded π-systems such as cyclic phenyleneethyny lenes and unsymmetrically substituted ditriazol.
- Peng, Lifen,Xu, Feng,Shinohara, Kenta,Orita, Akihiro,Otera, Junzo
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p. 1610 - 1612
(2014/12/11)
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- Mechanistic insight into the copper-catalyzed phosphorylation of terminal alkynes: A combined theoretical and experimental study
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The reaction mechanism of copper-catalyzed phosphorylation of terminal alkynes under different conditions has been investigated experimentally and theoretically. The important role of dioxygen has been elucidated, including the formation of η1-superoxocopper(II), η2- superoxocopper(III), μ-η2:η2-peroxodicopper(II) , and bis(μ-oxo)dicopper(III) complexes. More importantly, the proton transfer from the dialkyl phosphonate (in the form of phosphite) to the bridging oxygen atom entails the migration of the deprotonated phosphonate to the terminal alkyne, leading to the formation of a C-P bond with an activation barrier of only 1.8 kcal/mol. In addition, a particularly stable six-centered dicopper(I) species is formed with the migration of both of the Ph 2P(O) groups from the copper atoms to the oxygen atoms of the bis(μ-oxo) bridge, explaining the experimental observation that secondary phosphine oxides can be oxidized to the phosphinic acids. Thus, the diphenylphosphine oxide was added to the reaction mixture dropwise to minimize the concentration during the reaction course. Gratifyingly, the coupling product was generated almost quantitatively when the reaction was completed.
- Liu, Liu Leo,Wu, Yile,Wang, Zeshu,Zhu, Jun,Zhao, Yufen
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p. 6816 - 6822
(2014/08/18)
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- One-pot transformation of Ph2P(O)-protected ethynes: Deprotection followed by transition metal-catalyzed coupling
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Ph2P(O)-protected ethynes were successfully transformed to arylethynes in one-pot manner through t-BuOK-catalyzed deprotection followed by Sonogashira coupling with aryl halide. The arylethynes were obtained similarly by Ph2P(O)-deprotection, stannylation of the resulting terminal ethynes, and Migita-Kosugi-Stille coupling. Deprotection followed by intramolecular Eglinton coupling could be carried out in one-pot to provide cyclic butadiynes.
- Peng, Lifen,Xu, Feng,Suzuma, Yoshinori,Orita, Akihiro,Otera, Junzo
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p. 12802 - 12808
(2014/01/17)
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- Ph(O) group for protection of terminal acetylenes
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A protecting group Ph(O) for terminal ethyne was newly developed. This protecting group can be introduced readily to terminal ethyne by CuI-catalyzed phosphination and subsequent oxidation with H Ph(O)-protected ethynes remained intact in Sonogashira coup
- Yang, Xin,Matsuo, Daisuke,Suzuma, Yoshinori,Fang, Jing-Kun,Xu, Feng,Orita, Akihiro,Otera, Junzo,Kajiyama, Shingo,Koumura, Nagatoshi,Hara, Kohjiro
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p. 2402 - 2406
(2011/11/05)
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- Copper-catalyzed C-P coupling through decarboxylation
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An acid for a phosphine: A versatile protocol for preparation of various di(phenyl)phosphoryl oxides was developed by copper-catalyzed decarboxylative coupling of alkenyl, alkynyl carboxylic acids, and N-benzylproline, respectively, with R2P(O)
- Hu, Jie,Zhao, Ning,Yang, Bin,Wang, Ge,Guo, Li-Na,Liang, Yong-Min,Yang, Shang-Dong
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supporting information; experimental part
p. 5516 - 5521
(2011/06/21)
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- Phosphine-catalyzed α-P-addition on activated alkynes: A new route to P-C-P backbones
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(Chemical Equation Presented) n-Tributylphosphine was found to efficiently catalyze the α-P addition of H-phosphonates, H-phosphinates, and H-phosphine oxide pronucleophiles on alkynes bearing phosphane oxide activating moieties. The reaction leads to 2-a
- Lecercle, Delphine,Sawicki, Marcin,Taran, Frederic
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p. 4283 - 4285
(2007/10/03)
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- Synthesis of (4Z)-1,1-diphenyl-1,2,4-heptatrien-6-ynes and their facile cycloaromatizations to α,3-didehydrotoluene biradicals having a triarylmethyl radical center
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The Horner reaction between enynyl aldehydes 12 and phosphinoxy carbanion 11 provided enyneallenes 14. Thermolysis (37-80°C) of 1,4-cyclohexadiene solutions of 14 gave 20 via α,3-didehydrotoluene biradicals 19 having a reactive aryl radical center and a stabilized triarylmethyl radical center. In the absence of 1,4-cyclohexadiene, 19e underwent intramolecular H-atom transfer between the proximal benzylic methyl group and the aryl radical center to give the more stable biradical 21, the ultimate precursor of 22.
- Liu, Bin,Wang, Kung K.,Petersen, Jeffrey L.
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p. 8503 - 8507
(2007/10/03)
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