- Method for green synthesis of simvastatin side chain (by machine translation)
-
The method, comprises the following steps, adding :(1) dimethyl butanoic acid 2,2 - thionyl chloride, to the reaction vessel in a pot method, to carry out the esterification reaction ;(2) to obtain the product (1) dimethyl - 1 1-oxobutyl 3 -methyl propionate, through a solventless method, thereby reducing the material cost 3 - [(2,2 - without using any acid-binding agent) in the esterification step] and reducing the pollution, to the environment by a one-pot, method, at the same time without using any acid-tie-acid-acid-tie-acid-acid methyl ester, to carry out esterification reaction in a solvent concentration step, in the, esterification step by using a solventless method in a step, in the esterification reaction step, to obtain the, product (dimethyl) chloride, in the esterification step. (by machine translation)
- -
-
Paragraph 0024-0029
(2020/04/17)
-
- Metal-Free Photoinduced Hydroalkylation Cascade Enabled by an Electron-Donor-Acceptor Complex
-
A metal- A nd photocatalyst-free photoinduced radical cascade hydroalkylation of 1,7-enynes has been disclosed. The process is triggered by a single electron transfer (SET) event involving a photoexcited electron-donor-acceptor complex between an NHPI ester and a Hantzsch ester, which decomposes to afford a tertiary radical that is readily trapped by the enyne. The method provides an operationally simple, robust, and step-economical approach toward the construction of diversely functionalized dihydroquinolinones bearing quaternary centers. A sequential one-pot hydroalkylation-isomerization approach is also offered, giving access to a family of quinolinones. A wide substrate scope and high functional group tolerance were observed in both approaches.
- Correia, José Tiago M.,Piva Da Silva, Gustavo,Kisukuri, Camila M.,André, Elias,Pires, Bruno,Carneiro, Pablo S.,Paixa?, Márcio W.
-
p. 9820 - 9834
(2020/09/03)
-
- Naphthalimide and quinoline derivatives as inhibitors for insect N-acetyl-β-D-hexosaminidase
-
Insect chitinolytic β-N-acetyl-D-hexosaminidase, such as OfHex1 from Ostrinia furnacalis, is a potential target for insecticide design. Among the known OfHex1 inhibitors, Q2 is of great interest because it is the first non-carbohydrate inhibitor. In this study, we designed and synthesized a series of Q2 derivatives by replacing the thiadiazole and naphthalimide groups and changing the linker length. Compound 3m showed the best inhibitory activity with a Ki value of 0.34 μmol/L against OfHex1, which is about one-quarter that of Q2 (Ki = 1.4 μmol/L). Compound 6a showed the best inhibitory activity among the quinoline-containing derivatives (Ki = 2.3 μmol/L). Molecular docking indicated that although 3m, 6a, and Q2 binding the active pocket of OfHex1 in similar mode, compound 3m engaged better than the other compounds in intermolecular interaction with OfHex1.
- Yang, Huibin,Qi, Huitang,Liu, Tian,Shao, Xusheng,Yang, Qing,Qian, Xuhong
-
supporting information
p. 977 - 980
(2019/02/13)
-
- Pd/Cu-Catalyzed Cascade C(sp3)-H Arylation and Intramolecular C-N Coupling: A One-Pot Synthesis of 3,4-2 H-Quinolinone Skeletons
-
In this letter, we successfully explored a cascade Pd/Cu-catalyzed intermolecular C(sp3)-H arylation of amides and intramolecular C-N coupling reaction. This method provides a one-pot strategy to synthesize 3,4-2H-quinolinone with good regioselectivity of C-H arylation and C-N coupling from C-I and C-X bonds from readily available starting materials.
- Xiao, Han-Zhi,Wang, Wen-Shu,Sun, Yu-Song,Luo, Hao,Li, Bo-Wen,Wang, Xiao-Dong,Lin, Wei-Li,Luo, Fei-Xian
-
supporting information
p. 1668 - 1671
(2019/03/11)
-
- 2-Amino-5,6-difluorophenyl-1 H-pyrazole-Directed PdII Catalysis: Arylation of Unactivated β-C(sp3)-H Bonds
-
Palladium-catalyzed arylation of unactivated β-C(sp3)-H bonds in carboxylic acid derivatives with aryl iodides is described for the first time using 2-amino-5,6-difluorophenyl-1H-pyrazole as an efficient and readily removable directing group. Two fluoro groups are installed at the 5- and 6-position of the anilino moiety in 2-aminophenyl-1H-pyrazole, clearly enhancing the directing ability of the auxiliary. In addition, the protocol employs Cu(OAc)2/Ag3PO4 (1.2/0.3) as additives, evidently reducing the stoichiometric amount of expensive silver salts. Furthermore, this process exhibits high β-site selectivity, compatibility with diverse substrates containing α-hydrogen atoms, and excellent functional group tolerance.
- Yang, Jinyue,Fu, Xiaopan,Tang, Shibiao,Deng, Kezuan,Zhang, Lili,Yang, Xianjin,Ji, Yafei
-
p. 10221 - 10236
(2019/08/20)
-
- Palladium-catalyzed 2-pyridylmethyl-directed β-C(sp3)–H activation and cyclization of aliphatic amides with gem-dibromoolefins: A rapid access to γ-lactams
-
The direct Pd-catalyzed β-C(sp3)–H activation and cyclization of aliphatic amides bearing a removable 2-pyridylmethyl directing group with gem-dibromoolefins is described for the first time to construct a variety of γ-lactams. The resulting products with Z- and E-configurations can be easily separated and purified after the reaction, demonstrating the effectiveness and applicability of the method herein developed.
- Zhou, Danni,Wang, Chunxia,Li, Mingliang,Long, Zheng,Lan, Jingbo
-
p. 191 - 193
(2017/11/17)
-
- COLORED CURABLE COMPOSITION, COLORED CURED FILM, COLOR FILTER AND PRODUCTION METHOD THEREOF, DISPLAY APPARATUS, SOLID-STATE IMAGING DEVICE, AND COMPOUND
-
A colored curable composition is provided, which has excellent storage stability and can be used to obtain a colored cured film and a color filter having excellent heat resistance, brightness, contrast and pattern shapes. The colored curable composition contains: a polymerizable compound, and at least one selected from groups consisting of a compound represented by the following general formula (I) and a tautomer thereof. General Formula (I)
- -
-
Paragraph 0182; 0186; 0188
(2018/11/02)
-
- Direct C-C Bond Formation from Alkanes Using Ni-Photoredox Catalysis
-
A method for direct cross coupling between unactivated C(sp3)-H bonds and chloroformates has been accomplished via nickel and photoredox catalysis. A diverse range of feedstock chemicals, such as (a)cyclic alkanes and toluenes, along with late-stage intermediates, undergo intermolecular C-C bond formation to afford esters under mild conditions using only 3 equiv of the C-H partner. Site selectivity is predictable according to bond strength and polarity trends that are consistent with the intermediacy of a chlorine radical as the hydrogen atom-abstracting species.
- Ackerman, Laura K. G.,Martinez Alvarado, Jesus I.,Doyle, Abigail G.
-
p. 14059 - 14063
(2018/10/24)
-
- Palladium-Catalyzed β-Mesylation of Simple Amide via Primary sp3 C-H Activation
-
A β-mesylation of primary sp3 C-H bonds from simple amides with methanesulfonic anhydride (Ms2O) has been established successfully at 80 °C in a Pd(OAc)2 (catalyst)/K2S2O8 (oxidant)/CF3CH2OH (solvent) system. These amide substrates involve N-monosubstituted linear, branch, or cyclic alkanes, and electron-deficient benzyl compounds. The β-mesylated amide products can be converted easily to β-fluoroamides or β-lactams through inter- or intramolecular SN2 processes.
- Zhao, Ren,Lu, Wenjun
-
supporting information
p. 1768 - 1771
(2017/04/11)
-
- Nickel-Catalyzed oxidative coupling of unactivated C(sp3)-H bonds in aliphatic amides with terminal alkynes
-
In this work, we demonstrated Ni-catalyzed oxidative coupling of unactivated C(sp3)-H bonds with terminal alkynes for construction of C(sp3)-C(sp) bonds to synthesize alkyl-substituted internal alkynes. Different amides exhibited good compatibility. Preliminary mechanistic studies were conducted to account for this alkynylation.
- Luo, Fei-Xian,Cao, Zhi-Chao,Zhao, Hong-Wei,Wang, Ding,Zhang, Yun-Fei,Xu, Xing,Shi, Zhang-Jie
-
supporting information
p. 18 - 21
(2017/04/04)
-
- A General Approach to Quaternary Center Construction from Couplings of Unactivated Alkenes and Acyl Xanthates
-
A general, radical-mediated approach to quaternary center construction using unactivated alkenes as coupling partners is reported. In this strategy, acyl xanthates, readily accessed from carboxylic acids, serve as precursors to tertiary radicals. This strategy leverages the unique reactivity of xanthates to participate in efficient radical-mediated additions to unactivated alkenes, expanding the scope of quaternary center construction.
- Jenkins, Ernest N.,Czaplyski, William L.,Alexanian, Erik J.
-
supporting information
p. 2350 - 2353
(2017/05/12)
-
- Thioamide-Directed Cobalt(III)-Catalyzed Selective Amidation of C(sp3)?H Bonds
-
A mild, oxidant-free, and selective Cp*CoIII-catalyzed amidation of thioamides with robust dioxazolone amidating agents via C(sp3)?H bond activation to generate the desired amidated products is reported. The method is efficient and allows for the C?H amidation of a wide range of functionalized thioamides with aryl-, heteroaryl-, and alkyl-substituted dioxazolones under the Cp*CoIII-catalyzed conditions. The observed regioselectivity towards primary C(sp3)?H activation is supported by computational studies and the cyclometalation is proposed to proceed by means of an external carboxylate-assisted concerted metalation/deprotonation mechanism. The reported method is a rare example of the use of a directing group other than the commonly used pyridine and quinolone classes for Cp*CoIII-catalyzed C(sp3)?H functionalization and the first to exploit thioamides.
- Tan, Peng Wen,Mak, Adrian M.,Sullivan, Michael B.,Dixon, Darren J.,Seayad, Jayasree
-
supporting information
p. 16550 - 16554
(2017/12/07)
-
- Copper(II)/Silver(I)-Catalyzed Sequential Alkynylation and Annulation of Aliphatic Amides with Alkynyl Carboxylic Acids: Efficient Synthesis of Pyrrolidones
-
A highly efficient protocol for the synthesis of pyrrolidones by the copper-catalyzed alkynylation/annulation of aliphatic amides with alkynyl carboxylic acids is discussed in this paper. A broad range of easily accessible alkynyl carboxylic acids were introduced at the β-methyl group of aliphatic amides with the assistance of an 8-aminoquinolyl auxiliary group via decarboxylation to achieve the subsequent cyclic C-N bond formation within one hour. High selectivity of β-methyl groups over methylene groups was observed, and the extension of this catalytic system to the activation of methylene C-H bonds failed. The substrates with two different groups at the α-position of the aliphatic amides lead to the formation of diastereoisomers which is determined by 1H NMR spectroscopy. The initially produced products with Z-configurations can be easily transformed to the corresponding products with E-configurations by the treatment with dilute p-toluenesulfonic acid after the reaction. This catalytic tandem decarboxylative cyclization provides a new opportunity for the direct functionalization of sp3 C-H bonds.
- Zhang, Jitan,Li, Danyang,Chen, Hui,Wang, Binjie,Liu, Zhanxiang,Zhang, Yuhong
-
supporting information
p. 792 - 807
(2016/03/09)
-
- Unprecedented copper-mediated oxidative demethylation of propionamides via bidentate-chelation assistance
-
A copper-mediated directed demethylation of propionamides has been developed. This reaction proceeds predominantly at the α-methyl groups of aliphatic amides with high efficiency and provides a unique tool for the direct cleavage of unactivated C(sp3)-C(sp3) bonds. The directing groups can be smoothly removed to afford the corresponding alkyl carboxylic acids.
- Liu, Jing-Hui,Cui, Mian,Lu, Xiao-Yu,Zhang, Zhen-Qi,Xiao, Bin,Fu, Yao
-
supporting information
p. 1242 - 1245
(2016/01/15)
-
- NECROSIS INHIBITORS
-
The invention provides amides that inhibit cellular necrosis and/or human receptor interacting protein 1 kinase (RIP1), including corresponding sulfonamides, and pharmaceutically acceptable salts, hydrides and stereoisomers thereof. The compounds are employed in pharmaceutical compositions, and methods of making and use, including treating a person in need thereof with an effective amount of the compound or composition, and detecting a resultant improvement in the person's health or condition.
- -
-
Paragraph 0182; 0183; 0184
(2016/07/27)
-
- Nickel-catalyzed direct thioetherification of β-C(sp3)-H bonds of aliphatic amides
-
The nickel-catalyzed β-thioetherification of unactivated C(sp3)-H bond of propionamides is established with the assistance of 8-aminoquinoline auxiliary, leading to the β-thio carboxylic acid derivatives. A broad range of functional groups is compatible with this thioetherfication reaction. The process represents the first successful example of metal-catalyzed C-S bond formation from unactivated C(sp3)-H bonds.
- Lin, Cong,Yu, Wenlong,Yao, Jinzhong,Wang, Bingjie,Liu, Zhanxiang,Zhang, Yuhong
-
supporting information
p. 1340 - 1343
(2015/03/14)
-
- Synthesis of oxazolines from amides via palladium-catalyzed functionalization of unactivated C(sp3)-H bond
-
A complementary method that enables the expeditious synthesis of oxazolines from amides via Pd-catalyzed C(sp3)-H functionalization has been described. Preliminary studies indicate that the reaction might go through a chlorination/nucleophilic cyclization sequence, and the high efficiency of this sequence is enhanced by the in situ cyclative capture of the chlorinated intermediate. The resulting oxazolines can be further converted into the corresponding β-amino alcohols without chromatography.
- Li, Bo,Wang, Si-Qing,Liu, Bin,Shi, Bing-Feng
-
supporting information
p. 1200 - 1203
(2015/03/14)
-
- Nickel-catalyzed direct thiolation of C(sp3)-H bonds in aliphatic amides
-
Nickel-catalyzed thiolation of the inactivated methyl C(sp3)-H bonds of aliphatic amides with disulfide is described. It is a novel strategy for the synthesis of thioethers with the ultimate goal of generating thioether carboxylic acids with various functional groups.
- Wang, Xie,Qiu, Renhua,Yan, Chunyang,Reddy, Vutukuri Prakash,Zhu, Longzhi,Xu, Xinhua,Yin, Shuang-Feng
-
supporting information
p. 1970 - 1973
(2015/04/27)
-
- Palladium(0)/PAr3-catalyzed intermolecular amination of C(sp3)-H bonds: Synthesis of β-amino acids
-
An intermolecular C(sp3)-H amination using a Pd0/PAr3 catalyst was developed. The reaction begins with oxidative addition of R2N-OBz to a Pd0/PAr3 catalyst and subsequent cleavage of a C(sp3)-H bond by the generated Pd-NR2 intermediate. The catalytic cycle proceeds without the need for external oxidants in a similar manner to the extensively studied palladium(0)-catalyzed C-H arylation reactions. The electron-deficient triarylphosphine ligand is crucial for this C(sp3)-H amination reaction to occur.
- He, Jian,Shigenari, Toshihiko,Yu, Jin-Quan
-
supporting information
p. 6545 - 6549
(2015/06/08)
-
- Copper-mediated aryloxylation and vinyloxylation of β-C(sp3)-H bond of propionamides with organosilanes
-
A novel copper-mediated method for the aryloxylation and vinyloxylation of β-C(sp3)-H bonds of propioamides with organosilanes is described. The reaction proceeds with the assistance of an 8-aminoquinolyl auxiliary in a tandem way by the first oxidation of β-C(sp3)-H bonds and subsequent arylation/vinylation to give the aryloxylation/vinyloxylation products. This unusual aryloxy/vinyloxy forming reaction offers a new avenue for the functionalization of unactivated sp3 C-H bonds in organic synthesis.
- Zhang, Jitan,Chen, Hui,Wang, Binjie,Liu, Zhanxiang,Zhang, Yuhong
-
supporting information
p. 2768 - 2771
(2015/06/16)
-
- Cobalt-Catalyzed Cyclization of Aliphatic Amides and Terminal Alkynes with Silver-Cocatalyst
-
A new method of cobalt-catalyzed synthesis of pyrrolidinones from aliphatic amides and terminal alkynes was discovered through a C-H bond functionalization process on unactivated sp3 carbons with the silver cocatalyst using a bidentate auxiliary. For the first time, a broad range of easily accessible alkynes are exploited as the reaction partner in C(sp3)-H bond activation to give the important 5-ethylidene-pyrrolidin-2-ones in a site-selective fashion. The reaction tolerates a wide variety of functional groups including -F, -Cl, -Br, -CF3, ether, cyclopropane, and thiophene. Both pyridine ligand and aromatic solvent play the important role for the promotion of reactivity. This cobalt-catalyzed cyclization reaction can be successfully extended to a variety of aromatic amides to afford a variety of isoindolinones. Attractive features of this catalytic system include its low cost, easy operation, and convenient access to a wide range of pyrrolidinones and isoindolinones.
- Zhang, Jitan,Chen, Hui,Lin, Cong,Liu, Zhanxiang,Wang, Chen,Zhang, Yuhong
-
supporting information
p. 12990 - 12996
(2015/10/28)
-
- Readily Removable Directing Group Assisted Chemo- and Regioselective C(sp3)-H Activation by Palladium Catalysis
-
Currently used directing groups for selective aliphatic β-functionalization of carbonyl compounds show excellent reactivity and selectivity with an amide as a linker. Described herein is 2-piconimide, used for the first time with commercially available 2-picolinamide/2-picolic acid as precursors, to direct C-H arylation/alkenylation by palladium catalysis. The directing group is essential for promoting the sequnetial primary and secondary C(sp3)-H arylation with different aryl iodides in one substrate. The directing group was easily removed under simple reaction conditions at room temperature.
- Zhang, Yun-Fei,Zhao, Hong-Wei,Wang, Hui,Wei, Jiang-Bo,Shi, Zhang-Jie
-
supporting information
p. 13686 - 13690
(2015/11/16)
-
- Nickel-Catalyzed Direct C (sp3)-H Arylation of Aliphatic Amides with Thiophenes
-
Nickel-catalyzed heteroarylation of the inactive methyl C(sp3)-H bond of aliphatic amide with heteroarenes is described. The method takes advantage of chelation assistance by an 8-aminoquinolinyl moiety. The synthetic reaction has good tolerance toward functional groups, and it can be used in the construction of various kinds of alkyl-substituted heteroarenes.
- Wang, Xie,Zhu, Longzhi,Chen, Sihai,Xu, Xinhua,Au, Chak-Tong,Qiu, Renhua
-
supporting information
p. 5228 - 5231
(2015/11/18)
-
- Palladium(II)-catalyzed enantioselective C(sp3)-H activation using a chiral hydroxamic acid ligand
-
An enantioselective method for Pd(II)-catalyzed cross-coupling of methylene β-C(sp3)-H bonds in cyclobutanecarboxylic acid derivatives with arylboron reagents is described. High yields and enantioselectivities were achieved through the development of chiral mono-N-protected α-amino-O- methylhydroxamic acid (MPAHA) ligands, which form a chiral complex with the Pd(II) center. This reaction provides an alternative approach to the enantioselective synthesis of cyclobutanecarboxylates containing α-chiral quaternary stereocenters. This new class of chiral catalysts also show promises for enantioselective β-C(sp3)-H activation of acyclic amides.
- Xiao, Kai-Jiong,Lin, David W.,Miura, Motofumi,Zhu, Ru-Yi,Gong, Wei,Wasa, Masayuki,Yu, Jin-Quan
-
supporting information
p. 8138 - 8142
(2014/06/23)
-
- 1,2,4-TRIAZOL-5-ONES AND ANALOGS EXHIBITING ANTI-CANCER AND ANTI-PROLIFERATIVE ACTIVITIES
-
Described are compounds of Formula I which find utility in the treatment of cancer, autoimmune diseases and metabolic bone disorders through inhibition of c-FMS (CSF-lR), c-KIT, and/or PDGFR kinases. These compounds also find utility in the treatment of other mammalian diseases mediated by c-FMS, c-KIT, or PDGFR kinases.
- -
-
Paragraph 0390
(2014/09/29)
-
- Steric effects and mechanism in the formation of hemi-acetals from aliphatic aldehydes
-
Some physical properties (pKa, log POW, boiling points) of hexanoic acid 1 (X = COOH) and its seven isomers 2, 3, 4, 5, 6, 7, 8 (X = COOH) are reported. Hexanal 1 (X = CHO) and its seven isomeric aldehydes 2, 3, 4, 5, 6, 7, 8 (X = CHO) are shown to equilibrate, in methanol solution, with their hemi-acetals. Logarithms of equilibrium constants correlate with values of Es for the isomeric C5H11 substituents, and with logs of relative rates for saponification of the corresponding methyl esters with ρ = 0.52, reflecting the reduced steric demand of hydrogen compared to oxygen in the quaternization of ester and aldehydic carbonyl groups. Rates of equilibration have also been measured in buffered methanol. For hexanal, with a 2:1 Et3N:AcOH buffer, the buffer-independent contribution is dominated by the methoxide catalysed pathway. Rates in this medium have been determined for isomers 1, 2, 3, 4, 5, 6, 7, 8 (X = CHO), and their logarithms do not correlate with logarithms of equilibrium constants for hemi-acetal formation or with substituent steric parameters derived from ester formation or saponification, indicating that the steric changes associated with full quaternization of the carbonyl group are not mirrored in the transition structures for hemi-acetal formation. It is suggested that transition states for hemi-acetal formation are relatively early so that steric interactions are effectively those between the nucleophile and ground state conformations of the aldehydes. A comparison of the entropies of hemi-acetal formation with entropies of activation has provided a basis for a suggested transition structure. Comparisons with acid chloride hydrolyses are made. Copyright 2013 John Wiley & Sons, Ltd. Logarithms of equilibrium constants for formation hemi-acetals of hexanal and its seven isomeric aldehydes correlate well with values of Es for the isomeric C5H11 substituents, and with logs of relative rates for saponification of the corresponding methyl esters. Logarithms of rate constants for hemi-acetal formation do not, indicating that the steric changes associated with full quaternization of the carbonyl group are not mirrored in the transition structures for hemi-acetal formation. The reasons for this are discussed. Copyright
- Daw, Graham,Regan, Andrew C.,Watt, C. Ian F.,Wood, Evan
-
p. 1048 - 1057
(2014/01/06)
-
- β-Arylation of carboxamides via iron-catalyzed C(sp3)-H bond activation
-
A 2,2-disubstituted propionamide bearing an 8-aminoquinolinyl group as the amide moiety can be arylated at the β-methyl position with an organozinc reagent in the presence of an organic oxidant, a catalytic amount of an iron salt, and a biphosphine ligand at 50 C. Various features of selectivity and reactivity suggest the formation of an organometallic intermediate via rate-determining C-H bond cleavage rather than a free-radical-type reaction pathway.
- Shang, Rui,Ilies, Laurean,Matsumoto, Arimasa,Nakamura, Eiichi
-
supporting information
p. 6030 - 6032,3
(2013/05/22)
-
- Highly regioselective carbonylation of unactivated C(sp3)-H bonds by ruthenium carbonyl
-
The regioselective carbonylation of unactivated C(sp3)-H bonds of aliphatic amides was achieved using Ru3(CO)12 as a catalyst. The presence of a 2-pyridinylmethylamine moiety in the amide is crucial for a successful reaction. The reaction shows a preference for C-H bonds of methyl groups as opposed to methylene C-H bonds and tolerates a variety of functional groups. The stoichiometric reaction of an amide with Ru 3(CO)12 gave a dinuclear ruthenium complex in which the 2-pyridinylmethylamino moiety was coordinated to the ruthenium center in an N,N manner.
- Hasegawa, Nao,Charra, Valentine,Inoue, Satoshi,Fukumoto, Yoshiya,Chatani, Naoto
-
supporting information; experimental part
p. 8070 - 8073
(2011/07/08)
-
- Pd(ll)-Catalyzed olefination of sp3 C-H bonds
-
"Chemical equation presented" The first Pd(II)-catalyzed sp3 C-H olefination reaction has been developed using N-arylamide directing groups. Following olefination, the resulting intermediates were found to undergo rapid 1,4-addition to give the corresponding &-lactams. Notably, this method was effective with substrates containing (-hydrogen atoms and could be applied to effect methylene C-H olefination of cyclopropane substrates.
- Wasa, Masayuki,Engle, Keary M.,Yu, Jin-Quan
-
supporting information; experimental part
p. 3680 - 3681
(2010/05/15)
-
- Pd(II)-catalyzed carbonylation of C(sp3)-H bonds: A new entry to 1,4-dicarbonyl compounds
-
Pd(II)-catalyzed β-C(sp3)-H carbonylation of N-arylamides under CO (1 atm) has been achieved. Following amide-directed C(sp3)-H cleavage and insertion of CO into the resulting [Pd(II)-C(sp3)] bond, intramolecular C-N reductive elimination gave the corresponding succinimides, which could be readily converted to 1,4-dicarbonyl compounds. This method was found to be effective with substrates containing α-hydrogen atoms and could be applied to effect methylene C(sp3)-H carbonylation of cyclopropanes.
- Yoo, Eun Jeong,Wasa, Masayuki,Yu, Jin-Quan
-
supporting information; experimental part
p. 17378 - 17380
(2011/02/24)
-
- Analogs of isovaleramide, a pharmaceutical composition including the same, and a method of treating central nervous system conditions or diseases
-
An isovaleramide analog having at least one of an increased potency, an increased half-life, and an increased stability compared to isovaleramide. The isovaleramide analog is a cyclic analog or a noncyclic analog. The isovaleramide analog is formulated into a pharmaceutical composition. A method of treating a central nervous system condition or disease is also disclosed. The method comprises administering an isovaleramide analog to a patient suffering from the central nervous system condition or disease.
- -
-
Page/Page column 6
(2010/02/15)
-
- Converting gem-dimethyl groups into cyclopropanes via Pd-catalyzed sequential C-H activation and radical cyclization
-
(Diagram presented) A novel route to the synthesis of cyclopropane derivatives is described. 1,1-Dimethyls in 2-(1,1-dimethylalkyl) dimethyloxazolines are first converted into 1,3-diiodide derivatives via Pd-catalyzed sequential C-H activation and then radically cyclized to provide 2-(1-alkylcylclopropyl)-dimethyloxazolines. The use of EtOAc as a solvent is crucial for the diiodination of the functionalized substrates.
- Giri, Ramesh,Wasa, Masayuki,Breazzano, Steven P.,Yu, Jin-Quan
-
p. 5685 - 5688
(2007/10/03)
-
- CATALYTICS ASYMMETRIC ACTIVATION OF UNACTIVATED C-H BONDS, AND COMPOUNDS RELATED THERETO
-
One aspect of the present invention is directed in part to catalytic and stereoselective functionalization of unactivated C-H bonds of simple organic substrates. The compounds and methods provided herein allow one to control the stereochemistry in a C-H activation step, activate substrates containing α-hydrogens next to the directing group, and remove a directing group under mild conditions. One aspect of the present invention relates to a transition-metal-catalyzed method for selective and asymmetric oxidation of carbons located in a β- or γ-position relative to an auxiliary. Another aspect of the invention relates to the enantiomerically-enriched substrates and the enantiomerically-enriched products formed via said method. In certain embodiments, oxazoline and oxazinone directing groups are used. In addition, the Boc protecting group has been identified as a directing group which does not necessitate removal.
- -
-
Page/Page column 76-77
(2010/10/20)
-
- Palladium-catalyzed asymmetric iodination of unactivated C-H bonds under mild conditions
-
(Chemical Equation Presented) Specific, asymmetric, and mild: Oxazoline (Oxa), a removable chelating chiral auxiliary, assists in the asymmetric activation of C(sp3)-H bonds at the β position and C(sp 2)-H bonds at the γ position. Pd-(OAc)2 is an effective catalyst for the selective and asymmetric iodination of methyl, cyclopropyl, and aryl groups at room temperature (see formulae).
- Giri, Ramesh,Chen, Xiao,Yu, Jin-Quan
-
p. 2112 - 2115
(2007/10/03)
-
- Pyrazole urea-based inhibitors of p38 MAP kinase: From lead compound to clinical candidate
-
We report on a series of N-pyrazole, N′-aryl ureas and their mode of binding to p38 mitogen activated protein kinase. Importantly, a key binding domain that is distinct from the adenosine 5′-triphoshate (ATP) binding site is exposed when the conserved activation loop, consisting in part of Asp168-Phe169-Gly170, adopts a conformation permitting lipophilic and hydrogen bonding interactions between this class of inhibitors and the protein. We describe the correlation of the structure-activity relationships and crystallographic structures of these inhibitors with p38. In addition, we incorporated another binding pharmacophore that forms a hydrogen bond at the ATP binding site. This modification affords significant improvements in binding, cellular, and in vivo potencies resulting in the selection of 45 (BIRB 796) as a clinical candidate for the treatment of inflammatory diseases.
- Regan, John,Moss, Neil,Pargellis, Chris,Pav, Sue,Proto, Alfred,Swinamer, Alan,Tong, Liang,Torcellini, Carol,Breitfelder, Steffen,Cirillo, Pier,Gilmore, Thomas,Graham, Anne G.,Hickey, Eugene,Klaus, Bernhard,Madwed, Jeffrey,Moriak, Monica
-
p. 2994 - 3008
(2007/10/03)
-
- Process to simvastatin ester
-
A process is disclosed, for the formation of simvastatin, which comprises the sequential acylation of a diol lactone to form a bis acylated intermediate followed by selective deacylation and lactone ring closure to form simvastatin.
- -
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- 3-Hydroxy-3-methylglutaryl-coenzyme A Reductase Inhibitors. 4. Side Chain Ester Derivatives of Mevinolin
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Modification of the 2(S)-methylbutyryl moiety of mevinolin led to a series of side chain ester derivatives.A systematic exploration of the structure-activity relationships showed that the introduction of an additional aliphatic group on the carbon α to the carbonyl group increased potency.This obsrevation led to the synthesis of compound 16, which has about 2.5 times the intrinsic inhibitory activity of mevinolin.
- Hoffman, W. F.,Alberts, A. W.,Anderson, P. S.,Chen, J. S.,Smith, R. L.,Willard, A. K.
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p. 849 - 852
(2007/10/02)
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- Insecticidal 2,6-difluorobenzoyl derivatives of 4-substituted-1,3-thiazole-2-acetonitriles
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Compounds of the formulas I, II, or III STR1 wherein R is an alkyl group containing 2 to 6 carbon atoms optionally substituted by one or more halogen atoms, a cycloalkyl group containing 3 to 6 ring carbon atoms optionally substituted by one of more alkyl groups containing 1 or 2 carbon atoms, an aryl or aralkyl group containing 6 to 10 carbon atoms optionally ring-substituted by one or more halogen atoms or alkyl groups containing 1 or 2 carbon atoms or an alkoxycarbonyl alkyl group in which the alkyl portions contain from 1 to 6 carbon atoms, are useful as insecticides, particularly against the species of the Order Lepidoptera.
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- LONG-ACTING CONTRACEPTIVE AGENTS: ESTER OF NORETHISTERONE WITH α- AND/OR β-CHAIN BRANCHING
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The synthesis of eighteen esters of norethisterone (17α-ethynyl-17β-hydroxyestr-4-en-3-one) is described.These all possess some form of α- and/or β-substitution in the ester side-chain.The work was undertaken in order to evaluate any long-acting fertility control effect intrinsic in such compounds.A pentamethyl disiloxy ether was also included in the group of substances prepared for testing because of its similar substitution pattern.
- Watson, T. G.,Hosking, M.,Herz, J. E.,Torres, J. V.,Muller, J.,et al.
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p. 255 - 266
(2007/10/02)
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