- The synthesis method of one-carbon ring expansion of cycloketone dericatives from β-selenyl cycloketone dericatives
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The present invention relates to a method for preparing a cyclic ketone derivative with an increased carbon number by performing a ring expansion reaction of a β-selenyl cyclic ketone derivative. The present invention was first developed by performing the
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Paragraph 0041; 0044-0048; 0068-0072
(2020/09/08)
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- Electrochemical Radical Selenylation/1,2-Carbon Migration and Dowd-Beckwith-Type Ring-Expansion Sequences of Alkenylcyclobutanols
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Electrochemical oxidative radical selenylation/1,2-carbon migration and Dowd-Beckwith-type ring-expansion sequences of alkenylcyclobutanols were developed in this study. This approach is environmentally benign and uses shelf-stable diselenides as selenium
- Kim, Yeon Joo,Kim, Dae Young
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supporting information
p. 1021 - 1025
(2019/02/14)
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- Rh-catalyzed 1,4-addition reactions of arylboronic acids accelerated by co-immobilized tertiary amine in silica mesopores
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Mesoporous silica-supported Rh complex catalysts were prepared by simple silane-coupling, followed by complexation, and characterized by FT-IR, SEM, Rh K-edge XAFS, and elemental analysis. Local structures of the Rh complexes in each sample were almost similar to those of a nonporous silica-supported diaminorhodium complex. Co-immobilization of a tertiary amine on the same silica surface induced slight changes to the Rh complex structure in the case of the support with smaller pores. The prepared catalysts showed high activity for the 1,4-addition reaction of phenylboronic acids. Co-immobilization of the tertiary amine increased the reaction rate by more than 7-fold, with turnover number of nearly 8500. The catalytic performance achieved with this novel system is with much higher than that reported previously with a nonporous silica-supported catalyst. The mesoporous silica-supported Rh complex-tertiary amine showed a wide substrate scope, including unsaturated ketones and nitriles. This co-immobilized tertiary amine may activate phenylboronic acid to enhance its reactivity in the transmetalation step with Rh-OH species.
- Motokura, Ken,Hashiguchi, Kohei,Maeda, Kyogo,Nambo, Masayuki,Manaka, Yuichi,Chun, Wang-Jae
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- Electronic and Steric Tuning of an Atropisomeric Disulfoxide Ligand Motif and Its Use in the Rh(I)-Catalyzed Addition Reactions of Boronic Acids to a Wide Range of Acceptors
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A novel chiral disulfoxide ligand pair bearing fluorine atoms at the 6 and 6′ position of its atropisomeric backbone, (M,S,S)- and (P,S,S)-p-Tol-6F-BIPHESO, was synthesized. Complexation to a rhodium(I) precursor gave rise to μ-Cl- and μ-OH-bridged rhodiu
- Zhao, Guang-Zhen,Foster, Daven,Sipos, Gellért,Gao, Pengchao,Skelton, Brian W.,Sobolev, Alexandre N.,Dorta, Reto
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p. 9741 - 9755
(2018/09/06)
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- 2-allyl-1-oxo-2, 3-dihydro-1, 2-benzisothiazole
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The invention discloses chiral 2-allyl-1-oxo-2, 3-dihydro-1, 2-benzisothiazole and its preparation method and use. The chiral 2-allyl-1-oxo-2, 3-dihydro-1, 2-benzisothiazole is a racemate or an optical isomer shown in the formula I and is characterized in
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Paragraph 0033; 0043
(2017/02/02)
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- The promoting effect of pyridine ligands in the Pd-catalysed Heck-Matsuda reaction
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An efficient Pd-catalyzed arylation reaction of challenging acyclic olefins, in the presence of an organic ligand, has been disclosed. Commercially available cheap pyridine-based ligands are able to promote good to excellent yields for poorly efficient Heck-Matsuda arylation reactions of several allylic alcohols. A wide range of electronically different arenediazonium salts bearing either electron-releasing or withdrawing groups have been used allowing the synthesis of a range of β-aryl-methoxy-lactols. The catalytic system has been optimised, along with the reaction conditions, in order to achieve remarkable yields in less than 1 h.
- Khodja, Walid,Leclair, Alexandre,Rull-Barrull, Jordi,Zammattio, Fran?oise,Kutonova, Ksenia V.,Trusova, Marina E.,Felpin, Fran?ois-Xavier,Rodriguez-Zubiri, Mireia
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p. 8855 - 8862
(2016/10/11)
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- Heterogeneous double-activation catalysis: Rh complex and tertiary amine on the same solid surface for the 1,4-addition reaction of aryl- and alkylboronic acids
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Double-activation catalysis by a rhodium complex/tertiary amine catalyst for the 1,4-addition of organoboronic acids was investigated. A rhodium complex and a tertiary amine were co-immobilized on the same silica surface by silane-coupling reactions follo
- Noda, Hiroto,Motokura, Ken,Chun, Wang-Jae,Miyaji, Akimitsu,Yamaguchi, Sho,Baba, Toshihide
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p. 2714 - 2727
(2015/05/27)
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- Efficient 1,4-addition of enones and boronic acids catalyzed by a Ni-Zn hydroxyl double salt-intercalated anionic rhodium(III) complex
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Intercalation of an in situ prepared [Rh(OH)6]3- complex into an anion exchangeable Ni-Zn layered hydroxy double salt (Rh/NiZn) was demonstrated. The resulting Rh/NiZn effectively catalyzed the 1,4-addition of diverse enones and phenylboronic acids to their corresponding β-substituted carbonyl compounds. In the case of 2-cyclohexen-1-one and phenylboronic acid, a turnover frequency (TOF) of 920 h-1 based on Rh was achieved. The [Rh(OH)6]3- complex maintained its original monomeric trivalent state within the NiZn interlayer following catalysis, attributable to a strong electrostatic interaction between the NiZn host and anionic Rh(III) complex.
- Hara, Takayoshi,Fujita, Nozomi,Ichikuni, Nobuyuki,Wilson, Karen,Lee, Adam F.,Shimazu, Shogo
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p. 4040 - 4046
(2015/02/19)
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- Palladium-catalyzed desulfitative conjugate addition of aryl sulfinic acids and direct ESI-MS for mechanistic studies
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A new and efficient method for palladium(II) catalytic desulfitative conjugate addition of arylsulfinic acids with α,β-unsaturated carbonyl compound has been developed. The key reacting intermediates including aryl Pd(II) sulfinic intermediate, aryl Pd(II), and C=O-Pd complexes were captured by ESI-MS/MS, which provide new experimental evidence for the understanding of addition mechanism.
- Wang, Huifeng,Li, Yaming,Zhang, Rong,Jin, Kun,Zhao, Defeng,Duan, Chunying
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supporting information; experimental part
p. 4849 - 4853
(2012/07/02)
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- Rhodium-grafted hydrotalcite catalyst for heterogeneous 1,4-addition reaction of organoboron reagents to electron deficient olefins
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A rhodium-grafted hydrotalcite (Rh/HT) was prepared by the treatment of a Mg-Al mixed hydroxide (hydrotalcite, HT) with an aqueous RhCl 3·nH2O solution. The formation of the Rh III species on the HT surface was confirmed by X-ray absorption fine structure spectroscopy. The Rh/HT catalyst was demonstrated to effectively promote the 1,4-addition reaction of organoboron reagents to electron-deficient olefins in both organic and aqueous solvents. The strong surface basicity of HT facilitates the formation of a Rh-OH species, which possesses high nucleophilicity, leading to an efficient transmetalation with organoboron reagents. This catalyst system is also applicable in the one-pot three-component synthesis of 2-cyano-3,3-diphenyl propionate due to the bifunctionality of the Rh/HT surface.
- Motokura, Ken,Hashimoto, Norifumi,Hara, Takayoshi,Mitsudome, Takato,Mizugaki, Tomoo,Jitsukawa, Koichiro,Kaneda, Kiyotomi
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experimental part
p. 2416 - 2422
(2011/10/13)
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- Well-defined [Rh(NHC)(OH)] complexes enabling the conjugate addition of arylboronic acids to α,β-unsaturated ketones
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The synthesis and catalytic activity of three well-defined monomeric rhodium(i) hydroxide complexes bearing N-heterocyclic carbene (NHC) ligands are reported. [Rh(cod)(ICy)(OH)] promoted the 1,4-addition of arylboronic acids to cyclic enones, with TONs an
- Truscott, Byron J.,Fortman, George C.,Slawin, Alexandra M. Z.,Nolan, Steven P.
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experimental part
p. 7038 - 7041
(2011/11/05)
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- N-heterocyclic carbene-rhodium(I) complexes derived from proline for the 1,4-conjugate addition of arylboronic acids to enones in neat water
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N-Heterocyclic carbene-rhodium(I) complexes derived from N-benzyl substituted proline have been successfully synthesized and were found to be efficient catalysts for the 1,4-conjugate addition of arylboronic acids to enones in neat water at 40 °C. Under the optimal reaction conditions, all reactions gave the addition products in good to high yields.
- Tang, Yi-Qiang,Lv, Huan,He, Xiao-Na,Lu, Jian-Mei,Shao, Li-Xiong
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experimental part
p. 705 - 708
(2012/01/07)
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- Pd-catalysed conjugate addition of arylboronic acids to α,β-unsaturated ketones under microwave irradiation
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The Pd-catalysed conjugate addition of arylboronic acids to α,β-unsaturated cyclic ketones was studied under controlled microwave irradiation conditions. A variety of catalysts, bases and solvents was explored in order to achieve optimum yields in the sho
- Polackova, Viera,Bariak, Vladimir,Sebesta, Radovan,Toma, Stefan
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experimental part
p. 338 - 344
(2012/02/04)
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- PH-Dependent conjugate addition of arylboronic acids to α,β-unsaturated enones catalyzed by a reusable palladium(II)/cationic 2,2'-bipyridyl system in water under air
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A reusable Pd(NH3)2Cl2/cationic 2,2'-bipyridyl system for the catalysis of the conjugate addition of arylboronic acids to α,β-unsaturated enones in water under air was developed. Addition of arylboronic acids to both cyclic and acyclic enones progressed smoothly, providing the products in good to high yields, the best result being obtained when HBF4 was used to adjust the pH value to 1.0. After the reaction, the residual aqueous solution could be reused several times,making the reaction greener and reducing wastage of precious metals. Copyright
- Huang, Shao-Hsien,Wu, Tzu-Min,Tsai, Fu-Yu
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experimental part
p. 619 - 624
(2010/11/04)
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- New preparation and reactions of arylaluminum reagents using Barbier conditions
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The reaction of various aryl bromides with magnesium turnings, LiCl and R2AlCl (R = Et, i-Bu) provides at room temperature arylaluminum reagents in high yields. These organometallic species undergo readily 1,4-additions, acylations, allylations, and Pd-catalyzed cross-couplings with various aryl iodides and bromides. Georg Thieme Verlag Stuttgart.
- Gao, Hongjun,Knochel, Paul
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experimental part
p. 1321 - 1325
(2009/12/01)
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- Rhodium fluoroapatite catalyzed conjugate addition of arylboronic acids to α,β-unsaturated carbonyl compounds
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Rhodium fluoroapatite (RhFAP) is an efficient catalyst for conjugate addition of organoboron reagents to α,β-unsaturated carbonyl compounds. A variety of arylboronic acids and α,β-unsaturated carbonyl compounds were converted to the corresponding conjugat
- Kantam, Mannepalli Lakshmi,Subrahmanyam, Vura Bala,Kumar, Kota Balaji Shiva,Venkanna, Gopaladasu T.,Sreedhar, Bojja
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scheme or table
p. 1947 - 1953
(2009/02/07)
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- Platinum-catalyzed 1,4-addition of arylboronic acids to β-substituted α,β-unsaturated ketones
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Platinum salts represented by K2PtCl4 were found to catalyze the 1,4-addition of arylboronic acids to β-substituted α,β-unsaturated ketones to give high yields of β-arylated ketones. The reaction is completed in 1h in the presence of 1 mol % of the catalyst in dioxane/H2O at 70 °C. Copyright
- Hayashi, Tamio,Sasaki, Keigo
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p. 842 - 843
(2008/12/22)
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- Method of using rhodium quinonoid catalysts
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In accordance with aspects of the invention methods of using rhodium hydroquinone catalysts for the conjugate addition of boronic acids are disclosed.
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Page/Page column 13; 14
(2008/06/13)
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- Rhodium quinonoid catalysts
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In accordance with one aspect of the invention a rhodium quinonoid catalyst is disclosed.
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Page/Page column 9; 10; 13
(2008/06/13)
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- Palladium-bipyridine catalyzed conjugate addition of arylboronic acids to α,β-unsaturated carbonyl compounds in aqueous media
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Palladium/bipyridine catalyzed conjugate addition of arylboronic acids to α,β-unsaturated carbonyl compounds in aqueous media was developed with high yields.
- Lin, Shaohui,Lu, Xiyan
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p. 7167 - 7170
(2007/10/03)
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- A rhodium-grafted hydrotalcite as a highly efficient heterogeneous catalyst for 1,4-addition of organoboron reagents to α,β-unsaturated carbonyl compounds
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Treatment of a hydrotalcite with an aqueous solution of rhodium trichloride results in a Rh-grafted hydrotalcite (Rh/HT) with monomeric Rh species on the surface, which successfully promoted 1,4-addition of organoboron reagents to α,β-unsaturated carbonyl compounds. Furthermore, this catalyst was reusable and was found to be applicable to a one-pot synthesis of 3,3-diarylnitrile.
- Fujita, Noriaki,Motokura, Ken,Mori, Kohsuke,Mizugaki, Tomoo,Ebitani, Kohki,Jitsukawa, Koichiro,Kaneda, Kiyotomi
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p. 5083 - 5087
(2007/10/03)
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- Pd(II)-bipyridine catalyzed conjugate addition of arylboronic acid to α,β-unsaturated carbonyl compounds
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A Pd(II)-catalyzed conjugate addition of arylboronic acid to α,β-unsaturated ketones, aldehydes, esters, etc. in the presence of 2,2′-bipyridine was developed. A mechanism involving transmetalation, insertion of the carbon-carbon double bond into the C-Pd bond, and protonolysis of the resulting C-Pd bond is proposed. The reaction conditions are mild and the yield is high. The presence of 2,2′-bipyridine is crucial for the reaction to inhibit β-hydride elimination.
- Lu, Xiyan,Lin, Shaohui
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p. 9651 - 9653
(2007/10/03)
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- A New Catalytic Activity of Antimony(III) Chloride in Palladium(0)-Catalyzed Conjugate Addition of Aromatics to α,β-Unsaturated Ketones and Aldehydes with Sodium Tetraphenylborate and Arylboronic Acids
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A remarkable catalytic effect of antimony(III) chloride is disclosed in palladium(0)-catalyzed conjugate addition of aromatics to α,β-unsaturated ketones and aldehydes with sodium tetraphenylborate and arylboronic acids in acetic acid at 25 deg C.Several other metal chlorides such as AlCl3, SnCl4, AsCl3, TiCl4, FeCl3, MoCl5, and CeCl3 are also effective in some cases, but SbCl3 is the salt of choice.Two key steps are proposed for this reaction: one is the oxidative addition of a C-B bond to Pd(0) forming an arylpalladium species, and the other is the formation of an antimony enolate derived from the initial coordination of SbCl3 to the carbonyl oxygen of an organopalladium intermediate.
- Cho, Chan Sik,Motofusa, Shin-ichi,Ohe, Kouichi,Uemura, Sakae,Shim, Sang Chul
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p. 883 - 888
(2007/10/02)
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