- Pd(II)-catalyzed annulation reactions of epoxides with benzamides to synthesize isoquinolones
-
Epoxides as alkylating reagents are unprecedentedly applied in Pd(II)-catalyzed C?H alkylation and oxidative annulation of substituted benzamides to synthesize isoquinolones rather than isochromans, which is accomplished through alerting the previously reported reaction mechanism by the addition of oxidant and TEA. Under these conditions, various isoquinolones have been prepared with yields up to 92%. In addition, this methodology has been successfully employed in the total syntheses of rupreschstyril, siamine, and cassiarin A in an expedient fashion.
- Wang, Huihong,Cao, Fei,Gao, Weiwei,Wang, Xiaodong,Yang, Yuhang,Shi, Tao,Wang, Zhen
-
supporting information
p. 863 - 868
(2021/02/06)
-
- Pd/C-catalyzed aerobic oxidative C–H alkenylation of arenes in γ-valerolactone (GVL)
-
A novel methodology for the heterogeneous palladium-catalyzed C–H alkenylation of N-methoxybenzamides and anilides is presented. This approach is based on the use of commercially available Pd/C as catalyst and molecular oxygen as terminal oxidant, in comb
- Anastasiou, Ioannis,Ferlin, Francesco,Santoro, Stefano,Vaccaro, Luigi,Viteritti, Orlando
-
-
- Harnessing hypervalent iodonium ylides as carbene precursors: C-H activation of: N -methoxybenzamides with a Rh(iii)-catalyst
-
Hypervalent iodonium ylides expeditiously generate carbenes which undergo domino intermolecular C-H activation followed by intramolecular condensation in the presence of N-methoxybenzamide as a starting material and a Rh(iii)-catalyst to afford dihydrophenanthridines. KIE studies and DFT calculations were performed to substantiate the mechanistic pathway. To extend the synthetic utilisation, fluorescent pyranoisocoumarins were achieved by using Rh(iii)-catalyzed peri-C-H/O-H activation/annulation reactions.
- Mayakrishnan, Sivakalai,Tamizmani, Masilamani,Maheswari, Naryanan Uma
-
supporting information
p. 15462 - 15465
(2020/12/25)
-
- Palladium-Catalyzed Inert C?H Bond Activation and Cyclocarbonylation of Isoquinolones with Carbon Dioxide Leading to Isoindolo[2,1-b]isoquinoline-5,7-Diones
-
A palladium-catalyzed inert C?H bond activation and cyclocarbonylation of isoquinolones leading to isoindolo[2,1-b]isoquinoline-5,7-diones under 1 atm of carbon dioxide has been developed. This transformation features high regio- and chemo-selectivity, step-economy, and good functional group tolerance. Most of the corresponding products were obtained in moderate to good yields. It offers an alternative approach for the synthesis of useful diverse isoindolo[2,1-b]isoquinoline-5,7-dione derivatives. (Figure presented.).
- Yan, Kelu,Jin, Junbin,Kong, Yong,Li, Bin,Wang, Baiquan
-
supporting information
p. 3080 - 3085
(2019/05/21)
-
- Three-Component Synthesis of Isoquinoline Derivatives by a Relay Catalysis with a Single Rhodium(III) Catalyst
-
A rhodium(III)-catalyzed one-pot three-component reaction of N-methoxybenzamide, α-diazoester, and alkyne was developed, providing an alternative way to synthesize isoquinoline derivatives. Mechanistically, it is a relay catalysis, and the reaction occurred via successive O-alkylation and C-H activation processes, both of which were promoted by the same catalyst.
- Zhou, Chao,Jiang, Jijun,Wang, Jun
-
supporting information
p. 4971 - 4975
(2019/09/03)
-
- Rhodium(III)-catalyzed chemodivergent annulations between: N-methoxybenzamides and sulfoxonium ylides via C-H activation
-
Chemodivergent and redox-neutral annulations between N-methoxybenzamides and sulfoxonium ylides have been realized via Rh(iii)-catalyzed C-H activation. The sulfoxonium ylide acts as a carbene precursor, and coupling occurs under acid-controlled condition
- Xu, Youwei,Zheng, Guangfan,Yang, Xifa,Li, Xingwei
-
supporting information
p. 670 - 673
(2018/01/28)
-
- Indole- and Pyrrole-BX: Bench-Stable Hypervalent Iodine Reagents for Heterocycle Umpolung
-
The one-step synthesis of the bench-stable hypervalent iodine reagents IndoleBX and PyrroleBX using mild Lewis acid catalyzed conditions is reported. The new reagents are stable up to 150 °C and were applied in the C?H arylation of unactivated arenes using either rhodium or ruthenium catalysts. A broad range of heterocyclic systems of high interest for synthetic and medicinal chemistry was accessed in high yields. The developed C?H functionalization could not be achieved using reported reagents or methods, highlighting the unique reactivity of Indole- and Pyrrole-BX.
- Caramenti, Paola,Nicolai, Stefano,Waser, Jerome
-
supporting information
p. 14702 - 14706
(2017/09/11)
-
- Palladium-Nanoparticles-Catalyzed Oxidative Annulation of Benzamides with Alkynes for the Synthesis of Isoquinolones
-
A novel method to synthesize isoquinolones via oxidative annulation of N-alkoxy benzamides and alkynes using binaphthyl-stabilized palladium nanoparticles (Pd-BNP) as catalyst has been developed. This methodology affords various isoquinolone derivatives in good to excellent yields with high regioselectivities in the presence of air as oxidant. N-Methoxybenzothioamide was also found to undergo oxidative annulation with alkyne successfully and provided a sulfur analogue of isoquinolones in moderate yields. The Pd-BNP catalyst was easily recovered and reused up to four times without any apparent agglomeration. (Figure presented.).
- Sharma, Nidhi,Saha, Rajib,Parveen, Naziya,Sekar, Govindasamy
-
supporting information
p. 1947 - 1958
(2017/06/09)
-
- C-F bond cleavage enabled redox-neutral [4+1] annulation via C-H bond activation
-
Using α,α-difluoromethylene alkyne as a nontraditional one-carbon reaction partner, a synthetically novel method for the construction of isoindolin-1-one derivatives via Rh(III)-catalyzed [4+1] annulation reaction is reported. The 2-fold C-F bond cleavage not only enables the generation of desired product under an overall oxidant-free condition but also results in a net migration of carbon-carbon triple bond. In addition, the present reaction protocol exhibits a tolerance of a wide spectrum of functional groups due to the mild reaction conditions employed.
- Wang, Cheng-Qiang,Ye, Lu,Feng, Chao,Loh, Teck-Peng
-
supporting information
p. 1762 - 1765
(2017/02/15)
-
- Selective mono-alkylation of N-methoxybenzamides
-
We report our latest discovery of norbornene derivative modulated highly mono-selective ortho-C-H activation alkylation reactions on arenes bearing simple mono-dentate coordinating groups. The reaction features the use of readily available benzamides and alkyl halides. During the study, we prepared 30 mono-alkylated aryl amides in good yields with good mono-selectivity. We have also demonstrated that structurally rigid alkenes such as norbornene and its derivatives are a good class of ligand and could be used for future direct C-H functionalizations. The utilization of norbornene type ligands for assistance in C-H activation processes has opened a new window for future molecular design using direct C-H functionalization strategies.
- Chen, Zenghua,Hu, Le'an,Zeng, Fanyun,Zhu, Ranran,Zheng, Shasha,Yu, Qingzhen,Huang, Jianhui
-
supporting information
p. 4258 - 4261
(2017/04/21)
-
- Ir(III)-Catalyzed Carbenoid Functionalization of Benzamides: Synthesis of N-Methoxyisoquinolinediones and N-Methoxyisoquinolinones
-
A mild and efficient Ir(III)-catalyzed C-H carbenoid functionalization strategy has been developed to access N-methoxyisoquinolinediones and N-methoxyisoquinolinones. The reaction proceeds efficiently in high yield at room temperature over a broad range of substrates without requirement of any additional oxidants or a base.
- Phatake, Ravindra S.,Patel, Pitambar,Ramana, Chepuri V.
-
supporting information
p. 2828 - 2831
(2016/07/06)
-
- Rh-Catalyzed annulations of: N -methoxybenzamides with ketenimines: Synthesis of 3-aminoisoindolinones and 3-diarylmethyleneisoindolinones with strong aggregation induced emission properties
-
Rhodium-catalyzed C-H activation/annulation reactions of ketenimines with N-methoxybenzamides furnished 3-aminoisoindolin-1-ones and 3-(diarylmethylene)isoindolin-1-ones. The synthesized 3-(diarylmethylene)isoindolin-1-ones exhibited aggregation induced emissions in aqueous tetrahydrofuran solution and strong green-yellow emissions in solids.
- Zhou, Xiaorong,Peng, Zhixing,Zhao, Hongyang,Zhang, Zhiyin,Lu, Ping,Wang, Yanguang
-
supporting information
p. 10676 - 10679
(2016/09/02)
-
- Regiocontrolled Coupling of Aromatic and Vinylic Amides with α-Allenols to Form γ-Lactams via Rhodium(III)-Catalyzed C-H Activation
-
A mild, regiocontrolled coupling of aromatic and vinylic amides with α-allenols to form γ-lactams via rhodium(III)-catalyzed C-H activation has been demonstrated. This [4 + 1] annulation reaction provides an efficient method for the synthesis of isoindolinones and 1,5-dihydro-pyrrol-2-ones bearing a tetrasubstituted carbon atom α to the nitrogen atom with good functional group tolerance. The hydroxyl group in the allene substrate is essential in controlling the chemo- and regioselectivity of the reaction probably by coordination interaction with the rhodium catalyst.
- Zhou, Zhi,Liu, Guixia,Lu, Xiyan
-
supporting information
p. 5668 - 5671
(2016/11/17)
-
- Palladium-Catalyzed Deaminative Phenanthridinone Synthesis from Aniline via C-H Bond Activation
-
This work reports palladium-catalyzed phenanthridinone synthesis using the coupling of aniline and amide by formation of C-C and C-N bonds in a one-pot fashion via dual C-H bond activation. It involves simultaneous cleavage of four bonds and the formation of two new bonds. The present protocol is ligand-free, takes place under mild reaction conditions, and is environmentally benign as nitrogen gas and water are the only side products. This transformation demonstrates a broad range of aniline and amide substrates with different functional groups and has been scaled up to gram level.
- Yedage, Subhash L.,Bhanage, Bhalchandra M.
-
supporting information
p. 4103 - 4111
(2016/06/09)
-
- Rhodium(iii)-catalyzed C-H/C-C activation sequence: Vinylcyclopropanes as versatile synthons in direct C-H allylation reactions
-
Succession of C-H activation and C-C activation was achieved by using a single rhodium(iii) catalyst. Vinylcyclopropanes were used as versatile coupling partners. Mechanistic studies suggest that the olefin insertion step is rate-determining and a facile β-carbon elimination is involved, which represents a novel ring opening mode of vinylcyclopropanes. This journal is
- Wu, Jia-Qiang,Qiu, Zhi-Ping,Zhang, Shang-Shi,Liu, Jing-Gong,Lao, Ye-Xing,Gu, Lian-Quan,Huang, Zhi-Shu,Li, Juan,Wang, Honggen
-
supporting information
p. 77 - 80
(2015/01/09)
-
- Amides and Ethers as Chemoselective Surrogates for Copper(II)-Catalyzed ortho Benzoyloxylation of 2-Phenylpyridines
-
Chemoselective ortho benzoyloxylation of 2-phenylpyridine derivatives using amides and ethers as novel arylcarboxy sources using a Cu(II)/TBHP catalytic system has been reported. It is a simple protocol for ortho benzoyloxylation using amides and ethers as surrogates. A broad range of amides and ethers was found to be compatible under optimized reaction conditions to provide the corresponding products in good to excellent yield. The reaction proceeds through the cleavage of C-N, C-O, and C-H bonds and the formation of a new C-O bond via C-H functionalization.
- Yedage, Subhash L.,Bhanage, Bhalchandra M.
-
supporting information
p. 2161 - 2169
(2015/09/15)
-
- Tunable arylative cyclization of 1,6-enynes triggered by rhodium(III)-catalyzed C-H activation
-
Two tunable arylative cyclizations of cyclohexadienone-containing 1,6-enynes are reported via rhodium(III)-catalyzed C-H activation of O-substituted N-hydroxybenzamides. The use of different O substituents, i.e. O-Piv and O-Me, on the directing group allows the formation of either tetracyclic isoquinolones through an N-Michael addition process or hydrobenzofurans through a C-Michael addition process. Mechanistic investigations of these two cascade reactions clearly indicated that the C-H bond cleavage process was involved in the turnover-limiting step. Furthermore, the cyclization products could be subjected to various transformations for elaborating the pharmaceutically and synthetically valuable potential. This is the first example of a rhodium(III)-catalyzed arylative cyclization reaction of 1,6-enynes, and the results extend the application realm of CpRhIII-catalyzed C-H activation cascade reactions.
- Fukui, Yuki,Liu, Ping,Liu, Qiang,He, Zhi-Tao,Wu, Nuo-Yi,Tian, Ping,Lin, Guo-Qiang
-
supporting information
p. 15607 - 15614
(2014/12/11)
-
- A highly efficient Pd-catalyzed decarboxylative ortho-arylation of amides with aryl acylperoxides
-
An efficient Pd-catalyzed decarboxylative ortho-arylation of amides with aryl acylperoxides was developed. A variety of anilides reacted with aryl acylperoxides to afford the corresponding ortho-arylation products, and N-methoxyarylamides generated phenanthridinones. This journal is
- Li, Dengke,Xu, Ning,Zhang, Yicheng,Wang, Lei
-
supporting information
p. 14862 - 14865
(2014/12/11)
-
- Metal-free iodine(III)-promoted synthesis of isoquinolones
-
A metal-free oxidative cycloaddition reaction of substituted benzamides and alkynes has been developed for the synthesis of isoquinolones by using bis(trifluoracetoxy)iodobenzene (PIFA) and trifluoroacetic acid (TFA). Under mild conditions, a wide variety of isoquinolones were conveniently prepared via oxidative annulation of simple N-methoxybenzamide and diarylacetylene or aryl/alkyl acetylene derivatives in yields up to 87%.
- Chen, Zhi-Wei,Zhu, Yi-Zhou,Ou, Jin-Wang,Wang, Ya-Ping,Zheng, Jian-Yu
-
p. 10988 - 10998
(2015/01/08)
-
- Synthesis and thermal decomposition of N,N-dialkoxyamides
-
N,N-Dialkoxyamides 1c, a virtually unstudied member of the new class of anomeric amides, amides bearing two electronegative atoms at nitrogen, have been synthesised in useful yields directly from hydroxamic esters using phenyliodine(iii)bis(trifluoroacetate) (PIFA). Infrared carbonyl stretch frequencies and carbonyl 13C NMR properties have been reported, which support strong inhibition of amide resonance in these amides. Their thermal decomposition reactions in mesitylene at 155°C proceed by homolysis to form alkoxyamidyl and alkoxyl free radicals in preference to HERON rearrangements to esters. The reactions follow first-order kinetics and for a series of N,N-dimethoxy-4-substituted benzamides, activation energies of 125-135 kJ mol-1 have been determined together with weakly negative entropies of activation.
- Digianantonio, Katherine M.,Glover, Stephen A.,Johns, Jennifer P.,Rosser, Adam A.
-
scheme or table
p. 4116 - 4126
(2011/06/28)
-
- New heteroannulation reactions of N-Alkoxybenzamides by Pd(II) Catalyzed C-H activation
-
A new palladium(II) catalyzed methodology for the direct synthesis of alkylidene isoindolinones from N-alkoxybenzamides is presented. Isoindolinone formation proceeds through a highly efficient and E-selective C-H activation/Heck/Aza-Wacker sequence. Subs
- Wrigglesworth, Joe W.,Cox, Brian,Lloyd-Jones, Guy C.,Booker-Milburn, Kevin I.
-
supporting information; experimental part
p. 5326 - 5329
(2011/12/01)
-
- One-pot formation of C-C and C-N bonds through palladium-catalyzed dual C-H activation: Synthesis of phenanthridinones
-
Two cycles in one pot! The synthesis of biologically important phenanthridinones has been achieved by the one-pot formation of C-C and C-N bonds through a palladium-catalyzed dual C-H activation, which involves four bond ruptures and two bond formations (see scheme). The conversion of phenanthridinones into natural product like derivatives further demonstrates the utility of this synthetic achievement.
- Wang, Guan-Wu,Yuan, Ting-Ting,Li, Dan-Dan
-
supporting information; experimental part
p. 1380 - 1383
(2011/04/18)
-
- Synthesis of isoindolinones via palladium-catalyzed C-H activation of N-methoxybenzamides
-
The synthesis of isoindolinones from N-methoxybenzamides and alkenes has been achieved by Pd-catalyzed ortho sp2 C-H activation and intramolecular oxidative amidation, which involve the cleavage of four bonds and formation of two bonds.
- Li, Dan-Dan,Yuan, Ting-Ting,Wang, Guan-Wu
-
supporting information; experimental part
p. 12789 - 12791
(2012/01/05)
-
- Imino 1,2-Wittig rearrangement of hydroximates and its application to synthesis of cytoxazone
-
The imino 1,2-Wittig rearrangement of hydroximates provides a novel method for the construction of 2-hydroxyoxime ethers. Upon treatment with LDA, Z-hydroximates smoothly underwent stereoselective rearrangement to give Z-2-hydroxyoxime ethers in good yield, which were converted into amino alcohols. On the other hand, the rearrangement of E-hydroximates gave a mixture of E- and Z-2-hydroxyoxime ethers. This method was successfully applied to a practical synthesis of cytoxazone.
- Miyata, Okiko,Koizumi, Tomoko,Asai, Hiroshi,Iba, Ryuichi,Naito, Takeaki
-
p. 3893 - 3914
(2007/10/03)
-
- Reaction of 1-hydroxyphthalimide derivatives with aluminum chloride in benzene
-
The reaction of 1-hydroxyphthalimide derivatives with AlCl3 in benzene has been investigated. From 1-hydroxyphthalimide (1a) 2-hydroxy-3,3-diphenyl-2,3-dihydroisoindol-1-one (2) and 1,1-diphenyl-1H-benzo[d][1,2]oxazm-4-one (3) are obtained by initial attack of benzene on the imide carbonyl, assisted by the neighboring oxygen atom. Heating 2 with Lewis acid (Alcl3) in benzene results in ring expansion to afford 3, while heating 3 with protic acid (H2SO4) leads to ring contraction to give 2. From O-(2-phenethyl)- and O-benzoyl derivatives (1b and c), 1,2-diphenylethane (4) and benzophenone (5) are obtained, respectively, by the heterolytic cleavage of an C-O bond.
- Uto, Kensaku,Sakamoto, Takeshi,Matsumoto, Keita,Kikugawa, Yasuo
-
p. 633 - 640
(2007/10/03)
-
- Mechanism of Hydrolysis of (Z)- and (E)-O-Methylbenzohydroximoyl Chloride
-
The first-order rate constants for the hydrolysis (1:3 dioxane-water, pH = 7) of (E)-O-methylbenzohydroximoyl chloride and several 4-substituted derivatives have been measured.A Hammett plot of these rate constants vs ?+
- Johnson, James E.,Riesgo, Elvira C.,Jano, Issam
-
-
- Decomposition of N,N'-Diacyl-N,N'-dialkoxyhydrazines Revisited
-
N,N'-Diacyl-N,N'-dialkoxyhydrazines have been shown to decompose thermally to esters and nitrogen.An intramolecular crossover experiment has shown that the formation of esters is consistent with a three-centred rearrangement process which is characteristic of N-alkoxy N-amino amides.The four-centred mechanism previously proposed by earlier workers is less favourable energetically.AM1 molecular orbital calculations support these experimental findings.
- Buccigross, Jeanne M.,Glover, Stephen A.,Hammond, Gerard P.,Rowbottom, Colleen A.
-
p. 353 - 362
(2007/10/02)
-
- PHOTOCHEMISTRY OF HYDROXAMIC ACIDS
-
Photochemical reactions of hydroxamic acids have been studied.The intermediacy of a RCONH(.) radical is postulated, based on oxidations achieved with DCA under photochemical conditions.
- Hosangadi, B.D.,Chhaya, P.N.,Nimbalkar, M.M.,Patel, N.R.
-
p. 5375 - 5380
(2007/10/02)
-
- Mechanism of Solvolysis Reactions of O-Methylbenzohydroximoyl Halides. Stereoelectronic Control in Formation of and Nucleophilic Addition to Nitrilium Ions
-
The hydrolysis reactions of the Z and E isomers of O-methylbenzohydroximoyl chloride (3a and 2, respectively) have been investigated. The first-order rate constant for the hydrolysis of 3a (1) shows common-ion rate depression, (2) decreases with decreasin
- Johnson, James E.,Cornell, Sravanthi C.
-
p. 4144 - 4148
(2007/10/02)
-