- Palladium-Catalyzed Domino Cyclization/Phosphorylation of gem-Dibromoolefins with P(O)H Compounds: Synthesis of Phosphorylated Heteroaromatics
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We presented a palladium-catalyzed domino cyclization/phosphorylation of gem-dibromoolefins, which utilize H-phosphinates and secondary phosphine oxides as the phosphine sources, respectively. A variety of phosphorylated heteroaromatics were obtained in m
- Chen, Chen,Ding, Jie,Liu, Liying,Huang, Yujie,Zhu, Bolin
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supporting information
p. 200 - 205
(2021/10/29)
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- Counterion Control of t-BuO-Mediated Single Electron Transfer to Nitrostilbenes to Construct N-Hydroxyindoles or Oxindoles
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tert-Butoxide unlocks new reactivity patterns embedded in nitroarenes. Exposure of nitrostilbenes to sodium tert-butoxide was found to produce N-hydroxyindoles at room temperature without an additive. Changing the counterion to potassium changed the reaction outcome to yield solely oxindoles through an unprecedented dioxygen-transfer reaction followed by a 1,2-phenyl migration. Mechanistic experiments established that these reactions proceed via radical intermediates and suggest that counterion coordination controls whether an oxindole or N-hydroxyindole product is formed.
- Driver, Tom G.,Sung, Siyoung,Wink, Donald J.,Zadrozny, Joseph M.,Zhao, Yingwei,Zhu, Haoran
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supporting information
p. 19207 - 19213
(2021/08/09)
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- Synthesis of Azepino[1,2-a]indole-10-amines via [6+1] Annulation of Ynenitriles with Reformatsky Reagent
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Lewis acid-catalyzed [6+1] annulation reactions of 2-cyano-1-propargyl- and 2-alkynyl-1-cyanomethyl-indoles with Reformatsky reagent are described. 8-Aryl, 8-alkyl-, 8-hetaryl-, 9-aryl, and 9-alkyl-azepino[1,2-a]indole amines were obtained through a 7-endo-mode cyclization of the β-aminoacrylate intermediates. The antiproliferative activity of the azepino[1,2-a]indoles analogs against the HCT-116 cells were also examined.
- Iioka, Ryoya,Yorozu, Kohei,Sakai, Yoko,Kawai, Rika,Hatae, Noriyuki,Takashima, Katsuki,Tanabe, Genzoh,Wasada, Hiroaki,Yoshimatsu, Mitsuhiro
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supporting information
p. 1553 - 1558
(2021/02/26)
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- Synthesis of 3-Substituted Chalcogenophene-Fused Indoles from 2-Alkynylindoles
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The intramolecular electrophilic cyclization of 3-organoselanyl-2-alkynylindoles providing the synthesis of 3-iodo-selenophene-fused indoles is reported herein. The strategy was extended to the preparation of 3-iodo-thiophene-fused indoles in a one-pot iodine-promoted thiolation of 2-alkynylindoles, followed by an electrophilic cyclization sequence. Besides, the synthesis of 3-butylselanyl-selenophene-fused indoles from 3-butylselanyl-2-alkynylindoles was also developed using iron(III) chloride and dibutyl diselenide to promote the cyclization and functionalization of the heterocycle. The identification of the alkyl halide intermediate afforded evidence to the proposed mechanism, which indicated that the reactions proceed through the formation of an iodonium ion, followed by a selenium 5-endo-dig cyclization, to afford the indole derivatives. The 3-iodo-selenonophene-fused indoles prepared were applied as substrates in copper-catalyzed cross-coupling reactions with thiols to give the Ullmann type products in good yields. (Figure presented.).
- Leonel, Guilherme,Back, Davi F.,Zeni, Gilson
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p. 585 - 593
(2019/12/24)
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- TRANSGLUTAMINASE 2 (TG2) INHIBITORS
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Described herein are compounds and pharmaceutical compositions containing such compounds which inhibit transglutaminase 2 (TG2). Also described herein are methods for using such TG2 inhibitors, alone or in combination with other compounds, for treating diseases or conditions that would benefit from TG2 inhibition.
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Paragraph 00486
(2020/03/02)
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- Efficient synthesis of pyrano[4,3-b]indol-1(5H)-ones from CO2 and alkynyl indoles promoted by a protic ionic liquid
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An efficient method was developed for the synthesis of pyrano[4,3-b]indol-1(5H)-ones, which uses a protic ionic liquid [HTBD+][TFE–] as both the solvent and reaction promoter. The reactions could be efficiently carried out at atmosph
- Li, Chun,Jiang, Jian,Li, Linlin,Zhang, Ling,Chen, Qian,Wang, Mengna,Fu, Changli,Zhang, Lin
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supporting information
(2020/10/05)
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- Divergent Syntheses of Indoles and Quinolines Involving N1-C2-C3 Bond Formation through Two Distinct Pd Catalyses
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Pd-catalyzed annulative couplings of 2-alkenylanilines with aldehydes using alcohols as both the solvent and hydrogen source have been developed. These domino processes allow divergent syntheses of two significant N-heterocycles, indoles and quinolines, from the same substrate by tuning reaction parameters, which seems to invoke two distinct mechanisms. The nature of the ligand and alcoholic solvent had a profound influence on the selectivity and efficiency of these protocols. Particularly noteworthy is that indole formation was achieved by overcoming two significant challenges, regioselective hydropalladation of alkenes and subsequent reactions between the resulting Csp3-Pd species and less reactive imines.
- San Jang, Su,Kim, Young Ho,Youn, So Won
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supporting information
p. 9151 - 9157
(2020/11/03)
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- Pd-Catalyzed Tandem Coupling Reaction of 2-gem-Dibromovinylanilines and N-Tosylhydrazones to Construct 2-(1-phenylvinyl)-indoles
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A novel palladium(0)-catalyzed intermolecular coupling reaction of 2-gem-dibromovinylanilines and N-tosylhydrazones was reported to construct 2-(1-phenylvinyl)-indoles efficiently. The indole bearing 1, 1-disubstituted alkenes were obtained in one step wi
- Song, Jian,Chi, Xiaochen,Meng, Long,Zhao, Pingping,Sun, Fenggang,Zhang, Daopeng,Jiao, Luyang,Liu, Qing,Dong, Yunhui,Liu, Hui
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supporting information
p. 3599 - 3604
(2019/06/27)
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- Exploring the Reactivity of N-Alkynylated Sulfoximines: Acid-Catalyzed Cyclizations
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N-Alkynylated sulfoximines undergo acid-promoted cyclization processes under mild reaction conditions. The transformations proceed in short reaction times affording sulfoximidoyl-functionalized naphtho[2,1-b]thiophenes or pyrrolo[1,2-a]quinolines in up to
- Pirwerdjan, Ramona,Becker, Peter,Bolm, Carsten
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supporting information
p. 3307 - 3309
(2016/07/26)
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- Unusual 1,2-aryl migration in Pd(II)-catalyzed aza-Wacker-type cyclization of 2-alkenylanilines
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Inspired by the Hegedus aza-Wacker indole synthesis, we were intrigued with the fate of the aminopalladation intermediate if syn β-hydrogen is made inaccessible or unavailable. In contrast to our previously reported β-carbon elimination, cyclization of a
- Youn, So Won,Lee, So Ra
-
supporting information
p. 4652 - 4656
(2015/04/27)
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- The Dual Role of 1,8-Diazabicyclo[5.4.0]undec-7-ene (DBU) in the Synthesis of Terminal Aryl- and Styryl-Acetylenes via Umpolung Reactivity
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The dual role of the bicyclic amidine base 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) was demonstrated in a synthesis of terminal aryl- and styryl-acetylenes. Mechanistically, a tandem process involving elimination/Umpolung/protonation occurs in a single step to generate terminal aryl- and styryl-acetylenes from geminal dibromoalkenes. The key to the success of this transformation lies in the organobase-mediated generation of the acetylide from the 1-bromoalkynes at room temperature. The unique characteristics of DBU as an inherently safer reagent make it an attractive alternative to previous systems wherein required pyrophoric reagents and nonambient temperatures remain unsolved issues. The procedure does not work for the synthesis of alkyl-acetylenes.
- Morri, Ashok Kumar,Thummala, Yadagiri,Doddi, Venkata Ramana
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supporting information
p. 4640 - 4643
(2015/09/28)
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- Selective access to 3-cyano-1 H -indoles, 9 H -pyrimido[4,5- b ]indoles, or 9 H -Pyrido[2,3- b ]indoles through copper-catalyzed one-pot multicomponent cascade reactions
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Novel and selective synthetic approaches toward indole derivatives via copper-catalyzed one-pot multicomponent cascade reactions of 1-bromo-2-(2,2-dibromovinyl)benzenes with aldehydes and aqueous ammonia are presented. Intriguingly, the concentration of a
- Li, Bin,Guo, Shenghai,Zhang, Ju,Zhang, Xinying,Fan, Xuesen
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p. 5444 - 5456
(2015/06/16)
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- Metal-free C-H amination for indole synthesis
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An effective metal-free C-H amination of N-Ts-2-alkenylanilines by using DDQ as an oxidant has been developed to afford a diverse range of substituted indoles. This protocol is operationally simple and robust, obviates the need of expensive transition-metal catalysts, and offers a broad substrate scope. A mechanism involving a radical cation generated by SET and a migratorial process via a phenonium ion intermediate is proposed.
- Jang, Young Ho,Youn, So Won
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supporting information
p. 3720 - 3723
(2014/08/05)
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- CuI-catalyzed coupling of gem-dibromovinylanilides and sulfonamides: An efficient method for the synthesis of 2-amidoindoles and indolo[1,2-a] quinazolines
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A Cu(I)-catalyzed, intermolecular protocol for the synthesis of 2-amidoindoles and tetrahydroindolo[1,2-a]quinazolines in shorter time and high yields is reported. The key highlight of this disclosure is the formation of 2-amidoindole and tetrahydroindolo[1,2-a]quinazoline moieties directly from gem-dibromovinylanilides and sulfonamides in a one-pot fashion through the in situ formation of ynamides followed by a base-promoted intramolecular hydroamidation.
- Kiruthika, Selvarangam E.,Perumal, Paramasivan Thirumalai
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supporting information
p. 484 - 487
(2014/04/03)
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- Synthesis of pyrrolo-/indolo[1,2-a ]quinolines and naphtho[2,1- b ]thiophenes from gem -dibromovinyls and sulphonamides
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A highly efficient and simple route for the synthesis of pyrrolo-/indolo[1,2-a]quinolines and naphtho[2,1-b]thiophenes from gem-dibromovinyls and sulphonamides is reported. The noteworthy feature of this report is that the methodology involves a two-step protocol to synthesize tri- and tetracyclic heterocycles in a one-pot fashion through the Cu(I)-catalyzed formation of ynamide followed by a Ag(I)-assisted intramolecular hydroarylation. The photophysical properties of representative examples of pyrrolo- and indolo[1,2-a]quinolines in solid and solution states have also been studied.
- Kiruthika, Selvarangam E.,Nandakumar, Avanashiappan,Perumal, Paramasivan Thirumalai
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supporting information
p. 4424 - 4427
(2015/02/05)
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- Synthesis of biologically active pyridoimidazole/imidazobenzothiazole annulated polyheterocycles using cyanuric chloride in water
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An efficient and mild protocol for rapid access to N-fused polyheterocycles via Pictet-Spengler type 6-endo cyclization using cyanuric chloride in an aqueous reaction medium has been developed. The protocol was successfully applied to a wide range of compounds including aryl/heteroaryl aldehydes (8a-o), ketones (10a-e), an electron-rich metallocene aldehyde (8e) and indoline-2,3-diones (12a-c) using cyanuric chloride (15-20 mol%) with tetra-n-butylammonium bromide (TBAB) (2.0 eq.) as an additive at 80-90 °C to give a good to excellent yield (66-92%) of polyheterocycles. Some of the synthesized compounds were found to exhibit antiplasmodial activity against chloroquine-sensitive (CQ-S) 3D7 and chloroquine-resistant (CQ-R) K1 strains of Plasmodium falciparum. This journal is the Partner Organisations 2014.
- Pandey, Anand Kumar,Sharma, Rashmi,Singh, Awantika,Shukla, Sanjeev,Srivastava, Kumkum,Puri, Sunil K.,Kumar, Brijesh,Chauhan, Prem M. S.
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p. 26757 - 26770
(2014/07/21)
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- The application of a monolithic triphenylphosphine reagent for conducting Ramirez gem-dibromoolefination reactions in flow
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The application of a monolithic form of triphenylphosphine to the Ramirez gem-dibromoolefination reaction using flow chemistry techniques is reported. A variety of gem-dibromides were synthesised in high purity and excellent yield following only removal of solvent and no further off-line purification. It is also possible to perform the Appel reaction using the same monolith and the relationship between the mechanisms of the two reactions is discussed.
- Roper, Kimberley A.,Berry, Malcolm B.,Ley, Steven V.
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supporting information
p. 1781 - 1790
(2013/10/22)
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- An efficient one-pot synthesis of 3,5-diaryl-4-bromopyrazoles by 1,3-dipolar cycloaddition of in situ generated diazo compounds and 1-bromoalk-1-ynes
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A simple, highly efficient, one-pot synthesis of 3,5-di-aryl-4- bromopyrazoles via 1,3-dipolar cycloaddition of diazo compounds and alkynyl bromides has been developed. The diazo compounds and alkynyl bromides were generated in situ from tosylhydrazones and gem-dibromoalkenes, respectively. When ketone-derived hydrazones were used, 3,5-diaryl-4-bromo-3H-pyrazoles were obtained and the isomerization products 3,5-diaryl-4-bromo-1H-pyrazoles were formed when using aldehyde-derived hydrazones. The reaction system exhibited high regioselectivity and good functional group tolerance. Both electron-rich and electron-deficient-substituents on the aromatic ring of the hydrazones or the gem-dibromoalkenes gave desired products in moderate to good yields (67-86%). Georg Thieme Verlag Stuttgart - New York.
- Sha, Qiang,Wei, Yunyang
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supporting information
p. 413 - 420
(2013/03/14)
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- Synthesis of 6H-isoindolo[2,1-a]indol-6-ones through a sequential copper-catalyzed C-N coupling and palladium-catalyzed C-H activation reaction
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A series of 6H-isoindolo[2,1-a]indol-6-ones were synthesized through one-pot sequential coupling reactions, which were comprised of a copper-catalyzed C-N coupling cyclization and a palladium-catalyzed C-H activation course. General chemicals benzoyl chlorides and o-gem-dibromovinyl anilines were employed as the starting substrates.
- He, Hua-Feng,Dong, Sheng,Chen, Yi,Yang, Yang,Le, Yueqin,Bao, Weiliang
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supporting information; experimental part
p. 3112 - 3116
(2012/06/01)
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- Rapid, robust, clean, catalyst-free synthesis of 2-halo-3-carboxyindoles
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A novel synthesis of 2-halo-3-carboxyindoles from 2-(2,2-dihalovinyl) anilines was discovered. Reaction conditions and substrate applicability were studied. Optimally, the reaction takes only minutes when these substrates are heated in DMSO at 120 °C in t
- Kunzer, Aaron R.,Wendt, Michael D.
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supporting information; experimental part
p. 1815 - 1818
(2011/05/05)
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- Horner-Wadsworth-Emmons modification for Ramirez gem-dibromoolefination of aldehydes and ketones using P(Oi-Pr)3
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A simple procedure for the use of triisopropylphosphite in the Ramirez olefination is described. This reagent is equally or more reactive than PPh 3 toward aldehydes and ketones in the gem-dibromoolefination of aldehydes and ketones. Under the
- Fang, Yuan-Qing,Lifchits, Olga,Lautens, Mark
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p. 413 - 417
(2008/04/01)
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- A highly selective tandem cross-coupling of gem-dihaloolefins for a modular, efficient synthesis of highly functionalized indoles
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(Chemical Equation Presented) A highly efficient method of indole synthesis using gem-dihalovinylaniline substrates and an organoboron reagent was developed via a Pd-catalyzed tandem intramolecular amination and an intermolecular Suzuki coupling. Aryl, alkenyl, and alkyl boron reagents are all successfully employed, making for a versatile modular approach. The reaction tolerates a variety of substitution patterns on the aniline leading to indoles with group at C2-C7. The orthogonal approach of the sequential copper- and palladium-mediated synthesis of 1,2-diarylindoles exploited the wide availability of diverse organoboron reagents.
- Fang, Yuan-Qing,Lautens, Mark
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p. 538 - 549
(2008/09/17)
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- Tandem palladium-catalyzed N,C-coupling/carbonylation sequence for the synthesis of 2-carboxyindoles
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(Chemical Equation Presented) Tandem palladium-catalyzed N,C-coupling/carbonylation, under 10 aim of carbon monoxide and at 110 °C, is a novel and efficient method for the preparation of 2-carboxyindoles. The catalyst system tolerates a variety of functional groups, and the noted indoles were obtained in good isolated yields.
- Vieira, Tiago O.,Meaney, Laura A.,Shi, Yong-Ling,Alper, Howard
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supporting information; experimental part
p. 4899 - 4901
(2009/05/31)
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- 2-VINYL INDOLES, PYRIDO AND AZEPINO INDOLE DERIVATIVES, 2-ALKYNYL INDOLES, 2-ALKYNYL BENZO[b]FURANS, THEIR PRECURSORS AND NOVEL PROCESSES FOR THE PREPARATION THEREOF
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The present invention relates to the preparation of 2-vinyl indoles from ortho-gem-dibromovinylaniline compounds and alkene reagents using a palladium pre-catalyst, a base, and, in some instances, a ligand or additive. The present invention also relates t
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Page/Page column 66
(2008/06/13)
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- Discovery and structure-activity relationship studies of indole derivatives as liver X receptor (LXR) agonists
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A structurally novel liver X receptor (LXR) agonist (1) was identified from internal compound collection utilizing the combination of structure-based virtual screening and high-throughput gene profiling. Compound 1 increased ABCA1 gene expression by eightfold and SREBP1c by threefold in differentiated THP-1 macrophage cell lines. Confirmation of its agonistic activity against LXR was obtained in the co-factor recruitment and reporter transactivation assays. Structure-activity relationship studies on compound 1 are described.
- Bakir, Farid,Kher, Sunil,Pannala, Madhavi,Wilson, Norma,Nguyen, Trang,Sircar, Ila,Takedomi, Kei,Fukushima, Chiaki,Zapf, James,Xu, Kui,Zhang, Shao-Hui,Liu, Juping,Morera, Lisa,Schneider, Lisa,Sakurai, Naoki,Jack, Rick,Cheng, Jie-Fei
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p. 3473 - 3479
(2008/09/19)
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- 2-SUBSTITUTED INDOLES, THEIR PRECURSORS AND NOVEL PROCESSES FOR THE PREPARATION THEREOF
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Disclosed are processes for the preparation of 2-substituted indole compounds wherein the 2-substituent comprises an R4 group, wherein R4 is selected from the group consisting of monocyclic aromatic, polycyclic aromatic, monocyclic heteroaromatic, polycyclic heteroaromatic, 1° alkyl, and alkenyl, all of which are optionally substituted at one or more substitutable positions with one or more suitable substituents, and wherein R4 is bonded to the 2-position of the indole ring via a C-C bond; the process comprising reacting an ortho-gem-dihalovinylaniline compound of the formula (I): wherein Halo comprises Br, Cl, or I; each of the one or more R1 is independently selected from the group consisting of H, fluoro, lower alkyl, lower alkenyl, lower alkoxy, aryloxy, lower haloalkyl, lower alkenyl, -C(O)O-lower alkyl, monocyclic or polycyclic aryl or heteroaryl moiety, or R1 is an alkenyl group bonded so to as to form a 4- to 20-membered fused monocycle or polycyclic ring with the indole ring; all of which are optionally substituted with one or more suitable substituents at one or more substitutable positions; R2 comprises H, alkyl, cycloalkyl, aryl, heteroaryl, aryl-loweralkyl-, or heteroaryl-loweralkyl-, all of which are optionally substituted at one or more substitutable positions with one or more suitable substituents; R3 comprises H, alkyl, haloalkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, heterocycle, aryl-(C1-6)alkyl-, or heteroaryl-loweralkyl-, all of which are optionally substituted at one or more substitutable positions with one or more suitable substituents; with an organoboron reagent selected from the group consisting of a boronic ester of R4, a boronic acid of R4, a boronic acid anhydride of R4, a trialkylborane of R4 and a 9-BBN derivative of R4; in the presence of a base, a palladium metal pre-catalyst and a ligand under reaction conditions effective to form the 2-substituted indole compound. Also disclosed are processes for the preparation of ortho-gem-dihalovinylaniline compounds. Novel compounds prepared by the processes and novel uses of the compounds are likewise disclosed.
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Page/Page column 44; 74-75
(2010/11/08)
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- Cul-catalyzed tandem intramolecular amidation using gem-dibromovinyl systems
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Imidazoindolones are present as the key structural motif in the family of antifungals, fumiquinazolines, and the antagonist asperlicin. The first example of a Cul-catalyzed tandem intramolecular amidation forming substituted imidazoindolones from readily
- Yuen, Josephine,Fang, Yuan-Qing,Lautens, Mark
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p. 653 - 656
(2007/10/03)
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- Pd-catalyzed tandem C-N/C-C coupling of gem-dihalovinyl systems: A modular synthesis of 2-substituted indoles
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(Chemical Equation Presented) 2-Substituted indoles were synthesized via a Pd-catalyzed tandem C-N/Suzuki-Miyaura coupling from readily prepared ortho-gem-dihalovinylanilines. Optimal conditions used a Pd(OAc) 2/S-Phos catalyst in the presence of K3PO 4·H2O and an organoboron reagent, which included boronic acids, esters, alkyl 9-BBN derivatives, and trialkylboranes. Yields of the desired indoles were good to excellent using low catalyst loadings (typically 1 mol %).
- Fang, Yuan-Qing,Lautens, Mark
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p. 3549 - 3552
(2007/10/03)
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- An efficient method for one-carbon elongation of aryl aldehydes via their dibromoalkene derivatives
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Various aryl aldehydes were efficiently converted into one-carbon extended aryl acetamides or aryl acetic acids through the reaction of their dibromoalkene derivatives with pyrrolidine in the presence of water under very mild conditions.
- Huh, Dal Ho,Jeong, Ji Sang,Lee, Hee Bong,Ryu, Hoejin,Kim, Young Gyu
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p. 9925 - 9932
(2007/10/03)
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- A novel synthesis of β,β-dibromostyrenes
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A new simple and efficient transformation of aromatic aldehydes to β,β-dibromostyrenes and arylbromoacetylenes is described. The olefination procedure was conducted under mild conditions and in good yields.
- Shastin,Korotchenko,Nenajdenko,Balenkova
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p. 2081 - 2084
(2007/10/03)
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- The Stille Reaction of 1,1-Dibromo-1-alkenes: Preparation of Trisubstituted Alkenes and Internal Alkynes
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The Stille reaction of 1,1-dibromo-1-alkenes 1 with aryl- and vinylstannanes produces different products depending on the reaction conditions. When the reaction is run in toluene or 1,4-dioxane with tris(2-furyl)phosphine (TFP) as the ligand, (Z)-bromoalkenes 2 are obtained stereospecifically in good to excellent yields with most substrates. However, 2-aryl-1,1-dibromo-1-alkenes (1e,1g) having an electron-donating methoxy group in the para- or ortho- position give poor yields. This method has been applied to the one-pot syntheses of stereospecifically trisubstituted alkenes 5. When the Stille reaction is conducted in a highly dipolar solvent (DMF), monobromides 2 and/or internal alkynes 4 are the products. The less reactive phenylstannane favors the formation of alkynes 4, regardless of which ligand is used. More reactive organostannanes (vinyl, furyl) require a very electron rich ligand, tris(4-methoxyphenyl)phosphine, for the formation of alkynes 4. This new method for internal alkyne preparation is general, requires very mild reaction conditions, and gives high yields.
- Shen, Wang,Wang, Le
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p. 8873 - 8879
(2007/10/03)
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