- Novel transformation of aryl 2-iodophenyl ketones into 1,3-diarylisoquinolines with (TMS)2NH, styrenes, NIS, and tBuOK
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Treatment of aryl 2-iodophenyl ketones with TMS2NH in the presence of Sc(OTf)3 at warming conditions, followed by the reaction with styrenes and NIS gave N-(1-aryl-2-iodoethyl) aryl 2-iodophenyl ketimines. Further treatment of N-(1-aryl-2-iodoethyl) aryl 2-iodophenyl ketimines with tBuOK in the presence of 1,10-phenanthroline at 120 °C generated 1,3-diarylisoquinolines in moderate yields through SET from tBuOK onto the iodophenyl group to form aryl radicals, their 6-endo-trig cyclization onto the vinyl groups, and aromatization of the cyclized intermediates. The present method is a novel approach for the preparation of the isoquinoline core via two steps from aryl 2-iodophenyl ketones.
- Shibasaki, Kaho,Togo, Hideo
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- α-Oxocarboxylic Acids as Three-Carbon Insertion Units for Palladium-Catalyzed Decarboxylative Cascade Synthesis of Diverse Fused Heteropolycycles
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A novel palladium-catalyzed decarboxylative cascade cyclization for the assembly of diverse fused heteropolycycles by employing α-oxocarboxylic acids as three-carbon insertion units is reported. This protocol enables the synthesis of isoquinolinedione- and indolo[2,1-a]isoquinolinone-fused benzocycloheptanones in moderate to good yields by the use of different aryl iodides, including alkene-tethered 2-iodobenzamides and 2-(2-iodophenyl)-1H-indoles. Notably, the approach achieves simultaneous construction of both six- and seven-membered rings via sequential intramolecular carbopalladation, C-H activation, and decarboxylation.
- Zhou, Liwei,Qiao, Shujia,Zhou, Fengru,Xuchen, Xinyu,Deng, Guobo,Yang, Yuan,Liang, Yun
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supporting information
p. 2878 - 2883
(2021/05/05)
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- Palladium-Catalyzed Amination/Dearomatization Reaction of Indoles and Benzofurans
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This report describes a palladium-catalyzed dearomatization and amination tandem reaction of 2,3-disubstituted indoles and benzofurans via the Catellani strategy. This reaction provides a new method for the construction of amino-substituted indoline-fused cyclic and benzofuran spiro compounds in good yields. The reaction has broad functional group compatibility and substrate scope.
- Zhang, Zhe,Zhang, Bo-Sheng,Li, Kai-Li,An, Yang,Liu, Ce,Gou, Xue-Ya,Liang, Yong-Min
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p. 7817 - 7839
(2020/07/16)
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- Synthesis of Spiro[benzofuran-2,2'-benzo[b]thiophene]-3,3'-diones via PIDA/CuBr-Mediated Spirocyclization
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A phenyliodine(III) diacetate (PIDA)/CuBr-mediated construction of the novel 3H,3'H-spiro[benzofuran-2,2'-benzo[b]thiophene]-3,3'-dione skeleton was realized from the reaction of (Z)-3-hydroxy-1-(2-hydroxyphenyl)-3-(2-halogenphenyl)prop-2-en-1-ones with p
- Du, Yunfei,Li, Xuemin,Liang, Huiyuan,Sun, Fengxia,Wang, Donghua,Wang, Xi,Yang, Yaxin O,Zhang, Jingran
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supporting information
p. 6563 - 6569
(2020/11/16)
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- PPh3/I2/HCOOH: An efficient CO source for the synthesis of phthalimides
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A straightforward and general method has been developed for the synthesis of phthalimide derivatives from 2-iodobenzamides and PPh3/I2/HCOOH in the presence of a catalytic amount of Pd(OAc)2. The reaction results demonstrate that PPh3/I2/HCOOH is a facile, efficient and safe CO source. The whole process is carried out in toluene at 80 °C and furnishes the desired products in good to excellent yields.
- Wang, Yingying,Zhou, Yang,Lei, Min,Hou, Jinjun,Jin, Qinghao,Guo, Dean,Wu, Wanying
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supporting information
p. 1180 - 1185
(2019/01/26)
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- Forming Benzylic Iodides via a Nickel Catalyzed Diastereoselective Dearomative Carboiodination Reaction of Indoles
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A diastereoselective dearomative carboiodination reaction is reported. We report a novel metal-catalyzed approach to install reactive secondary benzylic iodides. Utilizing the unique reactivity of nickel, we have expanded the carboiodination reaction to n
- Marchese, Austin D.,Lind, Florian,Mahon, áine E.,Yoon, Hyung,Lautens, Mark
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supporting information
p. 5095 - 5099
(2019/03/17)
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- Palladium-Catalyzed Dearomative Arylvinylation Reaction of Indoles with N-Arylsulfonylhydrazones
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A Pd-catalyzed dearomative arylvinylation reaction of indoles with N-arylsulfonylhydrazones as coupling partners is developed, which proceeds via a domino sequence involving dearomative carbopalladation, Pd-carbene migratory insertion, and regioselective
- Liang, Ren-Xiao,Wang, Ke,Wu, Quan,Sheng, Wei-Jian,Jia, Yi-Xia
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p. 3927 - 3930
(2019/06/13)
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- Diastereoselective Nickel-Catalyzed Carboiodination Generating Six-Membered Nitrogen-Based Heterocycles
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A scalable, diastereoselective nickel-catalyzed carboiodination reaction is reported that avoids metal-based reducing agents. Novel anti-dihydroquinolones and previously unreported tetrahydroquinolines are now readily prepared. The generation of anti-dihydroquinolones is noteworthy, as this selectivity is opposite to that of the Pd variant. Mechanistic insight into the nature of the nickel-catalyzed carboiodination reaction was derived experimentally, suggesting a catalyst-controlled cyclization and stereoretentive reductive elimination.
- Marchese, Austin D.,Kersting, Louise,Lautens, Mark
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supporting information
p. 7163 - 7168
(2019/09/12)
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- Palladium-Catalyzed Domino Heck/C-H Activation/Decarboxylation: A Rapid Entry to Fused Isoquinolinediones and Isoquinolinones
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A new palladium-catalyzed tandem cyclization of various alkene-tethered aryl iodides has been presented. In this protocol, o-bromobenzoic acids are employed as coupling parters to achieve the insertion of aromatic rings by the cleavage of C(sp2)-Br and decarboxylation, thus assembling various dibenzoisoquinolinediones and dibenzoisoquinolinones. In addition, a seven-membered ring can be constructed by the use of 8-bromo-1-naphthoic acid. Notably, this approach enables regioselective product formation and features broad substrate scope.
- Luo, Xiai,Zhou, Liwei,Lu, Haiyan,Deng, Guobo,Liang, Yun,Yang, Chunming,Yang, Yuan
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supporting information
p. 9960 - 9964
(2019/12/24)
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- 2-Iodo-N-isopropyl-5-methoxybenzamide as a highly reactive and environmentally benign catalyst for alcohol oxidation
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Several N-isopropyliodobenzamides were evaluated as catalysts for the oxidation of benzhydrol to benzophenone in the presence of Oxone (2KHSO5·KHSO4·K2SO4) as a co-oxidant at room temperature. A study on the substituent effect of the benzene ring of N-isopropyl-2-iodobenzamide on the oxidation revealed that its reactivity increased in the following order of substitution: 5-NO2 2Me, 3-OMe 5-OAc 5-Cl H, 4-OMe 5-Me 5-OMe. The oxidation of various benzylic and aliphatic alcohols using a catalytic amount of the most reactive 5-methoxy derivative successfully resulted in moderate to excellent yields of the corresponding carbonyl compounds. The high reactivity of the 5-methoxy derivative at room temperature is a result of the rapid generation of the pentavalent species from the trivalent species during the reaction. 5-Methoxy-2-iodobenzamide would be an efficient and environmentally benign catalyst for the oxidation of alcohols, especially benzylic alcohols.
- Yakura, Takayuki,Fujiwara, Tomoya,Yamada, Akihiro,Nambu, Hisanori
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p. 971 - 978
(2019/11/11)
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- Direct Difluorination-Hydroxylation, Trifluorination, and C(sp2)-H Fluorination of Enamides
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A direct double functionalization involving both difluorination and hydroxylation of enamides is reported. With the appropriate combination of an electrophilic fluorinating reagent and H2O, the most convenient and ecofriendly hydroxylating agent, the preparation of 3-(difluoroalkyl)-3-hydroxyisoindolin-1-ones was achieved under basic or Br?nsted acidic conditions. Suitable conditions for trifluorination as well as C(sp2)-H fluorination were also identified. Subsequent asymmetric functionalization of the obtained gem-difluorinated products has also been demonstrated.
- Munoz, Socrates B.,Krishnamurti, Vinayak,Barrio, Pablo,Mathew, Thomas,Prakash, G. K. Surya
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supporting information
p. 1042 - 1045
(2018/02/23)
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- Palladium-Catalyzed Domino Allenamide Carbopalladation/Direct C-H Allylation of Heteroarenes: Synthesis of Primprinine and Papaverine Analogues
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Palladium-catalyzed intramolecular carbopalladation onto allenamides completed by direct C-H allylation of heterocycles is studied. The domino construction/heteroarylation of isoquinolone process is first achieved. A general three-step one-pot strategy, i
- Hédouin, Jonathan,Schneider, Cédric,Gillaizeau, Isabelle,Hoarau, Christophe
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supporting information
p. 6027 - 6032
(2018/10/05)
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- Ni-Catalyzed Alkene Carboacylation via Amide C-N Bond Activation
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We report Ni-catalyzed formal carboacylation of o-allylbenzamides with arylboronic acid pinacol esters. The reaction is triggered by oxidative addition of an activated amide C-N bond to a Ni(0) catalyst and proceeds via alkene insertion into a Ni(II)-acyl bond. The exo-selective carboacylation reaction generates 2-benzyl-2,3-dihydro-1H-inden-1-ones in moderate to high yields (46-99%) from a variety of arylboronic acid pinacol esters and substituted o-allylbenzamides. These results show that amides are practical substrates for alkene carboacylation via amide C-N bond activation, and this approach bypasses challenges associated with alkene carboacylation triggered by C-C bond activation.
- Walker, James A.,Vickerman, Kevin L.,Humke, Jenna N.,Stanley, Levi M.
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supporting information
p. 10228 - 10231
(2017/08/10)
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- Palladium-Catalyzed Alkylation with Alkyl Halides by C(sp3)?H Activation
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Utilizing halogens as traceless directing goups represents an attractive strategy for C?H functionalization. A two C?H alkylation system, initiated by the oxidative addition of organohalides to Pd0, has been developed. The first reaction involves an intermolecular alkylation of palladacycles to form C(sp3)?C(sp2) bonds followed by C(sp2)?H activation/cyclization to deliver alkylated benzocyclobutenes as the final products. In the second reaction, two C?C bonds are formed by the reaction of palladacycles with CH2Br2, and provides a facile and efficient method for the synthesis of indanes. The alkylated benzocyclobutene products can be transformed into tricyclic hyrocarbons, and the indane derivatives are essential structural motifs in bioactive and odorant molecules.
- Wu, Zhuo,Ma, Ding,Zhou, Bo,Ji, Xiaoming,Ma, Xiaotian,Wang, Xiaoling,Zhang, Yanghui
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supporting information
p. 12288 - 12291
(2017/09/06)
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- Magnetically recyclable copper modified GO/Fe3O4 catalyst for efficient synthesis of quinazolinones
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A series of bioactive quinazolinones were effectively synthesized by the condensation of halide benzamide with amino acid using magnetically recyclable GO/Fe3O4-CuI as catalyst. Magnetic GO/Fe3O4-CuI was prepared via a simple chemical method and characterized by FTIR, powder XRD, and SEM. This heterogeneous copper catalyst can be easily separated from reaction mixtures by an external permanent magnet and reused without any obvious loss in activity which shows its applicability as a reusable and promising catalyst for quinazolinones synthesis.
- Kong, Lu-Lu,Fan, Li-Yan
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supporting information
p. 827 - 831
(2016/06/14)
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- CHEMICAL COMPOUNDS
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The present invention provides compounds of formula (I) including stereoisomers or a racemate or a mixture or a pharmaceutically acceptable salt thereof: wherein X is NH, or O; Q is 5-6 membered heteroaryl group, which may be substituted by one or more su
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Paragraph 0178-0180
(2015/03/16)
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- Palladium-Catalyzed Carbonylative Annulation Reactions Using Aryl Formate as a CO Source: Synthesis of 2-Substituted Indene-1,3(2H)-dione Derivatives
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An efficient synthesis of 2-substituted indene-1,3(2H)-diones from stable and readily available 1-(2-halophenyl)-1,3-diones by employing phenyl formate as a CO source has been developed. The reaction occurred via palladium-catalyzed intramolecular carbonylative annulation using K3PO4 as a base and DMSO as a solvent at 95 °C. In this protocol, the reaction showed a broad substrate scope with good to excellent yields.
- Zhang, Ying,Chen, Jing-Lei,Chen, Zhen-Bang,Zhu, Yong-Ming,Ji, Shun-Jun
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p. 10643 - 10650
(2015/11/18)
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- Relative Rate Profiles of Functionalized Iodoarene Catalysts for Iodine(III) Oxidations
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A series of rate studies were conducted to evaluate the steric and electronic properties that govern the reactivity of iodoarene amide catalysts in the α-oxytosylation of propiophenone. A meta-substituted benzamide catalyst emerged as the most reactive. This catalyst was employed in the α-oxytosylation of a series of substituted propiophenones, returning the α-tosyloxy ketone products in excellent isolated yield.
- Lex, Timothy R.,Swasy, Maria I.,Whitehead, Daniel C.
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p. 12234 - 12243
(2016/01/09)
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- Palladium-catalyzed intramolecular asymmetric C-H functionalization/ cyclization reaction of metallocenes: An efficient approach toward the synthesis of planar chiral metallocene compounds
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A palladium-catalyzed asymmetric synthesis of planar chiral metallocene compounds is reported. The reaction stereoselectively functionalized one of the ortho C-H bonds of Cp rings by intramolecular cyclization to form indenone derivatives in high yields w
- Deng, Ruixian,Huang, Yunze,Ma, Xinna,Li, Gencheng,Zhu, Rui,Wang, Bin,Kang, Yan-Biao,Gu, Zhenhua
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supporting information
p. 4472 - 4475
(2014/04/17)
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- Additive effects in the palladium-catalyzed carboiodination of chiral N-allyl carboxamides
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The use of Pd catalysis as a means to synthesize organic halides has recently received increased attention. Among the reported methods is the Pd-catalyzed carboiodination, which uses extremely bulky ligands to facilitate carbon-halogen reductive eliminati
- Petrone, David A.,Yoon, Hyung,Weinstabl, Harald,Lautens, Mark
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supporting information
p. 7908 - 7912
(2014/08/05)
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- CHEMICAL COMPOUNDS
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The present invention provides compounds of formula (I) including stereoisomers or a racemate or a mixture or a pharmaceutically acceptable salt thereof: wherein X is NH, or O; Q is 5-6 membered heteroaryl group, which may be substituted by one or more su
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Page/Page column 25
(2013/10/08)
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- 3-(2-Aminocarbonylphenyl)propanoic acid analogs as potent and selective EP3 receptor antagonists. Part 1: Discovery and exploration of the carboxyamide side chain
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A series of 3-(2-aminocarbonyl-4-phenoxymethylphenyl)propanoic acid analogs were synthesized and evaluated for their EP3 antagonist activity in the presence of additive serum albumin. Several compounds were biologically evaluated for their in vivo efficacy with respect to the PGE2-induced uterine contraction in pregnant rats as well as their pharmacokinetics. The discovery process of these potent and selective EP3 antagonists and their structure activity relationship are also presented.
- Asada, Masaki,Obitsu, Tetsuo,Nagase, Toshihiko,Tanaka, Motoyuki,Yamaura, Yoshiyuki,Takizawa, Hiroya,Yoshikawa, Ken,Sato, Kazutoyo,Narita, Masami,Ohuchida, Shuichi,Nakai, Hisao,Toda, Masaaki
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experimental part
p. 80 - 90
(2010/04/05)
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- Palladium-catalyzed enantioselective cyclization of silyloxy-1,6-enynes
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The enantioselective intramolecular addition of silyl enol ethers and silyl ketene aminals onto alkyne is described. The reaction employs DTBMSegphos-Pd(II) or Binaphane-Pd(II) complexes as catalysts for the formation of methylene cyclopentane adducts fro
- Corkey, Britton K.,Toste, F. Dean
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p. 2764 - 2765
(2007/10/03)
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- Pd-catalyzed dynamic kinetic enantioselective arylation of silylphosphines
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Palladium-catalyzed cross-couplings represent a powerful method for the formation of new bonds. A catalytic, enantioselective P-C bond-forming reaction proceeding via a Pd-mediated arylation of silylphosphines was developed for the synthesis of P-stereoge
- Chan, Vincent S.,Bergman, Robert G.,Toste, F. Dean
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p. 15122 - 15123
(2008/09/18)
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