- 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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Read Online
- Hydrophosphorylation of terminal alkynes catalyzed by palladium
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A series of new 1-aryl-, 1-heteroaryl-, and 1-alkylethenylphosphonates was prepared by hydrophosphorylation of terminal acetylenes catalyzed by palladium. A stable in air complex Pd2(dba)3·CHCl3 was applied as catalyst. The reaction mechanism is discussed.
- Gulykina,Dolgina,Bondarenko,Beletskaya
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Read Online
- Stereoselective synthesis of vinylphosphonate
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Dialkyl vinylphosphonate is stereoselectively prepared by palladium-catalyzed reaction of vinyl bromide with dialkyl phosphite.
- Hirao, Toshikazu,Masunaga, Toshio,Ohshiro, Yoshiki,Agawa, Toshio
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Read Online
- Mizoroki-Heck Reaction of Unstrained Aryl Ketones via Ligand-Promoted C-C Bond Olefination
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Mizoroki-Heck reaction of unstrained aryl ketone with acrylate/styrene is accomplished via palladium-catalyzed ligand-promoted C-C bond cleavage. Various (hetero)aryl ketones are compatible in the reaction, affording the alkene product in good to excellent yields. Further applications in the late-stage olefination of some drugs, natural products, and fragrance-derived aryl ketones demonstrate the synthetic utility of this protocol. By employing ketone as both the directing group and the leaving group, 1,2-bifunctionalization is achieved via sequential ortho-C-H alkylation/ipso-Heck olefination.
- Wang, Mei-Ling,Xu, Hui,Li, Han-Yuan,Ma, Biao,Wang, Zhen-Yu,Wang, Xing,Dai, Hui-Xiong
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p. 2147 - 2152
(2021/04/05)
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- Inverting External Asymmetric Induction via Selective Energy Transfer Catalysis: A Strategy to β-Chiral Phosphonate Antipodes
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Enantiodivergent, catalytic reduction of activated alkenes relays stereochemical information encoded in the antipodal chiral catalysts to the pro-chiral substrate. Although powerful, the strategy remains vulnerable to costs and availability of sourcing bo
- Onneken, Carina,Bussmann, Kathrin,Gilmour, Ryan
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supporting information
p. 330 - 334
(2019/12/11)
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- SAR of non-hydrolysable analogs of pyridoxal 5′-phosphate against low molecular weight protein tyrosine phosphatase isoforms
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Kinases and phosphatases are key enzymes in cell signal transduction pathways. Imbalances in these enzymes have been linked to numerous disease states ranging from cancer to diabetes to autoimmune disorders. The two isoforms (IFA and IFB) of Low Molecular Weight Protein Tyrosine Phosphatase (LMW-PTP) appear to play a role in these diseases. Pyridoxal 5′-phosphate (PLP) has been shown to act as a potent but, impractical micromolar inhibitor for both isoforms. In this study, a series of non-hydrolysable phosphonate analogs of PLP were designed, synthesized and tested against the two isoforms of LMW-PTP. Assay results demonstrated that the best inhibitor for both isoforms was compound 5 with a Kis of 1.84 μM (IFA) and 15.6 μM (IFB). The most selective inhibitor was compound 16, with a selectivity of roughly 370-fold for IFA over IFB.
- DeSouza, Shirin R.,Flynn, Rebecca S.,Jakubowski, Henry V.,Marshall, Quinlen F.,McIntee, Edward J.,Olson, Maxwell C.,Sinner, Erica K.,Tinucci, Samantha L.
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supporting information
(2020/07/21)
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- TEMPO and Silver-Mediated Intermolecular Phosphonylation of Alkenes: Stereoselective Synthesis of (E)-Alkenylphosphonates
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An efficient method was developed towards the synthesis of alkenylphosphonates from simple olefins and phosphonate diesters. This method was enabled by the use of cheap and commercially available silver salts and TEMPO. This method exhibits of good functional group tolerance, specific (E)-selectivity for all olefins and vinyl selectivity for aliphatic olefins. A radical mechanism was proposed, and TEMPO was involved in the product formation step.
- Wang, Lei,Yang, Zhen,Zhu, Huijuan,Liu, Haitao,Lv, Shuaipeng,Xu, Yue
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supporting information
p. 2138 - 2142
(2019/03/17)
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- Decarbonylative Phosphorylation of Carboxylic Acids via Redox-Neutral Palladium Catalysis
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We describe the direct synthesis of organophosphorus compounds from ubiquitous aryl and vinyl carboxylic acids via decarbonylative palladium catalysis. The catalytic system shows excellent scope and tolerates a wide range of functional groups (>50 examples). The utility of this powerful methodology is highlighted in the late-stage derivatization directly exploiting the presence of the prevalent carboxylic acid functional group. DFT studies provided insight into the origin of high bond activation selectivity and P(O)-H isomerization pathway.
- Liu, Chengwei,Ji, Chong-Lei,Zhou, Tongliang,Hong, Xin,Szostak, Michal
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supporting information
p. 9256 - 9261
(2019/11/19)
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- Chemoselective Activation of Diethyl Phosphonates: Modular Synthesis of Biologically Relevant Phosphonylated Scaffolds
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Phosphonates have garnered considerable attention for years owing to both their singular biological properties and their synthetic potential. State-of-the-art methods for the preparation of mixed phosphonates, phosphonamidates, phosphonothioates, and phos
- Adler, Pauline,Pons, Amandine,Li, Jing,Heider, J?rg,Brutiu, Bogdan R.,Maulide, Nuno
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supporting information
p. 13330 - 13334
(2018/09/25)
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- Direct Aryloxylation/Alkyloxylation of Dialkyl Phosphonates for the Synthesis of Mixed Phosphonates
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A strategy for the direct functionalization strategy of inertial dialkyl phosphonates with hydroxy compounds to afford diverse mixed phosphonates with good yields and functional-group tolerance has been developed. Mechanistic investigations involving both NMR studies and DFT studies suggest that an unprecedented highly reactive PV species (phosphoryl pyridin-1-ium salt), a key intermediate for this new synthetic transformation, is generated in situ from dialkyl phosphonate in the presence of Tf2O/pyridine.
- Huang, Hai,Denne, Johanna,Yang, Chou-Hsun,Wang, Haobin,Kang, Jun Yong
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supporting information
p. 6624 - 6628
(2018/05/14)
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- Transition-metal-free C-P bond formation via decarboxylative phosphorylation of cinnamic acids with P(O)H compounds
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A novel, transition-metal-free phosphorylation of cinnamic acids with P(O)H compounds has been developed via radical-promoted decarboxylation under mild conditions. This method provides simple, efficient, and versatile access to valuable (E)-alkenylphosphine oxides in satisfactory yields with a wide variety of substrates.
- Liu, Lixin,Zhou, Dan,Dong, Jianyu,Zhou, Yongbo,Yin, Shuang-Feng,Han, Li-Biao
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p. 4190 - 4196
(2018/04/14)
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- Cu(i)/Fe(III)-Catalyzed C-P cross-coupling of styrenes with H-phosphine oxides: A facile and selective synthesis of alkenylphosphine oxides and β-ketophosphonates
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Cu(i)/Fe(iii)-Catalyzed phosphorylation and oxyphosphorylation of styrenes with H-phosphonates which can be controlled by varying the reaction temperature are developed. This study offers a new and expedient strategy for the synthesis of useful alkenylphosphine oxides and β-ketophosphonates in satisfactory yields. Moreover, the transformation is proposed to proceed via a radical process and exhibits a broad substrate scope and good functional group tolerance.
- Gu, Jian,Cai, Chun
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supporting information
p. 4226 - 4230
(2017/07/10)
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- A (E) - 2-aryl ethylene cinnamenyl method for preparing ester derivative
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The invention discloses method for preparing (E)-2-aryl vinyl phosphonate derivatives. The method comprises the specific following steps of dissolving 1-nitro-2-aryl-vinyl derivatives, a phosphorus reagent, an accelerator manganese acetate and a catalyst copper acetate in a solvent and reacting at 20-100 DEG C to obtain the (E)-2-aryl vinyl phosphonate derivatives. According to the method disclosed by the invention, the 1-nitro-2-aryl-vinyl derivatives are adopted as starting materials, the raw materials are easily available and have multiple varieties; the products obtained by the method disclosed by the invention are multiple and can be directly applied and can be also used for other further reaction; according to the method, the use of precious metal reagents and other additives is avoided; and meanwhile, the synthetic route is short, reaction conditions are mild, the reaction operation and post-treatment process are simple, the yield is high and the method is suitable for scale production.
- -
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Paragraph 0040; 0041
(2017/03/08)
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- Reaction of C-silyl-P-chloro-alkylidenephosphoranes with carbonyl compounds
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Reaction of P-chloroylides with carbonyl compounds leads to the formation of four-membered phosphorus heterocycles - 25-chloro-2,2-oxaphosphetanes. The 2-chloro-2,2-oxaphosphetanes depending on substituent R at α;-atom carbon, rearrange with formation of 2-chloroalkylphosphonates (R = H, Alk, Ar) or with elimination of trimethylchlorosilane (R = Me3Si) convert into trans-phosphorylated alkenes.
- Kolodiazhna, Olga O.,Kolodiazhnyi, Oleg I.
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p. 322 - 328
(2016/02/18)
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- Silver-catalyzed synthesis of 2-arylvinylphosphonates by cross-coupling of β-nitrostyrenes with: H -phosphites
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An efficient protocol for stereoselective synthesis of 2-arylvinylphosphonates has been developed via AgNO3-catalyzed cross-coupling of β-nitrostyrenes with dialkyl H-phosphites under mild conditions. By losing the nitro group of β-nitrostyrene
- Yuan, Jin-Wei,Yang, Liang-Ru,Mao, Pu,Qu, Ling-Bo
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p. 87058 - 87065
(2016/09/23)
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- Cross-metathesis reaction of functionalized and substituted olefins using group 8 transition metal carbene complexes as metathesis catalysts
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The invention pertains to the use of Group 8 transition metal carbene complexes as catalysts for olefin cross-metathesis reactions. In particular, ruthenium and osmium alkylidene complexes substituted with an N-heterocyclic carbene ligand are used to catalyze cross-metathesis reactions to provide a variety of substituted and functionalized olefins, including phosphonate-substituted olefins, directly halogenated olefins, 1,1,2-trisubstituted olefins, and quaternary allylic olefins. The invention further provides a method for creating functional diversity using the aforementioned complexes to catalyze cross-metathesis reactions of a first olefinic reactant, which may or may not be substituted with a functional group, with each of a plurality of different olefinic reactants, which may or may not be substituted with functional groups, to give a plurality of structurally distinct olefinic products. The methodology of the invention is also useful in facilitating the stereoselective synthesis of 1,2-disubstituted olefins in the cis configuration.
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Page/Page column 22; 43; 44
(2016/08/29)
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- Stereoselective synthesis of vinylphosphonates and phosphine oxides via silver-catalyzed phosphorylation of styrenes
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An efficient and stereoselective synthesis of vinylphosphonates and phosphine oxides was developed starting from styrenes using AgNO3 as the catalyst and K2S2O8 as the oxidant. The success of the reaction was fo
- Gui, Qingwen,Hu, Liang,Chen, Xiang,Liu, Jidan,Tan, Ze
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supporting information
p. 13922 - 13924
(2015/09/07)
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- Lewis Base Activation of Silyl Acetals: Iridium-Catalyzed Reductive Horner-Wadsworth-Emmons Olefination
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A Lewis base promoted deprotonative pronucleophile addition to silyl acetals has been developed and applied to the iridium-catalyzed reductive Horner-Wadsworth-Emmons (HWE) olefination of esters and the chemoselective reduction of the resulting enoates. Lewis base activation of silyl acetals generates putative pentacoordinate silicate acetals, which fragment into aldehydes, silanes, and alkoxides in situ. Subsequent deprotonative metalation of phosphonate esters followed by HWE with aldehydes furnishes enoates. This operationally convenient, mechanistically unique protocol converts the traditionally challenging aryl, alkenyl, and alkynyl esters to homologated enoates at room temperature within a single vessel.
- Dakarapu, Udaya Sree,Bokka, Apparao,Asgari, Parham,Trog, Gabriela,Hua, Yuanda,Nguyen, Hiep H.,Rahman, Nawal,Jeon, Junha
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supporting information
p. 5792 - 5795
(2015/12/11)
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- A new approach towards synthesis of phosphorylated alkenes
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New method of synthesis of trans-vinylphosphonates via reaction of trimethylsilyl(methyl)phosphonites with carbonyl compounds in the presence of carbon tetrachloride has been developed. The reaction involves formation of C-trimethylsilyl substituted ylide
- Kolodyazhnii,Kolodyazhnaya
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p. 359 - 365
(2015/04/14)
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- Manganese(iii)-mediated alkenyl Csp2-P bond formation from the reaction of β-nitrostyrenes with dialkyl phosphites
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Mn(OAc)3-mediated tandem phosphonyl radical addition to β-nitrostyrenes followed by denitration to form (E)-2-alkenyl phosphonates in good yield is described.
- Xue, Jian-Fei,Zhou, Shao-Fang,Liu, Ye-Ye,Pan, Xiangqiang,Zou, Jian-Ping,Asekun, Olayinka Taiwo
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p. 4896 - 4902
(2015/05/05)
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- Nickel-catalyzed decarboxylative C-P cross-coupling of alkenyl acids with P(O)H compounds
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The first nickel-catalyzed decarboxylative C-P coupling of a wide range of alkenyl acids with various P(O)H compounds, especially for H-phosphonates, has been developed, affording a versatile and efficient tool for the preparation of valuable (E)-1-alkeny
- Wu, Yile,Liu, Liu Leo,Yan, Kaili,Xu, Pengxiang,Gao, Yuxing,Zhao, Yufen
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p. 8118 - 8127
(2015/03/18)
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- Copper (II)-catalyzed regio- and stereoselective addition of H/P(O)R 2 to alkynes
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Cu(acac)2 is the new universal catalyst for β-E regio- and stereoselective syn-addition of the H-P(O)-bond of diphenylphosphine oxide, H-phosphinates, dialkylphosphites to various alkynes in the synthesis of P(O)-containing alkenes. Without additives and ligands Cu(II)-compounds showed better results than CuI or Ni(acac)2. The catalytic system developed is tolerant to typical organic functional groups present in the alkynes and to the nature of different substituents in the H-P(O)-compounds.
- Trostyanskaya, Inna G.,Beletskaya, Irina P.
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p. 2556 - 2562
(2014/04/03)
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- Experimental and theoretical studies on nickel-zinc-catalyzed cross-coupling of gem-dibromoalkenes with P(O)-H compounds
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A new stereoselective one-pot protocol for the preparation of E-alkenyl-phosphorus compounds under catalysis of an inexpensive nickel-zinc catalyst system has been developed, which provides a potential useful method for C-P bond formation. 31P NMR spectrum and density functional theory calculations were performed to study the reaction mechanism.
- Liu, Liu,Lv, Ye,Wu, Yile,Gao, Xiang,Zeng, Zhiping,Gao, Yuxing,Tang, Guo,Zhao, Yufen
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p. 2322 - 2326
(2014/01/06)
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- Nickel(II)-magnesium-catalyzed cross-coupling of 1,1-dibromo-1-alkenes with diphenylphosphine oxide: One-pot synthesis of (E)-1-alkenylphosphine oxides or bisphosphine oxides
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A novel nickel(II)-magnesium-mediated cross-coupling of diphenylphosphine oxide with a variety of 1,1-dibromo-1-alkenes has been developed, which provides a powerful and general methodology for the stereoselective synthesis of various (E)-1-alkenylphosphine oxides or bisphosphine oxides, with operational simplicity of the procedure, good to high yields and broad substrate applicability. Mechanistic studies reveal that the reaction might involve a Hirao reduction, cross-coupling and Michael addition. Copyright
- Liu, Liu,Wang, Yulei,Zeng, Zhiping,Xu, Pengxiang,Gao, Yuxing,Yin, Yingwu,Zhao, Yufen
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supporting information
p. 659 - 666
(2013/04/10)
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- CuSO4/Al2O3 as a new effective and recyclable catalyst for the arylation of dialkyl phosphites
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A new effective recycled catalyst CuSO4/Al2O 3, which performs the phosphorylation of aryl halides and bromostyrene, was proposed.
- Karlstedt,Anokhin,Beletskaya
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p. 2498 - 2499
(2014/11/08)
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- A catalytic Michael/Horner-Wadsworth-Emmons cascade reaction for enantioselective synthesis of thiochromenes
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A catalytic enantioselective sulfa-Michael/Horner-Wadsworth-Emmons reaction cascade has been developed, taking advantage of phosphonate as an electrophilic activator and a traceless binding site. Using a chiral bifunctional urea derivative as the catalyst, a variety of aryl and heteroaryl substituted thiochromenes was obtained in excellent yield with a high level of enantioselectivity. Copyright
- Choudhury, Abhijnan Ray,Mukherjee, Santanu
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supporting information
p. 1989 - 1995
(2013/08/23)
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- An efficient palladium(II) catalyst for oxidative Heck-type reaction under base-free conditions
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An efficient catalytic system for the palladium-catalyzed oxidative Heck reaction between arylboronic acids and various alkenes has been developed. Using the bis(aminoalkoxy)palladium complex of N,N-dimethylethanolamine as a catalyst, a series of substituted alkenes were obtained in moderate to excellent yields under mild reaction conditions. This protocol could be tolerated to arylboronic acids containing electron-donating or withdrawing groups and a wide range of olefins, such as acrylate, allyl esters, allyl ethers and alkenylphosphonate. A plausible reaction mechanism of the oxidative Heck reaction was proposed.
- Mi, Xia,Huang, Mengmeng,Guo, Hai,Wu, Yangjie
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p. 5123 - 5128
(2013/06/27)
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- Copper-mediated selective cross-coupling of 1,1-dibromo-1-alkenes and heteronucleophiles: Development of general routes to heterosubstituted alkynes and alkenes
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Efficient and general procedures for the cross-coupling of 1,1-dibromoalkenes and N-, O-, and P-nucleophiles are reported. Fine-tuning of the reaction conditions allows for either site-selective, double, or alkynylative cross-coupling, therefore providing
- Jouvin, Kevin,Coste, Alexis,Bayle, Alexandre,Legrand, Frederic,Karthikeyan, Ganesan,Tadiparthi, Krishnaji,Evano, Gwilherm
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p. 7933 - 7947
(2013/01/16)
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- Copper-catalyzed C-P bond construction via direct coupling of phenylboronic acids with H-phosphonate diesters
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A mild and efficient method was developed for the copper-catalyzed additions of H-phosphonate diesters to boronic acids under the copper catalyst system Cu2O/1,10-phenanthroline. To the best of our knowledge this finding is the first example of a copper-catalyzed synthesis of aryl phosphonates from arylboronic acids and H-phosphonate dialkyl esters.
- Zhuang, Rongqiang,Xu, Jian,Cai, Zhenshi,Tang, Guo,Fang, Meijuan,Zhao, Yufen
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supporting information; experimental part
p. 2110 - 2113
(2011/06/20)
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- Copper-mediated cross-coupling of 1,1-dibromo-1-alkenes with dialkyl phosphites: A convenient synthesis of 1-alkenylphosphonates
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An efficient and stereoselective procedure for the preparation of E-1-alkenylphosphonates by copper-mediated cross-coupling between 1,1-dibromo-1-alkenes and dialkyl phosphites is reported. The reaction allows for formal substitution of both bromine atoms
- Evano, Gwilherm,Tadiparthi, Krishnaji,Couty, Francois
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supporting information; experimental part
p. 179 - 181
(2011/02/25)
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- Synthesis of diethyl 2-(aryl)vinylphosphonate by the Heck reaction catalysed by supported palladium catalysts
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The synthesis of diethyl 2-(aryl)vinylphosphonate through direct Heck coupling reaction of the diethyl vinylphosphonate with aryl or heteroaryl halides catalysed by solid materials ([Pd(NH3)4]/NaY, Pd/C, PdO/SiO2) is reported. After optimising the reaction conditions (1.3 mol% [Pd(NH3)4]/NaY, DMF, K2CO 3, 110-140 °C), various aryl and heteroaryl halides were engaged in this reaction leading in all cases good to high yields. Interestingly, when using activated aryl bromides the palladium loading could be lowered to only 0.25 mol%. While highly active when coupling aryl iodides (i.e. only 0.15 mol% required), the PdO/SiO2 catalyst was found to be inactive when considering aryl bromides. Deep study of this catalytic material revealed that in the case of aryl bromides, absence of in situ reduction of the catalyst precursor prevents the cross-coupling reaction with this latter material.
- Tarabay, Jinane,Al-Maksoud, Walid,Jaber, Farouk,Pinel, Catherine,Prakash, Swamy,Djakovitch, Laurent
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experimental part
p. 124 - 133
(2011/02/23)
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- Synthesis of diethyl 2-(aryl)vinylphosphonates by the Heck reaction catalysed by well-defined palladium complexes
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Pd-catalysed procedures for the direct Heck arylation of diethyl vinylphosphonate with various aryl or heteroaryl halides toward the synthesis of diethyl 2-(aryl)vinylphosphonates are reported. Several homogeneous catalytic systems (i.e. Herrmann palladacycle, Nolan (NHC)-palladium catalyst, Pd(OAc)2/PPh3) were used and compared within the study. High conversions and selectivities were achieved under optimised conditions (2 mol% [Pd], NMP, K2CO3, 140 °C) whatever the homogeneous catalyst used.
- Al-Maksoud, Walid,Mesnager, Julien,Jaber, Farouk,Pinel, Catherine,Djakovitch, Laurent
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experimental part
p. 3222 - 3231
(2010/01/11)
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- Synthesis of stannylated allyl- and vinylphosphonates via molybdenum-catalyzed hydrostannations
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Syntheses of stannylated allyl and vinylphosphonates by molybdenum-catalyzed hydrostannation of the corresponding propargyl- and alkynylphosphonate derivatives proceed with high regioselectivities. The stannylated phosphonates obtained are versatile build
- Jena, Nivedita,Kazmaier, Uli
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experimental part
p. 3852 - 3858
(2009/04/08)
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- A new access to substituted tetraethyl N-Boc 2-aminoethylidene-1,1-bisphosphonates and phosphonyl-substituted aza-Morita-Baylis-Hillman-type adducts
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A general one-pot synthesis of substituted 2-aminoethylidene-1,1-bisphosphonates has been developed. The protocol involves base-induced addition of sodium tetraethyl methylenebisphosphonate to N-Boc imines generated in situ from N-Boc-α-amidoalkyl-p-tolyl
- Gajda, Anna,Gajda, Tadeusz
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p. 1233 - 1241
(2008/09/17)
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- Reaction of diethyl thiocyanatomethylphosphonate with aldehydes as a route to diethyl Z-1-alkenylphosphonates
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Diastereoselective synthesis of diethyl Z-1-alkenylphosphonates from easily available diethyl thiocyanatomethylphosphonate and aromatic aldehydes has been developed. Olefination of the aldehydes occurs under mild conditions and affords the title compounds with moderate yields. A plausible mechanism of the above-mentioned reaction is also discussed.
- Blaszczyk, Roman,Gajda, Tadeusz
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p. 732 - 739
(2008/03/18)
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- Copper-catalyzed β-boration of α,β-unsaturated carbonyl compounds: Rate acceleration by alcohol additives
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(Chemical Equation Presented) The efficient addition of bis(pinacolato)diboron to α/β-unsaturated carbonyl compounds with a copper-diphosphine catalyst has been carried out. A dramatic rate acceleration of the reaction was realized by adding alcohol additives. With use of this procedure, a variety of α,β-unsaturated carbonyl compounds including conjugated substrates at the acid oxidation level such as esters and nitrites were reacted to give to the corresponding β-boryl carbonyl compounds in high yields.
- Mun, Soungyun,Lee, Ji-Eon,Yun, Jaesook
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p. 4887 - 4889
(2007/10/03)
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- Metallo-phosphorylation of alkenes: a highly regioselective reaction of zirconocene-alkene complexes with chlorophosphate
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Zirconocene-alkene complexes Cp2Zr(CH2{double bond, long}CHR) reacted with chlorophosphate to form zircono-ethylphosphonate with high regioselectivity, which is versatile and could be converted into various functionalized organophosphonates.
- Lai, Chunbo,Xi, Chanjuan,Chen, Weixuan,Hua, Ruimao
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p. 6295 - 6302
(2007/10/03)
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- Synthesis of (E)-alkenes via hydroindation of C{triple bond, long}C in InCl3-NaBH4 system
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In InCl3-NaBH4-MeCN system, terminal aryl alkynes could couple with aryl iodides and bromides to give disubstituted alkenes via hydroindation of C{triple bond, long}C. In the similar way, (E)-alkenylsilanes were synthesized via reduction of alkynylsilanes in tetrahydrofuran (THF) in high yields. The processes showed high regio- and stereoselectivity.
- Wang, Chunyan,Yan, Lei,Zheng, Zhiguo,Yang, Deyu,Pan, Yuanjiang
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p. 7712 - 7717
(2007/10/03)
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- Tetraarylphosphonium halides as arylating reagents in Pd-catalyzed heck and cross-coupling reactions
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(Chemical Equation Presented) Highly efficient: Tetraarylphosphonium halides, Ar4P+X-, as arylating reagents efficiently deliver an aryl group in Pd-catalyzed reactions with olefins, organoboron compounds, and terminal alkynes (see scheme).
- Hwang, Lee Kyoung,Na, Youngim,Lee, Junseong,Do, Youngkyu,Chang, Sukbok
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p. 6166 - 6169
(2007/10/03)
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- A novel stereoselective synthesis of (E)-2-arylvinylphosphonates in InCl3-NaBH4-MeCN system
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Hydroindation of arylalkynylphosphonates gives a intermediate which can be hydrolyzed to (E)-2-arylvinylphosphonates in InCl3-NaBH 4-MeCN system, the stereoselectivity and yield are rather high, but under the same conditions 2-alkylalkynylphosphonates do not react very well.
- Wang, Chunyan,Pan, Yuanjiang,Yang, Deyu
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p. 1705 - 1709
(2007/10/03)
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- Ruthenium-Catalyzed Heck-Type Olefination and Suzuki Coupling Reactions: Studies on the Nature of Catalytic Species
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Ruthenium-catalyzed Heck olefination and Suzuki cross coupling reactions have been developed. When starting with a ruthenium complex [RuCl 2(p-cymene)]2 as a homogeneous catalyst precursor, induction periods were observed and ruthenium colloids of zero oxidation state were generated under catalytic conditions. Isolated ruthenium colloids carried out the olefination, implying that active catalytic species are ruthenium nanoclusters. To support this hypothesis, ruthenium nanoparticles stabilized with dodecylamine were independently prepared via a hydride reduction procedure, and their catalytic activity was subsequently examined. Olefination of iodobenzene with ethyl acrylate was efficiently catalyzed by the ruthenium nanoparticles under the same conditions, which could be also reused for the next runs. In poisoning experiments, the conversion of the olefination was completely inhibited in the presence of mercury, thus supporting our assumption on the nature of catalytic species. No residual ruthenium was detected from the filtrate at the end of the reaction. On the basis of the postulation, a heterogeneous catalyst system of ruthenium supported on alumina was consequently developed for the Heck olefination and Suzuki cross coupling reactions for the first time. It turned out that substrate scope and selectivity were significantly improved with the external ligand-free catalyst even under milder reaction conditions when compared to results with the homogeneous precatalyst. It was also observed that the immobilized ruthenium catalyst was recovered and reused up to several runs with consistent efficiency. Especially in the Suzuki couplings, the reactions could be efficiently carried out with as low as 1 molpercent of the supported catalyst over a wide range of substrates and were scaled up to a few grams without any practical problems, giving coupled products with high purity by a simple workup procedure.
- Na, Youngim,Park, Soyoung,Han, Soo Bong,Han, Hoon,Ko, Sangwon,Chang, Sukbok
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p. 250 - 258
(2007/10/03)
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- Polystyrene-Supported α-Seleno Carbanions: Efficient Reagents for Highly Stereocontrolled Syntheses of Vinylphosphonates and Vinylsulfones
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Polystyrene-supported selenomethyl-phosphonate and polystyrene-supported selenomethyl-sulfonates have been prepared. These novel reagents were treated with LDA (or n-BuLi) to produce polystyrene-supported α-seleno carbanions, which reacted with alkyl halides, followed by stereospecific selenoxide syn-elimination to give E-vinylphosphonates and E-vinylsulfones respectively. And also these novel polymer reagents can be regenerated and reused.
- Xu, Wei Ming,Tang, E,Huang, Xian
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p. 2094 - 2098
(2007/10/03)
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- Convenient synthesis of α,β-unsaturated phosphonates via a Mizoroki-Heck reaction of arylboronic acids with diethyl vinylphosphonate
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Palladium acetate catalyzed Mizoroki-Heck reactions of arylboronic acids with diethyl vinylphosphonates afford α,β-unsaturated phosphonates in good yields.
- Kabalka, George W.,Guchhait, Sankar K.,Naravane, Abhijit
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p. 4685 - 4687
(2007/10/03)
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- A Convenient Selenium-Linking Strategy for Traceless Solid-Phase Synthesis of Diethyl 1-Alkenephosphonates
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Treatment of a novel polymer-supported α-diethoxyphosphoryl methyl selenide with LDA followed by alkylation and oxidative deselenation efficiently afforded diethyl trans-1-alkenephosphonates in good yields and purities.
- Sheng, Shou-Ri,Zhou, Wei,Liu, Xiao-Ling,Song, Cai-Sheng
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p. 1011 - 1016
(2007/10/03)
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- Palladium- and nickel-catalyzed coupling reactions of α- bromoalkenylphosphonates with arylboronic acids and lithium alkenylborates
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The coupling reaction of the α-bromoalkenylphosphonates with organoboranes was investigated. The palladium-catalyzed arylation took place successfully with arylboronic acids, while alkenylation proceeded with lithium alkenylborates and a nickel catalyst. In addition, an intramolecular Diels-Alder reaction of the diene prepared by the alkenylation afforded the corresponding adduct.
- Kobayashi, Yuichi,William, Anthony D.
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p. 1749 - 1757
(2007/10/03)
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- Metallo-phosphorylation of alkynes: Reaction of alkynes with Cp 2Zr(1-butene)(PR3) and chlorophosphate
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Reaction of alkynes with Cp2ZrBu2 and chlorophosphate in the presence PR3 to form zircono- alkenylphosphonates, which can be converted into various β-functionalized alkenylphosphonates.
- Lai, Chunbo,Xi, Chanjuan,Chen, Chao,Ma, Mingming,Hong, Xiaoyin
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p. 2736 - 2737
(2007/10/03)
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- Synthesis of (E)- and (Z)-alkenylphosphonates using vinylboronates
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(Matrix presented) (E)- and (Z)-alkenylphosphonates have been prepared stereospecifically via the reaction of vinylboronate esters with triethyl phosphite in the presence of palladium acetate.
- Kabalka, George W.,Guchhait, Sankar K.
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p. 729 - 731
(2007/10/03)
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- Diastereoselective synthesis of 2-amino-4-phosphonobutanoic acids by conjugate addition of lithiated schoellkopf's bislactim ethers to vinylphosphonates
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Conjugate additions of lithiated bislactim ethers derived from cyclo-[Gly-Val] and cyclo-[Ala-Val] to α, β, or α,β -substituted vinylphosphonates allow direct and stereoselective access to a variety of 3- or 4-monosubstituted and 2,3-, 2,4-, or 3,4-disubstituted 2-amino-4-phosphonobutanoic acids (AP4 derivatives) in enantiomerically pure form. The relative stereochemistry was assigned by X-ray diffraction analysis or NMR study of 1,2-oxaphosphorinane derivatives. Competitive eight-membered "compact" and "relaxed" transition-state structures are invoked to rationalize the stereochemical outcome of the conjugate additions.
- Ruiz, Maria,Fernandez, M. Carmen,Diaz, Aniana,Quintela, Jose M.,Ojea, Vicente
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p. 7634 - 7645
(2007/10/03)
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- New type of metalloproteinase inhibitor: Design and synthesis of new phosphonamide-based hydroxamic acids
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A series of phosphonamide-based hydroxamate derivatives were synthesized, and the inhibitory activities were evaluated against various metalloproteinases in order to clarify its selectivity profile. Among the four diastereomeric isomers resulting from the
- Sawa, Masaaki,Kiyoi, Takao,Kurokawa, Kiriko,Kumihara, Hiroshi,Yamamoto, Minoru,Miyasaka, Tomohiro,Ito, Yasuko,Hirayama, Ryoichi,Inoue, Tomomi,Kirii, Yasuyuki,Nishiwaki, Eiji,Ohmoto, Hiroshi,Maeda, Yu,Ishibushi, Etsuko,Inoue, Yoshimasa,Yoshino, Kohichiro,Kondo, Hirosato
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p. 919 - 929
(2007/10/03)
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- Coupling reactions of α-bromoalkenyl phosphonates with aryl boronic acids and alkenyl borates
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(equation presented) Transition metal-catalyzed arylation and alkenylation of the α-bromoalkenyl phosphonates were investigated with organoboranes and -borates. Arylation was successful with the aryl boronic acids and a palladium catalyst, while alkenylation was found to proceed with alkenyl borates and a nickel catalyst. In addition, an intramolecular Diels-Alder reaction of the diene prepared by the alkenylation afforded the corresponding adduct.
- Kobayashi, Yuichi,William, Anthony D.
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p. 4241 - 4244
(2007/10/03)
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- Synthesis of vinyl- and allylphosphonates by olefin cross-metathesis
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Substituted allyl and vinyl phosphonates have been prepared for the first time via intermolecular olefin cross-metathesis (CM) using 1,3-dimesityl-4,5-dihydro-imidazol-2-ylidene ruthenium alkylidene complex 3 in good yield. A variety of terminal olefins, styrenes, and geminally disubstituted olefins have been successfully employed in these reactions. In addition, CM of vinylphosphonates provide exclusive E olefin stereochemistry.
- Chatterjee,Choi,Grubbs
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p. 1034 - 1037
(2007/10/03)
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