- Cp?Co(III)-Catalyzed enantioselective hydroarylation of unactivated terminal alkenes via C-H activation
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Enantioselective hydroarylation of unactivated terminal akenes constitutes a prominent challenge in organic chemistry. Herein, we reported a Cp*Co(III)-catalyzed asymmetric hydroarylation of unactivated aliphatic terminal alkenes assisted by a new type of tailor-made amino acid ligands. Critical to the chiral induction was the engaging of a novel noncovalent interaction (NCI), which has seldomly been disclosed in the C-H activation area, arising from the molecular recognition among the organocobalt(III) intermediate, the coordinated alkene, and the well-designed chiral ligand. A broad range of C2-alkylated indoles were obtained in high yields and excellent enantioselectivities. DFT calculations revealed the reaction mechanism and elucidated the origins of chiral induction in the stereodetermining alkene insertion step.
- Fan, Jun,Hong, Xin,Liu, Lei,Liu, Yan-Hua,Shi, Bing-Feng,Xie, Pei-Pei,Zhang, Zhuo-Zhuo
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supporting information
p. 19112 - 19120
(2021/11/26)
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- Pd- And Ni-Based Systems for the Catalytic Borylation of Aryl (Pseudo)halides with B2(OH)4
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Despite recent advancements in metal-catalyzed borylations of aryl (pseudo)halides, there is a continuing need to develop robust methods to access both early-stage and late-stage organoboron intermediates amendable for further functionalization. In particular, the development of general catalytic systems that operate under mild reaction conditions across a broad range of electrophilic partners remains elusive. Herein, we report the development and application of three catalytic systems (two Pd-based and one Ni-based) for the direct borylation of aryl (pseudo)halides using tetrahydroxydiboron (B2(OH)4). For the Pd-based catalyst systems, we have identified general reaction conditions that allow for the sequestration of halide ions through simple precipitation that results in catalyst loadings as low as 0.01 mol % (100 ppm) and reaction temperatures as low as room temperature. We also describe a complementary Ni-based catalyst system that employs simple unligated Ni(II) salts as an inexpensive alternative to the Pd-based systems for the borylation of aryl (pseudo)halides. Extrapolation of all three systems to a one-pot tandem borylation/Suzuki-Miyaura cross-coupling is also demonstrated on advanced intermediates and drug substances.
- Munteanu, Charissa,Spiller, Taylor E.,Qiu, Jun,Delmonte, Albert J.,Wisniewski, Steven R.,Simmons, Eric M.,Frantz, Doug E.
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p. 10334 - 10349
(2020/09/18)
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- A NaH-promoted N-detosylation reaction of diverse p-toluenesulfonamides
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A NaH-mediated detosylation reaction of various Ts-protected indoles, azaheterocycles, anilines and dibenzylamine was reported. The method features cheap reagent, convenient operations, mild reaction conditions and broad substrate scope. Moreover, this study revealed that the loading of NaH in tosylation reactions of nitrogen-containing compounds with NaH as a base in DMA or DMF should be controlled due to the possibility of adverse detosylation.
- Sun, Wanwan,Chen, Xiaobei,Hu, Ying,Geng, Huihui,Jiang, Yuanrui,Zhou, Yuxin,Zhu, Wenjing,Hu, Min,Hu, Haohua,Wang, Xingyi,Wang, Xinli,Zhang, Shilei,Hu, Yanwei
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supporting information
(2020/10/05)
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- Concatenating Suzuki Arylation and Buchwald–Hartwig Amination by A Sequentially Pd-Catalyzed One-Pot Process—Consecutive Three-Component Synthesis of C,N-Diarylated Heterocycles
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The concatenation of Suzuki coupling and Buchwald-Hartwig amination in a consecutive multicomponent reaction opens a concise, modular and efficient one-pot approach to diversely functionalized heterocycles, as exemplified for 3,10-diaryl 10H-phenothiazines, 3,9-diaryl 9H-carbazoles, and 1,5-diaryl 1H-indoles, in high yields starting from simple staring materials. Moreover, this one-pot reaction is a sequentially palladium-catalyzed process that does not require additional catalyst loading after the first coupling step.
- Mayer, Laura,Kohlbecher, Regina,Müller, Thomas J. J.
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supporting information
p. 15130 - 15134
(2020/10/20)
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- Synthesis of heterobiaryls via Suzuki-Miyaura coupling reaction of potassium aryltrifluoroborates with heteroaryl halides in aqueous systems
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A variety of heterobiaryl compounds have been synthesized by the Suzuki-Miyaura coupling reactions of heteroaryl halides with potassium aryltrifluoroborates. Pd (OAc)2 was found to be highly efficient for the Suzuki-Miyaura coupling reactions of various heteroaryl halides with potassium aryltrifluoroborates in aqueous systems, delivering the corresponding heterobiaryl compounds in good to excellent yields.
- Liu, Leifang,Zhao, Kai,Li, Wenbo,Liu, Mingli,Chen, Yuting,Dong, Yan
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- Total synthesis of (±) aspidostomide B, C, regioisomeric N-methyl aspidostomide D and their derivatives
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A full account of the total synthesis of aspidostomide B, C, their analogues and our synthetic efforts towards the synthesis of aspidostomide D, which led to the synthesis of regioisomeric N-methyl aspidostomide D, its analogues via epoxide opening strategy is presented. The synthesis of regioisomeric N-methyl aspidostomide D involves an efficient, five-step sequence, with 36.3% overall yield, starting from 3,4,5-tribromo-1H-pyrrole-2-carboxylic acid. The key features of this protocol are intramolecular cyclization, dehydration, oxidation, and a Lewis acid-mediated regioselective epoxide ring opening by C-3 position of 2,5-dibromo-1H-indole to furnish the title compounds.
- Hussain, Mulla Althafh,Khan, Faiz Ahmed
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supporting information
(2019/08/20)
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- Acyclic aminocarbene-like palladium complex-catalyzed Suzuki-Miyaura reaction at low catalyst loadings
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A series of air-stable aminocarbene-like palladium(II) complexes were easily prepared by the reaction of bis-aromaticisocyanide-dichloropalladium(II) with N-arylbenzamidines. 0.1 mol % of the optimal palladium complex 3a showed excellent catalytic activity for Suzuki-Miyaura cross-coupling reaction at room temperature and the desired products were isolated in up to 98% yields. Moreover, a large-scale reaction showed that 0.01 mol % 3a was enough to catalyze the coupling reaction efficiently at room temperature to give the desired product in 93% yield.
- Fang, Yi,Wang, Shun-Yi,Ji, Shun-Jun
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p. 9679 - 9683
(2015/12/04)
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- Superstable palladium(0) complex as an air-and thermostable catalyst for Suzuki coupling reactions
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An unprecedentedly thermo-and air-stable Pd0 complex from readily available electron-poor trifluoromethylated phosphine was serendipitously discovered. As detailed and comparative DFT calculations indicate, the stability of the complex is associated with unusually strong ligand-ligand noncovalent interactions. The unique stability and the presence of hydrophobic structural elements of the complex offer several practical advantages, which were exploited in catalytic Suzuki-Miyaura coupling reactions.
- Jakab, Alexandra,Dalicsek, Zoltn,Holczbauer, Tams,Hamza, Andrea,Ppai, Imre,Finta, Zoltn,Timri, Gza,Sos, Tibor
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- A general Suzuki cross-coupling reaction of heteroaromatics catalyzed by nanopalladium on amino-functionalized siliceous mesocellular foam
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Suzuki-Miyaura cross-coupling reactions of heteroaromatics catalyzed by palladium supported in the cavities of amino-functionalized siliceous mesocellular foam are presented. The nanopalladium catalyst effectively couples not only heteroaryl halides with
- Bratt, Emma,Verho, Oscar,Johansson, Magnus J,Baeckvall, Jan-Erling
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p. 3946 - 3954
(2014/05/20)
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- Synthesis, characterization and X-ray structures of N-heterocyclic carbene palladium complexes based on calix[4]arenes: Highly efficient catalysts towards Suzuki-Miyaura cross-coupling reactions
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A new series of calix[4]arene supported N-heterocyclic carbene palladium complexes were developed and fully characterized. A mono-substituted calix[4]arene was prepared through conventional procedures, following with the attachment of imidazolyl derivative groups to compose the precursors of novel NHCs ligands. Undergoing the alkylation with n-butylbromide and corresponding metallation with palladium and pyridine, original complexes were obtained. After a full characterization in solution and solid state, the evaluation of catalytic activity was taken out in Suzuki-Miyaura cross-coupling reactions, which revealed good performances.
- Ren, Hui,Xu, Yong,Jeanneau, Erwann,Bonnamour, Isabelle,Tu, Tao,Darbost, Ulrich
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p. 2829 - 2837
(2014/04/17)
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- Scope of the two-step, one-pot palladium-catalyzed borylation/Suzuki cross-coupling reaction utilizing bis-boronic acid
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The use of bis-boronic acid for the direct synthesis of boronic acids has greatly facilitated the two-step, one-pot borylation/Suzuki cross-coupling reaction between aryl and heteroaryl halides. With use of Buchwald's second-generation XPhos preformed catalyst, high yields of cross-coupled products were obtained for most substrates. The method also allows an efficient two-step, one-pot synthesis, providing access to three distinct cross-coupled products after column chromatography. The method also provides a rapid and convenient route to teraryl compounds.
- Molander, Gary A.,Trice, Sarah L. J.,Kennedy, Steven M.
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p. 8678 - 8688
(2012/11/07)
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- A NEW PALLADIUM CATALYST, METHOD FOR ITS PREPARATION AND ITS USE
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The invention relates to palladium(0)-tetrakis{tri-[3,5-bis(trifluoromethyl)- phenylj-phosphine} complex of formula (I), as well as to its preparation and use. This compound is outstandingly stable, and can be used as catalyst with excellent results.
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Page/Page column 17-18
(2012/07/27)
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- Copper-catalyzed tandem synthesis of indolo-, pyrrolo[2,1-a]isoquinolines, naphthyridines and bisindolo/pyrrolo[2,1-a]isoquinolines via hydroamination of ortho-haloarylalkynes followed by C-2 arylation
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An efficient approach for the copper-catalyzed regioselective tandem synthesis of diversely substituted indolo[2,1-a]isoquinolines 11a-r, pyrrolo[2,1-a]isoquinolines 12a-d, and indolo-, pyrrolo[2,1-f ][1,6]naphthyridines 14a-f via preferential addition of the heterocyclic amines onto the ortho-haloarylalkynes over N-arylation followed by intramolecular C-2 arylation is described. The scope of the developed chemistry was successfully extended for the direct synthesis of bisindolo-, pyrrolo[2,1-a]isoquinolines 15a-g, a regioisomer of the bisindolo[1,2-a]quinolines used as organic single-crystal field-effect transistor. Hydroxymethyl benzotriazole, which is an inexpensive and air stable compound, has been used as a ligand to carry out this onestep conversion of simple, readily available starting materials into an interesting class of heterocyclic compounds.
- Verma, Akhilesh K.,Jha, Rajeev R.,Chaudhary, Ritu,Tiwari, Rakesh K.,Reddy, Kotla Siva K.,Danodia, Abhinandan
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p. 8191 - 8205,15
(2020/10/15)
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- Room-temperature highly efficient Suzuki-Miyaura reactions in water in the presence of Stilbazo
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An efficient catalytic system for the ligand-free Suzuki-Miyaura reaction in water at room temperature is disclosed, promoted by Stilbazo (stilbene-4,4′-bis[(1-azo)-3,4-dihydroxybenzene]-2,2′-disulfonic acid diammonium salt). The desired carbon-carbon bond formation proceeded well under mild conditions with high efficiency and good functional group tolerance.
- Peng, Yi-Yuan,Liu, Jinbiao,Lei, Xiaoli,Yin, Zenlan
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supporting information; experimental part
p. 1072 - 1075
(2010/08/04)
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- A preparatively convenient ligand-free catalytic PEG 2000 suzuki-miyaura coupling
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A ligand-free Suzuki-Miyaura reaction for the cross-coupling of aryl and heteroaryl bromides with aryl and heteroarylboronic acids has been developed utilizing catalytic polyethylene glycol 2000 (PEG 2000). This preparatively convenient system afforded the corresponding cross-coupled products in good to excellent isolated yields after a simple aqueous workup. Transmission electron microscopy (TEM) analysis of the Pd-PEG 2000 catalyst system revealed in situ-generated palladium nanoparticles after only 1 min of reaction.
- Razler, Thomas M.,Hsiao, Yi,Qian, Feng,Fu, Ruiling,Khan, Rana Kashif,Doubleday, Wendel
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supporting information; experimental part
p. 1381 - 1384
(2009/06/28)
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- Efficient microwave-assisted synthesis of 1-(1H-indol-1-yl)-2-phenyl-3-(1H-1,2,4-triazol-1-yl)propan-2-ols as antifungal agents
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New conazole antifungals, in the series of triazole alcohols 23a-d and 24a-e incorporating an indole moiety substituted at 5-position by halogens, a cyano or 4-methoxyphenyl group, have been synthesized by ring opening of corresponding oxiranes 15 and 16. These dihalogeno intermediates and their congeneers could be prepared in high yields by Corey-Chaykovsky reaction under microwave irradiation.
- Lebouvier, Nicolas,Giraud, Francis,Corbin, Typhanie,Na, Young Min,Le Baut, Guillaume,Marchand, Pascal,Le Borgne, Marc
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p. 6479 - 6483
(2007/10/03)
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- Microwave-promoted Suzuki reactions of aryl chlorides in aqueous media
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(Chemical Equation Presented) The microwave-promoted Suzuki coupling reaction of aryl chlorides with boronic acids performed in an aqueous media was studied using the air- and moisture-stable catalyst POPd2 (dihydrogen di-μ-chlorodichlorobis(di-test-butylphosphinito-κP)dipalladate (2-)). This catalyst system under microwave conditions (150°C, 15 min) provided coupled products with yields ranging from 64% to 99%. This method tolerated a variety of substituents and sterically hindered substrates.
- Miao, Guobin,Ye, Ping,Yu, Libing,Baldino, Carmen M.
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p. 2332 - 2334
(2007/10/03)
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- Arylboronic acids and arylpinacolboronate esters in suzuki coupling reactions involving indoles. Partner role swapping and heterocycle protection
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Yields of Suzuki couplings involving indoles depended upon (i) whether arylboronic acids or arylpinacolboronate esters were used, (ii) whether the heterocycle was the aryl halide or the arylboron coupling partner, and (iii) whether the heterocycle was protected or not. Highest yields, which were unaffected by incorporating Boc or Tos protection at the heterocyclic nitrogen, were obtained when indole bromides were reacted with phenylboronic acids. When indolylboronic acids were reacted with phenyl bromides, yields were somewhat lower and depended on the nitrogen substituent, being highest in the absence of protection, lower in the presence of the Boc group, and lowest of all with the Tos group. Arylpinacolboronate esters were less reactive than arylboronic acids. They required considerably longer reaction times and furnished generally lower yields of biaryl. Furthermore, irrespective of whether the heterocycle was the aryl bromide or the arylpinacolboronate ester, these yields were highest when it was protected with the Tos group. Yields were lower with the Boc group, and unprotected heterocycles gave only traces of biaryl. Careful selection of arylboron reagent, of coupling partner roles, and of protecting groups are essential to ensuring optimum results in these Suzuki couplings. These results may also be relevant to couplings involving other substrates.
- Prieto, Monica,Zurita, Esther,Rosa, Esmeralda,Munoz, Lourdes,Lloyd-Williams, Paul,Giralt, Ernest
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p. 6812 - 6820
(2007/10/03)
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- SYNTHESIS OF 5-ARYLATED INDOLES VIA PALLADIUM-CATALYZED CROSS-COUPLING REACTION OF 5-INDOLYLBORONIC ACID WITH ARYL AND HETEROARYL HALIDES
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Palladium(0)-catalyzed cross-coupling reaction of 5-indolylboronic acid with various aryl and heteroaryl halides results in regioselective formation of 5-arylated indoles in good yields.
- Yang, Youhua,Martin, Arnold R.
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p. 1395 - 1398
(2007/10/02)
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