16780-82-8Relevant articles and documents
Tetra- And Dinuclear Palladium Complexes Based on a Ligand of 2,8-Di-2-pyridinylanthyridine: Preparation, Characterization, and Catalytic Activity
Lin, Shih-Chieh Aaron,Liu, Shiuh-Tzung,Liu, Yi-Hung,Peng, Shie-Ming,Su, Bo-Kai
, p. 2081 - 2089 (2021/07/26)
Complexation of L [L = 5-phenyl-2,8-di-2-pyridinyl-anthyridine] with [Pd(CH3CN)4](BF4)2 and [Pd(CH3CN)3Cl](BF4) in a molar ratio of 1:2 rendered the corresponding dinuclear complexes [Pd2L (CH3CN)4](BF4)4 (1) and [Pd2L (CH3CN)2Cl2](BF4)2 (2), respectively. However, treatment of L with (COD)PdCl2 followed by anion exchange yielded a tetranuclear complex [Pd4L3Cl4](PF6)4(4a). Structures of these complexes are characterized by both spectroscopy and X-ray crystallography. Interconversion of these three complexes was studied via the manipulation of stoichiometric ratio of ligand to metal precursor. The catalytic activity of these complexes for carbonylative Suzuki-Miyaura cross-coupling was investigated. Complex 2 shows an excellent catalytic activity on the reaction of aryl iodide with arylboronic acid in the presence of atmospheric pressure of CO to give the corresponding benzophenones.
BF3-Etherate-catalyzed tandem reaction of 2-formylarylketones with electron-rich arenes/heteroarenes: An assembly of isobenzofurans
Mishra, Pawan K.,Kumar, Ankit,Verma, Akhilesh K.
supporting information, p. 6122 - 6125 (2020/06/18)
An efficient and BF3·Et2O-catalyzed chemoselective synthesis of diversified 1,3-diarylisobenzofuran in a high yield has been described. The reaction proceeds through sequential hydroarylation-cyclization between 2-formylarylketones and electron-rich arenes/heteroarenes. Advantageous features of the developed methodology include operational simplicity, a broad substrate scope, and applicability towards gram scale synthesis. The utility of isobenzofuran derivatives as the diene was extended to the synthesis of [4+2] cyclo-adducts with DMAD and the synthesis of 1,2-dicarbonylarenes in good yields.
Controlled photo-flow oxidative reaction (UV-FOR) platform for ultra-fast phthalide and API synthesis
Aand, Dnyaneshwar,Karekar, Sanjeev,Mahajan, Bhushan,Pawar, Amit B.,Singh, Ajay K.
supporting information, p. 4584 - 4590 (2018/10/23)
An integrated photo-flow oxidative reaction (UV-FOR) platform approach is presented for the synthesis of phthalides. The current protocol is catalyst-free, and uses economical and abundant hydro-carbons and hydrocarbon derivatives such as benzoic acid, benzene, and xylene, as starting materials. The reaction is performed using oxygen as a green oxidant in a time- and labour-efficient manner. This integrated approach has been shown to be successful in making a UV-FOR platform suitable for the on-demand synthesis of phthalides and their further syntheses to 2-arylmethylbenzoic acids and arylogous Michael addition products under relatively mild conditions. The current protocol was further extended to the gram scale synthesis of an ischemic stroke-relevant active pharmaceutical ingredient (API), 3-N-butylphthalide (NBP), in a continuous flow process.
Enantioselective Synthesis of Indolines, Benzodihydrothiophenes, and Indanes by C?H Insertion of Donor/Donor Carbenes
Souza, Lucas W.,Squitieri, Richard A.,Dimirjian, Christine A.,Hodur, Blanka M.,Nickerson, Leslie A.,Penrod, Corinne N.,Cordova, Jesus,Fettinger, James C.,Shaw, Jared T.
supporting information, p. 15213 - 15216 (2018/10/31)
We employ a single catalyst/oxidant system to enable the asymmetric syntheses of indolines, benzodihydrothiophenes, and indanes by C?H insertion of donor/donor carbenes. This methodology enables the rapid construction of densely substituted five-membered rings that form the core of many drug targets and natural products. Furthermore, oxidation of hydrazones to the corresponding diazo compounds proceeds in situ, enabling a relatively facile one- or two-pot protocol in which isolation of potentially explosive diazo alkanes is avoided. Regioselectivity studies were performed to determine the impact of sterics and electronics in donor/donor metal carbene C?H insertions to form indolines. This methodology was applied to a variety of substrates in high yield, diastereomeric, and enantiomeric ratios and to the synthesis of a patented indane estrogen receptor agonist with anti-cancer activity.
General Method for the Suzuki-Miyaura Cross-Coupling of Primary Amide-Derived Electrophiles Enabled by [Pd(NHC)(cin)Cl] at Room Temperature
Lei, Peng,Meng, Guangrong,Ling, Yun,An, Jie,Nolan, Steven P.,Szostak, Michal
, p. 6510 - 6513 (2017/12/26)
A general, highly selective method for the room temperature Suzuki-Miyaura cross-coupling of commonly encountered primary benzamides is reported. A combination of site-selective N,N-di-Boc-activation (tert-butoxycarbonyl activation) of the amide nitrogen with practical air- and moisture-stable, well-defined, and highly reactive [Pd(NHC)(cin)Cl] (NHC = N-heterocyclic carbene; cin = cinnamyl) provides a highly effective route to biaryl ketones from primary amides in high yields. For the first time, a TON of >1000 has been achieved in amide acyl cross-coupling.
N-Acylsuccinimides: Twist-controlled, acyl-transfer reagents in Suzuki-Miyaura cross-coupling by N-C amide bond activation
Osumi, Yuki,Liu, Chengwei,Szostak, Michal
supporting information, p. 8867 - 8871 (2017/11/09)
The palladium-catalyzed Suzuki-Miyaura cross-coupling of N-acylsuccinimides as versatile acyl-transfer reagents via selective amide N-C bond cleavage is reported. The method is user-friendly since it employs commercially-available, air-stable reagents and catalysts. The cross-coupling is enabled by half-twist of the amide bond in N-acylsuccinimides. These highly effective, crystalline acyl-transfer reagents present major advantages over perpendicularly twisted N-acylglutarimides, including low price of the succinimide activating ring, selective metal insertion under redox neutral conditions and high stability of the amide bond towards reaction conditions. Mechanistic studies indicate that oxidative addition is the rate limiting step in this widely applicable protocol.
Palladium-Catalyzed Suzuki-Miyaura Cross-Coupling of N-Mesylamides by N-C Cleavage: Electronic Effect of the Mesyl Group
Liu, Chengwei,Liu, Yongmei,Liu, Ruzhang,Lalancette, Roger,Szostak, Roman,Szostak, Michal
supporting information, p. 1434 - 1437 (2017/03/23)
A general Pd-catalyzed Suzuki-Miyaura cross-coupling of N-mesylamides with arylboronic acids by selective N-C cleavage has been developed. The presented results represent the first example of a transition-metal-catalyzed cross-coupling of amides activated by an atom-economic, cheap, and benign mesyl group. The reaction delivers arylated products featuring a range of useful functional groups by chemoselective cleavage of the amide N-C bond with high efficiency. Both the scope and the origin of high selectivity are discussed. A beneficial effect of the N-mesyl substituent on the bond activation in acyclic amides is presented.
Heteropoly acid encapsulated into zeolite imidazolate framework (ZIF-67) cage as an efficient heterogeneous catalyst for Friedel-Crafts acylation
Ammar, Muhammad,Jiang, Sai,Ji, Shengfu
, p. 303 - 310 (2015/11/17)
A new strategy has been developed for the encapsulation of the phosphotungstic heteropoly acid (H3PW12O40 denoted as PTA) into zeolite imidazolate framework (ZIF-67) cage and the PTA@ZIF-67(ec) catalysts with different PTA content were prepared. The structure of the catalysts was characterized by XRD, BET, SEM, FT-IR, ICP-AES and TG. The catalytic activity and recovery properties of the catalysts for the Friedel-Crafts acylation of anisole with benzoyl chloride were evaluated. The results showed that 14.6-31.7 wt% PTA were encapsulated in the ZIF-67 cage. The PTA@ZIF-67(ec) catalysts had good catalytic activity for Friedel-Crafts acylation. The conversion of anisole can reach ~100% and the selectivity of the production can reach ~94% over 26.5 wt% PTA@ZIF-67(ec) catalyst under the reaction condition of 120 °C and 6 h. After reaction, the catalyst can be easily separated from the reaction mixture by the centrifugation. The recovered catalyst can be reused five times and the selectivity can be kept over 90%.
Efficient synthesis of functionalized 1,3-dihydroisobenzofurans from salicylaldehydes: Application to the synthesis of escitalopram
Wang, Peng,Zhang, Rui,Cai, Jin,Chen, Jun-Qing,Ji, Min
, p. 549 - 552 (2014/05/06)
An efficient synthesis of substituted 1,3-dihydroisobenzofurans is developed. In this novel route, o-aroylbenzaldehydes, as key intermediates, can be obtained by lead tetraacetate oxidation of N-aroylhydrazones of salicylaldehydes. The mild and general st
Pd-catalyzed decarboxylative ortho-acylation of O-methyl oximes with phenylglyoxylic acids
Yang, Zhiyong,Chen, Xiang,Liu, Jidan,Gui, Qingwen,Xie, Kai,Li, Miaomiao,Tan, Ze
, p. 1560 - 1562 (2013/03/13)
Aryl ketones were synthesized via Pd-catalyzed decarboxylative coupling between O-methyl oximes and phenylglyoxylic acids using (NH4) 2S2O8 as the oxidant. The Royal Society of Chemistry 2013.
