- Use of Imidazo[1,5-a]pyridin-3-ylidene as a Platform for Metal-Imidazole Cooperative Catalysis: Silver-Catalyzed Cyclization of Alkyne-Tethered Carboxylic Acids
-
Silver complexes with 5-(4-(tert-butyl)-1H-imidazol-1-yl)-imidazo[1,5-a]pyridin-3-ylidene ligands were synthesized as metal-imidazole acid-base cooperative catalysts. Single crystal XRD analysis revealed that the silver atom was located in the vicinity of
- Rawat, Vishal Kumar,Higashida, Kosuke,Sawamura, Masaya
-
supporting information
p. 1631 - 1637
(2021/02/03)
-
- Regioselective Synthesis of 4-Aryl-1,3-dihydroxy-2-naphthoates through 1,2-Aryl-Migrative Ring Rearrangement Reaction and their Photoluminescence Properties
-
4-Aryl-1,3-dihydroxy-2-naphthoates having the less accessible 1,2,3,4-tetrasubstituted naphthalene scaffold and that show photoluminescence emission from solid state as well as in solutions, were selectively synthesized from brominated lactol silyl ethers
- Yanai, Hikaru,Kawazoe, Teru,Ishii, Nobuyuki,Witulski, Bernhard,Matsumoto, Takashi
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p. 11442 - 11449
(2021/06/28)
-
- Triflic acid mediated sequential cyclization of ortho-alkynylarylesters with ammonium acetate
-
A triflic acid (TfOH) mediated sequential cyclization of ortho-alkynylarylesters and ammonium acetate (NH4OAc) was reported. The reaction took place via a Br?nsted acid-mediated intramolecular cyclization of ortho-alkynylarylesters followed by an ammonium acetate participated substitution reaction, forming isoquinolin-1-ones as the major products. Different from most of the known synthetic methods of isoquinolin-1-ones, no metal catalyst was required in the reported reaction. The regioisomers – isoindolin-1-ones were obtained together with isoquinolin-1-ones in a few cases. The intermediate compounds – isochromen-1-ones and isobenzofuran-1-ones were also isolated. The interconversion experiments showed that the regioisomers formed during the Br?nsted acid induced intramolecular cyclization of ortho-alkynylarylesters. A natural product – ruprechstyril was prepared in a moderate yield employing the new method.
- Domaradzki, Maciej E.,Liu, Xiaochen,Ong, Jiye,Yu, Gyeongah,Zhang, Gan,Simantov, Ariel,Perl, Eliyahu,Chen, Yu
-
-
- Iridium-Catalyzed Cycloisomerization of Alkynoic Acids: Synthesis of Unsaturated Lactones
-
The iridium-catalyzed cycloisomerization of various alkynoic acids was successfully developed, and a series of five-, six-, and especially seven-membered unsaturated lactones were constructed with moderate yields and excellent regioselectivities (up to 68
- Huang, Yi,Zhang, Xianghe,Dong, Xiu-Qin,Zhang, Xumu
-
supporting information
p. 782 - 788
(2020/01/08)
-
- Copper-Catalyzed Modular Access to N-Fused Polycyclic Indoles and 5-Aroyl-pyrrol-2-ones via Intramolecular N—H/C—H Annulation with Alkynes: Scope and Mechanism Probes
-
Copper-catalyzed intramolecular N—H/C—H annulation with alkynes has been developed. A variety of densely functionalized heterocycles, such as pyrrolo[1,2-a]indoles, indolo[1,2-c]quinazolin-2-ones, oxazolo[3,4-a]indoles, and imidazo[1,5-a]indoles, were synthesized in an atom- and step-economical manner, owing to the high modularized feature of aniline moiety, the linker moiety, as well as the alkyne moiety. By simply changing the oxidant from di-tert-butyl peroxide (DTBP) to 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO), the reaction could readily be transformed to the aminooxygenation pathway, which grabs one oxygen atom from the TEMPO to generate 5-aroyl-pyrrol-2-ones. Mechanistic experiments indicate that vinyl radical is involved in this reaction and an amidyl-radical-initiated radical cascade might be responsible for this transformation.
- Liu, Yan-Hua,Song, Hong,Zhang, Chi,Liu, Yue-Jin,Shi, Bing-Feng
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supporting information
p. 1545 - 1552
(2020/09/09)
-
- Continuous Electrochemical Synthesis of Iso-Coumarin Derivatives from o-(1-Alkynyl) Benzoates under Metal- and Oxidant-Free
-
A non-oxidant and metal-free strategy for synthesizing iso-coumarin by using a continuous electrochemical microreactor to initiate an oxidative cyclization reaction of o-(1-alkynyl) benzoate and radicals. This efficient and clean continuous electrosynthesis method not only avoids the complicated gas protection operation and production of by-products in the batch processes, but also help to overcome the difficulty that batch metal catalysis and electrocatalysis are difficult to scale up, and has the potential for pilot-scale experiment.
- Lin, Xinxin,Fang, Zheng,Zeng, Cuilian,Zhu, Chenlong,Pang, Xinyan,Liu, Chengkou,He, Wei,Duan, Jindian,Qin, Ning,Guo, Kai
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supporting information
p. 13738 - 13742
(2020/10/02)
-
- Gold-catalyzed Rapid Construction of Nitrogen-containing Heterocyclic Compound Library with Scaffold Diversity and Molecular Complexity
-
1,3-unsubstituted 2-(1H-indol-2-yl)ethanamines were employed for the first time to react with alkynoic acids (AAs) to achieve gold-catalyzed highly selective cascade reactions to furnish novel indole-fused skeletons. Furthermore, with this powerful gold catalytic system, a library of indole/pyrrole/thiophene/benzene/naphthalene/pyridine-based nitrogen-containing heterocyclic compounds (NCHCs) with scaffold diversity and molecular complexity was constructed rapidly using various amine nucleophiles (ANs) and diverse AAs as the building blocks. This general protocol features excellent selectivity, extraordinarily broad substrate scope, readily available inputs, good to high yields, high bond-forming efficiency, and step economy, thus providing a facile and efficient access to a variety of valuable nitrogen-containing heterocycles.
- Qiao, Jin,Jia, Xiuwen,Li, Pinyi,Liu, Xiaoyan,Zhao, Jingwei,Zhou, Yu,Wang, Jiang,Liu, Hong,Zhao, Fei
-
-
- Metal-Free Synthesis of 4-Chloroisocoumarins by TMSCl-Catalyzed NCS-Induced Chlorinative Annulation of 2-Alkynylaryloate Esters
-
4-Chloroisocoumarins can be conveniently prepared from 2-alkynylaryloate esters via the activation of alkynes by electrophilic chlorine, generated in situ from N-chlorosuccinimide (NCS) in the presence of 10 mol % trimethylsilyl chloride (TMSCl), which leads to 6-endo-dig-selective chlorinative annulation to give the desired products in moderate to quantitative yields. The procedure employs readily available reagents and can be conveniently carried out on a wide scope of substrates under mild conditions (0 °C to rt). Furthermore, the reaction is scalable for gram-scale preparation of 4-chloroisocoumarins. Additionally, 4-bromo- and 4-iodoisocoumarins can be prepared in moderate to good yields by replacing NCS with N-bromosuccinimide (NBS) and N-iodosuccinimide (NIS), respectively.
- Norseeda, Krissada,Chaisan, Nattawadee,Thongsornkleeb, Charnsak,Tummatorn, Jumreang,Ruchirawat, Somsak
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p. 16222 - 16236
(2019/12/25)
-
- Copper-Catalyzed Modular Amino Oxygenation of Alkenes: Access to Diverse 1,2-Amino Oxygen-Containing Skeletons
-
Copper-catalyzed alkene amino oxygenation reactions using O-acylhydroxylamines have been achieved for a rapid and modular access to diverse 1,2-amino oxygen-containing molecules. This transformation is applicable to the use of alcohols, carbonyls, oximes, and thio-carboxylic acids as nucleophiles on both terminal and internal alkenes. Mild reaction conditions tolerate a wide range of functional groups, including ether, ester, amide, carbamate, and halide. The reaction protocol allows for starting with free amines as the precursor of O-benzoylhydroxylamines to eliminate their isolation and purification, contributing to broader synthetic utilities. Mechanistic investigations reveal the amino oxygenation reactions may involve distinct pathways, depending on different oxygen nucleophiles.
- Hemric, Brett N.,Chen, Andy W.,Wang, Qiu
-
supporting information
p. 1468 - 1488
(2019/01/25)
-
- Gold-Catalyzed Oxidation of Internal Alkynes into Benzils and its Application for One-Pot Synthesis of Five-, Six-, and Seven-Membered Azaheterocycles
-
Internal alkynes have been shown to undergo oxidation to substituted benzils (1,2-diarylethane-1,2-diones) by α-picoline N-oxide in the presence of Ph3PAuNТf2 (5 mol-%). In addition to the unsubstituted benzil, the method allows preparing, under markedly mild conditions (50 °C in chlorobenzene), various non-symmetrical products, including heteroaromatic versions thereof which are much more difficult to obtain otherwise. This gold(I)-catalyzed transformation was integrated into one-pot reaction sequence delivering a range of 5- to 7-membered ring systems (imidazoles, quinoxalines, 1,2,4-triazines, pyrazines, and 1,4-diazepines), thus linking these important heterocyclic motifs to the internal alkyne reagent space.
- Dubovtsev, Alexey Yu.,Dar'in, Dmitry V.,Krasavin, Mikhail,Kukushkin, Vadim Yu.
-
supporting information
p. 1856 - 1864
(2019/02/19)
-
- Preparation method of 3-hydroxy-2,3-dihydroisoquinoline-1,4-dione compound
-
The invention belongs to the technical field of organic synthesis, and particularly relates to a preparation method of a 3-hydroxy-2,3-dihydroisoquinoline-1,4-dione compound. In the preparation methodprovided by the invention, N-alkoxy-2-alkynyl benzamide
- -
-
Paragraph 0045; 0046; 0060; 0061
(2019/08/01)
-
- Green preparation method of 3-hydroxy isoindole-1-one compounds
-
The invention discloses a green preparation method of 3-hydroxy isoindole-1-one compounds, and belongs to the technical field of organic synthesis. The method comprises the following steps: adopting 2-alkynyl benzamide as a reaction substrate, adding a br
- -
-
Paragraph 0037; 0042; 0045
(2020/01/03)
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- Silver triflate/: P -TSA co-catalysed synthesis of 3-substituted isocoumarins from 2-alkynylbenzoates
-
In this paper, we describe the silver triflate/p-toluenesulfonic acid co-catalysed synthesis of seventeen isocoumarins and two thieno[2,3-c]pyran-7-ones starting from 2-alkynylbenzoates and 3-alkynylthiophene-2-carboxylates, respectively. The reaction proceeds with absolute regioselectivity under mild reaction conditions and low catalyst loading, to afford the desired products in good to excellent yields. A conceivable reaction mechanism is proposed and supported by isotope-exchange tests, 1H NMR studies and ad hoc experiments.
- Gianni, Jonathan,Pirovano, Valentina,Abbiati, Giorgio
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p. 3213 - 3219
(2018/05/17)
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- Boron Trichloride-Mediated Synthesis of Indoles via the Aminoboration of Alkynes
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We describe an efficient catalyst- and metal-free aminoboration of alkynes to 3-borylated indoles using one of the least expensive boron sources, BCl3. The major dichloro(indolyl)borane products can be used for the in situ construction of usefu
- Lv, Jiahang,Zhao, Binlin,Liu, Li,Han, Ying,Yuan, Yu,Shi, Zhuangzhi
-
supporting information
p. 4054 - 4059
(2018/09/25)
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- Divergent Syntheses of (Z)-3-Alkylideneisobenzofuran-1(3 H)-ones and 1 H-Isochromen-1-ones by Copper-Catalyzed Cycloisomerization of 2-Alkynylbenzoic Acids in Ionic Liquids
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The cycloisomerization of readily available 2-alkynylbenzoic acids 1 in ionic liquids (ILs) as recyclable reaction media has been studied under the catalytic action of CuCl2. With substrates bearing an aryl group on the triple bond, a mixture o
- Mancuso, Raffaella,Pomelli, Christian S.,Chiappetta, Piera,Gioia, Katia F.,Maner, Asif,Marino, Nadia,Veltri, Lucia,Chiappe, Cinzia,Gabriele, Bartolo
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p. 6673 - 6680
(2018/06/01)
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- A Sustainable, User-Friendly Protocol for the Pd-Free Sonogashira Coupling Reaction
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We herein present a new catalytic system for the palladium-free Sonogashira coupling reaction. The catalytically active moiety is formed in situ, in a straightforward and user-friendly manner, by combining a widely available low-cost copper salt and an N-
- Liori, Aggeliki A.,Stamatopoulos, Ioannis K.,Papastavrou, Argyro T.,Pinaka, Afroditi,Vougioukalakis, Georgios C.
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p. 6134 - 6139
(2018/09/06)
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- Stoichiometric and Catalytic C?C and C?H Bond Formation with B(C6F5)3 via Cationic Intermediates
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This work showcases a new catalytic cyclization reaction using a highly Lewis acidic borane with concomitant C?H or C?C bond formation. The activation of alkyne-containing substrates with B(C6F5)3 enabled the first catalytic intramolecular cyclizations of carboxylic acid substrates using this Lewis acid. In addition, intramolecular cyclizations of esters enable C?C bond formation as catalytic B(C6F5)3 can be used to effect formal 1,5-alkyl migrations from the ester functional groups to unsaturated carbon–carbon frameworks. This metal-free method was used for the catalytic formation of complex dihydropyrones and isocoumarins in very good yields under relatively mild conditions with excellent atom efficiency.
- Soltani, Yashar,Wilkins, Lewis C.,Melen, Rebecca L.
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p. 11995 - 11999
(2017/09/20)
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- Hydroiodination-Triggered Cascade Reaction with I2/PPh3/H2O: Metal-Free Access to 3-Substituted Phthalides from 2-Alkynylbenzoates
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Phthalide is an important scaffold found in several biologically active compounds. Therefore, effective methods for the synthesis of phthalides are strongly desired. Herein, we describe the metal-free synthesis of 3-substituted phthalides by the reductive hydroiodination of 2-alkynylbenzoates through an I2/PPh3/H2O-triggered cascade reaction. A variety of 3-substituted phthalides were synthesized in excellent yields by a one-pot reaction involving four processes: desilylation, hydroiodination, cyclization, and reduction.
- Kawaguchi, Shin-Ichi,Nakamura, Kentaro,Yamaguchi, Kotaro,Sato, Yuki,Gonda, Yuhei,Nishioka, Masaaki,Sonoda, Motohiro,Nomoto, Akihiro,Ogawa, Akiya
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supporting information
p. 5343 - 5346
(2017/09/06)
-
- Divergent syntheses of iodinated isobenzofuranones and isochromenones by iodolactonization of 2-alkynylbenzoic acids in ionic liquids
-
The regiochemical outcome of the iodolactonization of 2-alkynylbenzoic acids, carried out at 100 °C in ionic liquids (ILs) as unconventional solvents and with molecular iodine as the iodine source, in the absence of external bases, was found to be strongl
- Mancuso, Raffaella,Pomelli, Christian C.,Malafronte, Francesco,Maner, Asif,Marino, Nadia,Chiappe, Cinzia,Gabriele, Bartolo
-
supporting information
p. 4831 - 4841
(2017/07/10)
-
- Copper-Catalyzed Amino Lactonization and Amino Oxygenation of Alkenes Using O-Benzoylhydroxylamines
-
A copper-catalyzed amino lactonization of unsaturated carboxylic acids has been achieved as well as the analogous intermolecular three-component amino oxygenation of olefins. The transformation features mild conditions and a remarkably broad substrate sco
- Hemric, Brett N.,Shen, Kun,Wang, Qiu
-
p. 5813 - 5816
(2016/06/09)
-
- Cobalt-Catalyzed Bis-alkynylation of Amides via Double C-H Bond Activation
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The first example of cobalt-catalyzed selective bis-alkynylation of amides via double C-H bond activation with the directing assistance of a removable bidentate auxiliary is reported. The developed alkynylation strategy is simple, efficient, and tolerant
- Landge, Vinod G.,Jaiswal, Garima,Balaraman, Ekambaram
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p. 812 - 815
(2016/03/01)
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- Catalyst-Free Synthesis of Borylated Lactones from Esters via Electrophilic Oxyboration
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A catalyst-free oxyboration reaction of alkynes is developed. The resulting borylated isocoumarins and 2-pyrones are isolated as boronic acids, pinacolboronate esters, or potassium organotrifluoroborate salts, providing a variety of bench-stable organobor
- Faizi, Darius J.,Issaian, Adena,Davis, Ashlee J.,Blum, Suzanne A.
-
supporting information
p. 2126 - 2129
(2016/03/05)
-
- Synthesis of 1,2,3,4-tetrasubstituted naphthalenes through a cascade reaction triggered by silyl acetal activation
-
1,2,3,4-Tetrasubstituted naphthalenes bearing four different substituents were synthesized in a regioselective manner through a fluoride-induced cascade reaction of lactol silyl ethers, which could be easily prepared from 4-alkynylisocoumarins and ketene silyl acetal.
- Yanai, Hikaru,Ishii, Nobuyuki,Matsumoto, Takashi
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supporting information
p. 7974 - 7977
(2016/07/06)
-
- Synthesis of isocoumarins: Rhenium complex-catalyzed cyclization of 2-ethynylbenzoic acids
-
When 2-ethynylbenzoic acids were treated with a catalytic amount of a rhenium complex, such as ReCl(CO)5, 6-endo cyclization of 2-ethynylbenzoic acids proceeded with a high selectivity to give the corresponding isocoumarins in moderate to good yields.
- Umeda, Rui,Yoshikawa, Shunya,Yamashita, Kouji,Nishiyama, Yutaka
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p. 2172 - 2179
(2015/12/12)
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- Chemoselective synthesis of unsymmetrical internal alkynes or vinyl sulfones via palladium-catalyzed cross-coupling reaction of sodium sulfinates with alkynes
-
A highly efficient and mild palladium-catalyzed cross-coupling of sodium sulfinates and alkynes for the selective synthesis of unsymmetrical internal alkynes and vinyl sulfones has been developed. This methodology has advantages of easily accessible starting materials, functional group tolerance and a wide range of substrates, which provides rapid access to alkynes and vinyl sulfones.
- Xu, Yanli,Zhao, Jinwu,Tang, Xiaodong,Wu, Wanqing,Jiang, Huanfeng
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p. 2029 - 2039
(2014/07/07)
-
- Cu-catalyzed coupling-cyclization in PEG 400 under ultrasound: A highly selective and greener approach towards isocoumarins
-
The combination of CuI-K2CO3-PEG 400 facilitated the coupling-cyclization of o-iodobenzoic acid with terminal alkynes under ultrasound, affording a greener and practical approach towards 3-substituted isocoumarins with remarkable regioselectivity. This inexpensive and Pd and ligand free methodology gave rise to various isocoumarins of potential pharmacological interest.
- Chary, R. Gangadhara,Reddy, G. Rajeshwar,Ganesh,Prasad, K. Vara,Chandra, S. K. Phani,Mukherjee, Soumita,Pal, Manojit
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p. 9641 - 9644
(2013/09/02)
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- Palladium and copper catalyzed one-pot Sonogashira reaction of 2-nitroiodobenzenes with aryl acetylenes and subsequent regioselective hydration in water: Synthesis of 2-(2-nitrophenyl)-1-aryl ethanones
-
An attempted Sonogashira reaction of 2-nitroiodobenzene and phenyl acetylene catalyzed by Pd(PPh3)4/Cu in water in the presence of pyrrolidine proceeds with simultaneous regioselective hydration of the Sonogashira alkyne leading to the corresponding aryl ketone. A series of functionalized 2-(2-nitrophenyl)-1-aryl ethanones are obtained in high yields by this procedure.
- Ahammed, Sabir,Dey, Raju,Ranu, Brindaban C.
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p. 3697 - 3701
(2013/07/05)
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- Palladium(II)-catalyzed tandem annulation reaction of o-alkynylbenzoates with methyl vinyl ketone for the synthesis of isocoumarins
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A palladium(II)-catalyzed highly regioselective tandem reactions of o-alkynylbenzoates with methyl vinyl ketone for the synthesis of isocoumarins was developed. It is a convenient, mild and environmentally benign reaction with moderate to high yield. The
- Wang, Huan,Han, Xiuling,Lu, Xiyan
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p. 8626 - 8631
(2013/09/12)
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- On homogeneous gold/palladium catalytic systems
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Two substrates containing an aryl iodide and an allenoate ester were prepared and the goldinduced cycloisomerisation to vinylgold(I) species and their proto-deauration as well as the intramolecular palladium-catalysed cross-coupling reactions were investigated. Switching to catalytic amounts of gold and palladium and stoichiometric amounts of silver did indeed furnish the product of a cycloisomerisation/ intramolecular cross-coupling. Control experiments revealed that silver cannot substitute for gold or palladium in these reactions, but a different palladium catalyst in a different oxidation state also afforded the cycloisomerisation/intramolecular crosscoupling products in only slightly reduced yields. By ICP analysis the palladium was shown to contain gold only at the sub-ppm level. This shows how carefully results obtained with such systems have to be interpreted. Then a series of allylic and benzylic o-alkynylbenzoates were investigated in gold-and palladium-catalysed reactions. For esters of benzyl alcohol and cinnamyl alcohol no palladium co-catalyst was needed for the conversion. All reagents were thoroughly checked for palladium traces by ICP analysis in order to thoroughly exclude a gold/palladium cocatalysis. Optimisation of the gold complex, counter ion and solvent showed that gold(I) isonitrile precatalysts and silver triflate as activator in dioxane are suitable to convert a number of substrates with aryl, alkyl and even cyclopropyl substituents. Crossover experiments proved an intermolecular allyl transfer.
- Hashmi, A. Stephen K.,Lothschuetz, Christian,Doepp, Rene,Ackermann, Martin,De Buck Becker, Janosc,Rudolph, Matthias,Scholz, Christian,Rominger, Frank
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supporting information; experimental part
p. 133 - 147
(2012/04/10)
-
- NHC-catalyzed oxidative cyclization reactions of 2-alkynylbenzaldehydes under aerobic conditions: Synthesis of O-Heterocycles
-
Chemical equations presented. An NHC-catalyzed, regio- and stereoselective oxidative cyclization of o-alkynylbenzaldehydes bearing an unactivated alkyne moiety as an internal electrophile has been developed to afford phthalides and isocoumarins. A single organocatalytic system enabled two sequential C-O bond formations to take place in an atom economical manner via highly efficient dual activation. Molecular oxygen in air could be utilized as a source of an oxygen atom for the oxidation of aldehydes to the corresponding benzoic acids under our newly developed reagent system.
- Park, Jong Hyub,Bhilare, Sachin V.,Youn, So Won
-
supporting information; experimental part
p. 2228 - 2231
(2011/07/09)
-
- Platinum(II)-catalyzed intramolecular cyclization of alkynylbenzonitriles: Synthesis of 1-alkoxyisoquinolines and isoquinolones
-
A facile synthesis of a series of 1-alkoxyisoquinolines and (2H)-isoquinolones by an intramolecular 6-endo-dig cyclization of ortho-alkynylbenzonitriles in the presence of a catalytic amount of hydrido(dimethylphosphinous acid-κP)[hydrogen bis(dimethylphosphinito- κP)]platinum(II) in various alcohols at 65-90 °C is described for the first time.
- Li, Jim,Chen, Lijing,Chin, Elbert,Lui, Alfred S.,Zecic, Hasim
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experimental part
p. 6422 - 6425
(2010/12/25)
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- A simple and mild synthesis of 1H-isochromenes and (Z)-1-alkylidene-1,3- dihydroisobenzofurans by the iodocyclization of 2-(1-alkynyl)benzylic alcohols
-
(Chemical Equation Presented) A variety of iodo-substituted isochromenes, dihydroisobenzofurans, and pyranopyridines are readily prepared in good to excellent yields under mild conditions by the iodocyclization of readily available 2-(1-alkynyl)benzylic a
- Mancuso, Raffaella,Mehta, Saurabh,Gabriele, Bartolo,Salerno, Giuseppe,Jenks, William S.,Larock, Richard C.
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supporting information; experimental part
p. 897 - 901
(2010/05/02)
-
- INHIBITORS OF HISTONE DEACETYLASE
-
ABSTRACT OF THE DISCLOSURE This invention relates to compounds and methods for the inhibition of HDAC enzymatic activity. More particularly, the invention provides for compounds of formula (I), (I) and N-oxides, hydrates, solvates, pharmaceutically acceptable salts, prodrugs and complexes thereof, and racemic and scalemic mixtures, diastereomers and enantiomers thereof, wherein L, M, n, R, W, X and Y are as defined in the specification.
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Page/Page column 82; 83
(2009/06/27)
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- Convenient copper- and solvent-free Sonogashira-type alkynylation of aryl iodides and bromides using Pd EnCat
-
A straightforward methodology is described for the copper- and solvent-free alkynylations of aryl iodides and bromides using 0.1-0.01 mol % of Pd as Pd EnCat 40 or TPP30. High yielding reactions can be achieved under aerobic conditions for a variety of activated and deactivated aryl iodides; a few examples with aryl bromides are also described. Microwave irradiation is able to enhance yields and rates of these reactions.
- Carpita, Adriano,Ribecai, Arianna
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scheme or table
p. 204 - 207
(2009/04/19)
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- A cycloalkane-based thermomorphic system for palladium-catalyzed cross-coupling reactions
-
In this paper, we describe a practical and efficient protocol for Sonogashira, Suzuki-Miyaura, and Mizoroki-Heck cross-coupling using a CBT system. The use of substrates with cycloalkane-soluble tags facilitates separation of the desired products and the
- Kim, Shokaku,Yamamoto, Keisuke,Hayashi, Kanako,Chiba, Kazuhiro
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p. 2855 - 2863
(2008/09/19)
-
- 6-endo-dig Cyclization of heteroarylesters to alkynes promoted by Lewis acid catalyst in the presence of Br?nsted acid
-
We report a regiocontrolled 6-endo-dig cyclization of 2-(2-arylethynyl)heteroaryl esters occurred under Br?nsted acidic conditions and in the presence of a catalytic amount of Lewis acids such as Cu(OTf)2, AuCl3, or (CF3CO
- Hellal, Malik,Bourguignon, Jean-Jacques,Bihel, Frédéric J.-J.
-
-
- Halocyclization of methyl 2-alkynylbenzoates to isocoumarins using cupric halides
-
Treatment of methyl 2-alkynylbenzoates with two to three equivalents of CuX2 (X = Cl or Br) in refluxing acetonitrile gave isocoumarins 2 in good to excellent chemical yields.
- Chin, Ling-Yu,Lee, Chia-Ying,Lo, Yu-Hsiang,Wu, Ming-Jung
-
body text
p. 643 - 648
(2009/05/11)
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- InBr3-promoted divergent approach to polysubstituted indoles and quinolines from 2-ethynylanilines: Switch from an intramolecular cyclization to an intermolecular dimerization by a type of terminal substituent group
-
(Chemical Equation Presented) Use of a 2-ethynylaniline having an alkyl or aryl group on the terminal alkyne selectively produced a variety of polyfunctionalized indole derivatives in moderate to excellent yields via indium-catalyzed intramolecular cyclization of the corresponding alkynylaniline. In contrast, employment of a substrate with a trimethylsilyl group or with no substituent group on the terminal triple bond, exclusively afforded polysubstituted quinoline derivatives in good yields via indium-promoted intermolecular dimerization of the ethynylaniline. This indium catalytic system successfully accommodated the intramolecular cyclization of other arylalkyne skeletons involving a carboxylic acid and an amide group.
- Sakai, Norio,Annaka, Kimiyoshi,Fujita, Akiko,Sato, Asuka,Konakahara, Takeo
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p. 4160 - 4165
(2008/09/21)
-
- Cycloisomerization of γ- and δ-acetylenic acids catalyzed by gold(I) chloride
-
We have developed a gold(I)-catalyzed intramolecular cyclization of γ- and δ-alkyne acids in mild conditions yielding various alkylidene lactones. Whereas a slight electronic effect of the R group was observed on the regioselectivity, bulky substituents o
- Marchal, Estelle,Uriac, Philippe,Legouin, Béatrice,Toupet, Lo?c,Weghe, Pierre van de
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p. 9979 - 9990
(2008/02/13)
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- Hypervalent organoantimony compounds 12-ethynyl-tetrahydrodibenz[c,f][1,5]azastibocines: Highly efficient new transmetallating agent for organic halides
-
Extremely efficient and high-speed ethynylation of acyl chlorides, aryl iodides and bromides was demonstrated by palladium-catalyzed cross-coupling reaction of N-t-butyl-Sb-ethynyl-5,6,7,12-tetrahydrodibenz[c,f][1,5]azastibocine under mild conditions. Optimization and generalization of the hypervalent antimony-mediated coupling reaction are presented in detail. Single-crystal X-ray analysis of the N-methyl-1,5-azastibocine revealed that the remarkable reactivity enhancement of the azastibocine was derived from elongation of the antimony-ethynyl carbon bond originated from Sb-N intramolecular non-bonding interaction.
- Kakusawa, Naoki,Tobiyasu, Yoshinori,Yasuike, Shuji,Yamaguchi, Kentaro,Seki, Hiroko,Kurita, Jyoji
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p. 2953 - 2968
(2007/10/03)
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- Copper-free palladium-catalyzed sonogashira-type coupling of aryl halides and 1-aryl-2-(trimethylsilyl)acetylenes
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A one-pot procedure for the direct coupling of 1-aryl-2- trimethylsilylacetylenes with aryl halides to give diaryl acetylenes is reported. The procedure does not involve the use of copper(I) iodide. Improvement in reaction yields has been obtained by replacing conventional oil bath heating with the use of microwave dielectric heating.
- S?rensen, Ulrik S.,Pombo-Villar, Esteban
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p. 2697 - 2703
(2007/10/03)
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- Copper(I)-catalyzed coupling of terminal acetylenes with aryl or vinyl halides
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Synthetic protocols using copper(I) catalysts for the formation of diaryl acetylenes, 1,3-enynes, benzofurans and indoles are described. Georg Thieme Verlag Stuttgart.
- Saejueng, Pranorm,Bates, Craig G.,Venkataraman
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p. 1706 - 1712
(2007/10/03)
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- Synthesis of isocoumarins and α-pyrones via electrophilic cyclization
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A variety of substituted isocoumarins and α-pyrones are readily prepared in excellent yields under very mild reaction conditions by the reaction of o-(1-alkynyl)benzoates and (Z)-2-alken-4-ynoates with ICl, I2, PhSeCl, p-O2NC6/
- Yao, Tuanli,Larock, Richard C.
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p. 5936 - 5942
(2007/10/03)
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- An easily accessible resin-supported palladium catalyst for Sonogashira coupling
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Readily available aminomethyl-polystyrene beads can be transformed in a one-pot reaction to an air-stable polymer-bound chelate phosphine, which can be used for the immobilization of homogeneous catalysts. Such prepared Pd catalysts have proven to be useful reagents for mediating Sonogashira-coupling reactions.
- Gonthier, Elisabeth,Breinbauer, Rolf
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p. 1049 - 1051
(2007/10/03)
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- Versatile synthesis of (Z)-1-alkylidene-1,3-dihydroisobenzofurans and 1H-isochromenes by palladium-catalyzed cycloisomerization of 2-alkynylbenzyl alcohols
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An easy synthesis of (Z)-1-alkylidene-1,3-dihydroisobenzofurans and 1H-isochromenes by palladium-catalyzed cycloisomerization of readily available 2-alkynylbenzyl alcohols under neutral conditions is reported. Reactions were carried out at 70-100°C in the
- Gabriele, Bartolo,Salerno, Giuseppe,Fazio, Alessia,Pittelli, Rosina
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p. 6251 - 6259
(2007/10/03)
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- On the diverse outcomes of base-induced cyclisations of 2-alkynylphenylhydroxamic acids
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Base-induced cyclisations of 2-alkynylphenylhydroxamic acids occur by attack of nitrogen onto the alkyne group in either exo or endo fashions to give the corresponding isoindol-1(2H)-ones or 1(2H)-isoquinolinones depending upon the alkyne substituent.
- Knight, David W.,Lewis, Paul B.M.,Abdul Malik,Mshvidobadze, Elena V.,Vasilevsky, Sergei F.
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p. 9187 - 9189
(2007/10/03)
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- New procedures for the selective synthesis of 2(2H)-pyranone derivatives and 3-aryl-4-iodoisocoumarins
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5-Iodo-2(2H)-pyranone derivatives have been selectively synthesized by reaction of stereodefined methyl 2-en-4-ynoates with iodine in MeCN, CH2Cl2 or C6H6 at 20°C (Method C) or by treatment of these esters with
- Biagetti, Matteo,Bellina, Fabio,Carpita, Adriano,Stabile, Paolo,Rossi, Renzo
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p. 5023 - 5038
(2007/10/03)
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- Formation of aryl-nitrogen, aryl-oxygen, and aryl-carbon bonds using well-defined copper(I)-based catalysts
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(Matrix Presented) We report mild synthetic protocols for the formation of aryl-carbon, aryl-nitrogen, and aryl-oxygen bonds based on soluble, well-defined copper(I) catalysts. These protocols do not require the use of palladium and/or expensive ligands.
- Gujadhur, Rattan K.,Bates, Craig G.,Venkataraman
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p. 4315 - 4317
(2007/10/03)
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- Synthesis of 6H-indolo[2,3-b][1,6]naphthyridines and related compounds as the 5-aza analogues of ellipticine alkaloids
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Treatment of 2-(1-alkynyl)phenyl isocyanates 6 with the iminophosphorane 14 produced in situ the benzoenynyl carbodiimides 15. Thermolysis of 15 under refluxing p-xylene furnished the 6H-indolo[2,3-b][1,6]naphthyridines 5, which could be regarded as the 5-aza analogues of ellipticine alkaloids. Similarly, condensation of 6 with the iminophosphorane 20 led to the formation of the 6H-indolo[2,3-b][1,5]naphthyridines 25 as the major isomer and the 10H-indolo[2,3-b][1,7]naphthyridines 26 as the minor isomer. The indolonaphthyridines 32, 33, and 34 having a methoxyl substituent were likewise synthesized. Treatment of the diisocyanate 43 with 2 equiv of the iminophosphorane 7 furnished 45 having two indoloquinoline units incorporated in a seven-fused-ring system.
- Zhang,Shi,Zhang,Wang
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p. 7977 - 7983
(2007/10/03)
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- Biradicals from thermolysis of N-[2-(1-alkynyl)phenyl]-N'- phenylcarbodiimides and their subsequent transformations to 6H-indolo[2,3- b]quinolines
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Thermolysis of the carbodiimide 9a in γ-terpinene at 138 °C produced 2-(phenylamino)quinoline (11a, 49%) and the parent 6H-indolo[2,3-b]quinoline (14a, 16%). Apparently, 11a was produced via the biradical 10a followed by hydrogen-atom abstraction from γ-terpinene. A two-step biradical pathway through 12a or a one-step intramolecular Diels-Alder reaction could furnish 13a, which then underwent tautomerization to give 14a. With the carbodiimide 9b having a trimethylsilyl substituent at the acetylenic terminus, thermolysis in refluxing p-xylene at 138 °C produced the 6H-indolo[2,3- b]quinoline 14b (86%) exclusively. Treatment of 14b with 6 N NaOH in refluxing ethanol then furnished 14a in 92% yield. Similarly, the 6H- indolo[2,3-b]quinolines 14c-f were obtained from thermolysis of the carbodiimides 9c-f. The use of the aza-Wittig reaction between 4- methoxyphenyl isocyanate and the iminophosphoranes 2d and 2f to produce the corresponding carbodiimides followed by thermolysis furnished the 6H- indolo[2,3-b]quinolines 16d and 16f having a methoxy substituent at the C-2 position. Thermolysis of the carbodiimides 25a and 25b produced 26a and 26b having two indoloquinoline units connected at the 11 and 11' positions with either a three-carbon or a five-carbon tether. Using 1,4-phenylene diisocyanate for the aza-Wittig reaction with 2 equiv of the iminophosphorane 2g followed by thermolysis furnished 31 (66%) having two indoloquinoline units incorporated in the seven fused rings.
- Shi, Chongsheng,Zhang, Quan,Wang, Kung K.
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p. 925 - 932
(2007/10/03)
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