- SET photochemistry of phthalimide anion and its reactivity with hydrogen donors
-
The investigation of the photochemistry of phthalimide anion has uncovered its exceptional reactivity with hydrogen donors such as alcohols, toluene, ethers and amines. Photoreactions can be conducted to high conversions and photoadducts are formed in high yield and with predictable regioselectivity. Exploratory studies have revealed that SET from the excited phthalimide anion to phthalimide is a thermodinamically favourable step that produces the electrophilic phthalimidyl radical and is the key step of the process.
- Sánchez-Sánchez, Cristobal,Pérez-Inestrosa, Ezequiel,García-Segura, Rafael,Suau, Rafael
-
-
Read Online
- Influence of N-Substitution in 3-Alkyl-3-hydroxyisoindolin-1-ones on the Stereoselectivity of Br?nsted Acid-Catalyzed Synthesis of 3-Methyleneisoindolin-1-ones
-
A comprehensive study on the influence of N-substitution on the stereoselective outcome of the synthesis of 3-methyleneisoindolin-1-ones from 3-alkyl-3-hydroxyisoindolin-1-ones is reported. The study was performed on an array of structurally diverse 3-alkyl-3-hydroxyisoindolin-1-ones with tunable sizes of N-substituents. In a methanesulfonic acid-catalyzed reaction, substrates without N-substituent (N?H) afforded exclusively the Z-isomer, while an increase in their size was followed by the formation of a stereoisomeric mixture with the E-isomer as the major component.
- Topolov?an, Nikola,Dupli?, Filip,Gredi?ak, Matija
-
supporting information
p. 3920 - 3924
(2021/08/24)
-
- Copper-mediated oxidative C-H/N-H activations with alkynes by removable hydrazides
-
The efficient copper-mediated oxidative C-H alkynylation of benzhydrazides was accomplished with terminal alkynes. Thus, a heteroaromatic removable N-2-pyridylhydrazide allowed for domino C-H/N-H functionalization. The approach featured remarkable functional group compatibility and ample substrate scope. Thereby, highly functionalized aromatic and heteroaromatic isoindolin-1-ones were accessed with high efficacy with rate-limiting C-H cleavage.
- Ackermann, Lutz,Gu, Linghui,Li, Bo,Ma, Wenbo,Mei, Ruhuai,Xiong, Feng,Yang, Chenrui,Zou, Liang
-
supporting information
p. 1591 - 1599
(2021/07/26)
-
- Highly stereoselective synthesis of (Z)-3-methoxy-1-methyleneisoindoles via DMAP catalyzed cyclization of methyl 2-alkynylbenzimidates
-
A DMAP (4-dimethylaminopyridine) catalyzed cyclization of methyl 2-alkynylbenzimidates has been developed, which affords 3-methoxy-1-methyleneisoindoles with excellent Z-stereoselectivity under mild and transition-metal-free conditions. The (Z)-3-methoxy-
- Yao, Tuanli,Liang, Xiujuan,Guo, Zhen,Yang, Dong
-
p. 3088 - 3100
(2019/05/07)
-
- Preparation method of cis-3-alkoxy-1-methylene isoindole derivative
-
The invention relates to a preparation method of a cis-3-alkoxy-1-methylene isoindole derivative. The preparation method comprises the following step: synthesizing cis- 3-alkoxy-1-methylene isoindolewith high stereoselectivity by taking a p-alkyne phenyl imidoate compound as a raw material and organic or inorganic alkali as a catalyst. The method is low in catalytic cost, mild in reaction condition, relatively high in synthetic yield and simple to operate. By deriving 3-alkoxy-1-methylene isoindole, isoindolinone, 3-amino-1-methylene isoindole and 1-alkyl-3-methylene isoindole can be synthesized efficiently. The derivatives are core structural units of many natural products, exist in molecules of various natural products and medicines widely and have relatively wide biological activity. The invention provides a novel method for synthesizing 3-alkoxy-1-methylene isoindole and the derivatives.
- -
-
Paragraph 0011; 0022
(2019/01/14)
-
- Phenylidene phenyl peptide compounds and medicinal composition and application thereof
-
The invention provides phenylidene phenyl peptide compounds, a medicinal composition using the phenylidene phenyl peptide compounds as active components, and application thereof as monoamine oxidase B(MAO-B) inhibitors and application thereof to preparation of medicines for treating Parkinson's disease (PD). Monoamine oxidase B (MAO-B) has been proved to be closely related to the pathogenesis ofthe Parkinson's disease (PD) and is a classic target for research and development of the medicines for treating the Parkinson's disease (PD). The invention provides application of the phenylidene phenyl peptide compounds to preparation of the monoamine oxidase B (MAO-B) inhibitors. In-vitro kinase activity experiments prove that the phenylidene phenyl peptide compounds have a significant monoamineoxidase B (MAO-B) inhibiting effect.
- -
-
Paragraph 0148-0152
(2018/11/22)
-
- Direct Difluorination-Hydroxylation, Trifluorination, and C(sp2)-H Fluorination of Enamides
-
A direct double functionalization involving both difluorination and hydroxylation of enamides is reported. With the appropriate combination of an electrophilic fluorinating reagent and H2O, the most convenient and ecofriendly hydroxylating agent, the preparation of 3-(difluoroalkyl)-3-hydroxyisoindolin-1-ones was achieved under basic or Br?nsted acidic conditions. Suitable conditions for trifluorination as well as C(sp2)-H fluorination were also identified. Subsequent asymmetric functionalization of the obtained gem-difluorinated products has also been demonstrated.
- Munoz, Socrates B.,Krishnamurti, Vinayak,Barrio, Pablo,Mathew, Thomas,Prakash, G. K. Surya
-
supporting information
p. 1042 - 1045
(2018/02/23)
-
- Synthesis of Secondary Unsaturated Lactams via an Aza-Heck Reaction
-
The preparation of unsaturated secondary lactams via the palladium-catalyzed cyclization of O-phenyl hydroxamates onto a pendent alkene is reported. This method provides rapid access to a broad range of lactams that are widely useful building blocks in alkaloid synthesis. Mechanistic studies support an aza-Heck-type pathway.
- Shuler, Scott A.,Yin, Guoyin,Krause, Sarah B.,Vesper, Caroline M.,Watson, Donald A.
-
p. 13830 - 13833
(2016/11/06)
-
- Synthesis of 3-substituted isoindolin-1-ones via a tandem desilylation, cross-coupling, hydroamidation sequence under aqueous phase-transfer conditions
-
A simple and expedient method for the synthesis of 3-methylene-isoindolin-1-ones 4 under aqueous phase-transfer conditions has been developed. Starting from 2-iodobenzamides 1 and (silyl)alkynes, the products are obtained in high yields and short reaction times (30 min) with the use of inexpensive CuCl/PPh3 catalyst system in the presence of n-Bu4NBr (TBAB) as a phase-transfer agent. Terminal alkynes are conveniently "unmasked" upon in situ desilylation under the reaction conditions. Alkynes possessing heterocyclic moieties were also found as amenable substrates. Furthermore, a one-pot process starting from 2-iodobenzamides 1, aryl halides (bromides or iodides) and trimethylsilylacetylene (TMSA) as a convenient acetylene surrogate was also shown to be feasible under Pd/Cu catalysis.
- Munoz, Socrates B.,Aloia, Alexandra N.,Moore, Alexander K.,Papp, Attila,Mathew, Thomas,Fustero, Santos,Olah, George A.,Surya Prakash
-
supporting information
p. 85 - 92
(2015/12/30)
-
- Cobalt(II)-Catalyzed Csp2-H Alkynylation/Annulation with Terminal Alkynes: Selective Access to 3-Methyleneisoindolin-1-one
-
A highly efficient cobalt(II)-catalyzed alkynylation/annulation of terminal alkynes assisted by an N,O-bidentate directing group is described. This protocol is characterized by wide substrate scope utilizing cheap cobalt catalysts, and offers a new approa
- Zhang, Lin-Bao,Hao, Xin-Qi,Liu, Zhan-Jiang,Zheng, Xin-Xiang,Zhang, Shou-Kun,Niu, Jun-Long,Song, Mao-Ping
-
p. 10012 - 10015
(2015/08/19)
-
- Copper-catalyzed selective synthesis of isoindolin-1-ones and isoquinolin-1-ones from the three-component coupling of 2-halobenzoic acid, alkynylcarboxylic acid and ammonium acetate
-
Isoindolin-1-ones and isoquinolin-1-ones were selectively synthesized from the reaction of 2-halobenzoic acid, arylalkynylcarboxylic acid and ammonium acetate (NH4OAc) in the presence of cesium carbonate (Cs2CO3) and a copper catalyst. Conducting the reaction under one-pot conditions provided isoindolin-1-ones in good yields. Changing the addition sequence of ammonium acetate after all reagents had reacted at 120 °C for 6 h selectively produced isoquinolin-1-ones. A variety of arylalkynylcarboxylic acids produced the corresponding isoindolin-1-ones and isoquinolin-1-ones in good yields.
- Irudayanathan, Francis Mariaraj,Noh, Jieun,Choi, Jinseop,Lee, Sunwoo
-
p. 3433 - 3442
(2015/01/09)
-
- Reductive coupling of phthalimides with ketones and aldehydes by low-valent titanium: One-pot synthesis of alkylideneisoindolin-1-ones
-
The reductive coupling of phthalimides with ketones and aldehydes by Zn-TiCl4 in THF gave two- and four-electron reduced products, 3-hydroxy-3-(1-hydroxyalkyl)isoindolin-1-ones and alkylideneisoindolin-1-ones, selectively by controlling the rea
- Kise, Naoki,Kawano, Yusuke,Sakurai, Toshihiko
-
p. 12453 - 12459
(2014/01/17)
-
- Copper(II)-catalyzed tandem synthesis of substituted 3-methyleneisoindolin- 1-ones
-
An efficient strategy for the synthesis of a variety of 3-methyleneisoindolin-1-ones has been developed. The reaction proceeded from coupling of 2-iodobenzamides (or 2-bromobenzamides) and terminal alkynes via Cu(OAc)2·H2O/2,2′-biimi
- Pan, Jie,Xu, Zhen,Zeng, Runsheng,Zou, Jianping
-
supporting information
p. 1022 - 1026
(2013/09/02)
-
- Efficient Synthesis of a (Z)-3-Methyleneisoindolin-1-one Library Using Cu(OAc)2·H2O/DBU under Microwave Irradiation
-
Microwave-promoted efficient synthesis of a (Z)-3-methyleneisoindolin-1-one library from 2-bromobenzamides and terminal alkynes using Cu(OAc) 2·H2O/DBU is described. Various benzamide substituents, ring substitutions, including heter
- Zhang, Li,Zhang, Yongliang,Wang, Xin,Shen, Jingkang
-
p. 654 - 665
(2013/03/14)
-
- Photo-induced sonogashira C-C coupling reaction catalyzed by simple copper(I) chloride salt at room temperature
-
The conventional thermal Sonogashira C-C coupling reaction requires the use of a palladium catalyst and a large amount of ligands. Although there were a few reports describing the use of inexpensive metal catalysts, such as, copper (Cu), iron (Fe), and nickel (Ni), for replacement of palladium (Pd) in the Sonogashira reactions, it was later questioned that the observed effects were due to ppb levels contamination of Pd present in the reagents used in the reactions. Herein, we report that simple copper(I) chloride (CuCl) salt, in the absence of Pd and ligands, can catalyze the Sonogashira reaction with high yields (80-99%) under blue LED light irradiation at room temperature. Control experiments show that no cross-coupling product was formed, when palladium(II) chloride (PdCl2) was used to replace CuCl as a catalyst. A series of electron-rich and electron-poor substituted aryl halides (bromides and iodides) as well as aryl- and alkylacetylenes are examined and the reaction mechanism is discussed.
- Sagadevan, Arunachalam,Hwang, Kuo Chu
-
supporting information
p. 3421 - 3427
(2013/02/22)
-
- Electroreductive intermolecular coupling of phthalimides with aldehydes: Application to the synthesis of alkylideneisoindolin-1-ones
-
The electroreduction of N-methyl, N-p-anisyl, and N-unsubstituted phthalimides with aldehydes in the presence of chlorotrimethylsilane and triethylamine gave intermolecularly coupled products, 3-hydroxy-3-(1- hydroxyalkyl)isoindolin-1-ones. The coupling p
- Kise, Naoki,Isemoto, Shinsaku,Sakurai, Toshihiko
-
p. 8805 - 8816
(2012/11/06)
-
- Microwave assisted copper-free Sonogashira coupling/5-exo-dig cycloisomerization domino reaction: Access to 3-(phenylmethylene)isoindolin-1- ones and related heterocycles
-
An efficient microwave assisted one-pot synthesis of substituted 3-(phenylmethylene)isoindolin-1-ones is reported via a copper-free Sonogashira coupling and a regioselective 5-exo-dig cycloisomerization. This domino reaction was also extended to other related heterocycles.
- Hellal, Malik,Cuny, Gregory D.
-
supporting information; experimental part
p. 5508 - 5511
(2011/10/31)
-
- Photodecarboxylative benzylations of phthalimide in pH 7 buffer: A simple access to 3-arylmethyleneisoindolin-1-ones
-
Photoadditions of phenylacetates to phthalimide in pH 7 buffer solution give the corresponding benzylated-hydroxyphthalimidines in moderate to high yields of up to 94%. In a micro-structured reactor, higher conversions and purities are achieved. With branched phenylacetates, photoaddition affords diastereoisomeric mixtures with low to moderate de values. Subsequent acid-catalyzed dehydration furnishes the corresponding 3- arylmethyleneisoindolin-1-ones in good to excellent yields and with high E-selectivities. Irradiation of the parent 3-phenylmethyleneisoindolin-1-one under oxidative conditions only leads to cis/trans-isomerization.
- Belluau, Vincent,Noeureuil, Pierre,Ratzke, Elfrun,Skvortsov, Aleksei,Gallagher, Sonia,Motti, Cherri Ann,Oelgem?ller, Michael
-
scheme or table
p. 4738 - 4741
(2010/10/02)
-
- Assembly of substituted 3-methyleneisoindolin-1-ones via a cul/l-proline-catalyzed domino reaction process of 2-bromobenzamides and terminal alkynes
-
Cul/L-proline catalyzed coupling of 2-bromobenzamides and terminal alkynes in i-Pr0H (or DMF and DMSO) at 85-110 °C and subsequent additive cyclization produces substituted 3-methyleneisoindolin-1-ones. Variation of N-substituents, aromatic ring, and meth
- Li, Li,Wang, Miao,Zhang, Xiaojing,Jiang, Yongwen,Ma, Dawei
-
supporting information; experimental part
p. 1309 - 1312
(2009/08/07)
-
- A tandem elimination-cyclization-suzuki approach: Efficient one-pot synthesis of functionalized (Z)-3-(arylmethylene)isoindolin-1-ones
-
(Chemical Equation Presented) A novel and efficient one-pot regioselective elimination-cyclization-Suzuki approach was developed to afford (Z)-3-arylmethyleneisoindolin-1-ones in good to excellent yields from easily accessible o-gem-dihalovinylbenzamides and organoboron reagents.
- Sun, Caiyun,Xu, Bin
-
supporting information; experimental part
p. 7361 - 7364
(2009/05/07)
-
- A stereoselective synthesis of (Z)-3-aryl and alkylmethylidene-1H- isoindolin-1-ones
-
A series of Z-configured (hetero)aryl and alkylmethylideneisoindolin-1-ones has been efficiently prepared by treatment of N-methoxycarbonylisoindolin-1- ones with a base and reaction with selected aldehydes. The parent N-acylated isoindolin-1-ones have be
- Lamblin, Marc,Couture, Axel,Deniau, Eric,Grandclaudon, Pierre
-
p. 1333 - 1338
(2007/10/03)
-
- Synthesis of polyfunctional indoles and related heterocycles mediated by cesium and potassium bases
-
A general preparation of 2-substituted indoles starting from functionalized 2-alkynylanilines has been developed. This base mediated reaction has also been used to synthesize the heterocyclic core of the marine alkaloid hinckdentine A. Furthermore the reaction was successfully adapted to the solid phase. Benzofurans and isoindolones could also be prepared with this method.
- Koradin, Christopher,Dohle, Wolfgang,Rodriguez, Alain L.,Schmid, Bertram,Knochel, Paul
-
p. 1571 - 1587
(2007/10/03)
-
- Substituent effect on anionic cycloaromatization of 2-(2-substituted ethynyl)benzonitriles and related molecules
-
Methanolysis of 2-(2-substituted ethynyl)benzonitriles based on the nature of substituents gave 5-exo product, isoindolones and 6-endo product, isoquinolones, respectively. When a bulky substituent, such as tert-butyl group, was employed in this cyclization reaction, a 5-exo adduct was obtained. Phenyl and thienyl groups which can stabilize the α-anion affect the cyclization reaction to produce the 5-exo adducts. Pyridinyl and pyrazinyl groups can also stabilize the α-anion, but the formation of a more stable intermediate by coordination of sodium with nitrogen atom leads to the 6-endo products.
- Lu, Wen-Der,Lin, Chi-Fong,Wang, Chyi-Jia,Wang, Shih-Jen,Wu, Ming-Jung
-
p. 7315 - 7319
(2007/10/03)
-
- Solvent effects on aza-anionic cycloaromatization of 2-(2-substituted-ethynyl)benzonitriles
-
The methanolysis of 2-(2-aryl ethynyl)benzonitriles is accelerated when the polar aprotic solvents are added, which could enhance the 6-endo pathway and give isoquinolones, though the 5-exo pathway is occupied mostly. The yields of products would also be
- Lin, Chi-Fong,Yang, Jia-Huei,Hsieh, Pei-Chen,Lu, Wen-Der,Wu, Ming-Jung
-
p. 211 - 214
(2007/10/03)
-
- Palladium-catalysed heteroannulation with terminal alkynes: A highly regio- and stereoselective synthesis of (Z)-3-aryl(alkyl)idene isoindolin-1- ones
-
A highly regio- and stereoselective method for the synthesis of (Z)-3- aryl(alkyl)idene isoindolin-1-ones through palladium-copper catalysis is described. 2-Iodobenzamide 1 and its substituted derivatives 2-10 were reacted with terminal alkynes 11-19 in the presence of (PPh3)2PdCl2, CuI, and Et3N in DMF mostly at 80°C for 16 h to yield the 2-alkynyl substituted benzamides 20-38, 40-45, 77 which could then be cyclised with NaOEt in EtOH to the 3-aryl(alkyl)idene isoindolin-1-ones 46-49, 51, 53-55, 57, 59-71, 73 and 75. In certain cases, the isoindolin-1-ones 50, 52, 56 and 58 could be directly obtained by the palladium-catalysed reactions. (C) 2000 Elsevier Science Ltd.
- Kundu, Nitya G.,Khan, M. Wahab
-
p. 4777 - 4792
(2007/10/03)
-
- A direct anionic cyclization of 2-alkynylbenzonitrile to 3- substituted-1(2H)-isoquinolones and 3-benzylideneisoindol-2ones initiated by methoxide addition
-
Treatment of 2-(2-alkylethynyl)benzonitrile with sodium methoxide in refluxing methanol for 12 h gave 3-alkyl-1(2H)- isoquinolone in modest yield. Under the same reaction conditions, methanolysis of 2-(2-arylethynyl)benzonitrile lead to the formation of 3
- Wu, Ming-Jung,Chang, Li-Juan,Wei, Li-Mei,Lin, Chi-Fong
-
p. 13193 - 13200
(2007/10/03)
-
- A highly regio and stereoselective synthesis of (Z)-3- aryl(alkyl)idene isoindolin-1-ones via palladium catalyzed annulation of terminal alkynes
-
o-Iodobenzamide or its N-substituted derivatives 4-10 and terminal alkynes 11-17 reacted in DMF in the presence of bis(triphenylphosphine)palladium(II)chloride, cuprous iodide and triethylamine leading to (Z)-3- arylidene isoindolin-1-ones (22, 24, 27 and 28) or o-alkynyl N-substituted benzamides (I). The latter could be cyclised with sodium in ethanol in a completely regio and stereoselective manner to (Z)-3-aryl(alkyl)idene isoindolin-1-ones 18-35.
- Khan, M. Wahab,Kundu, Nitya G.
-
p. 1435 - 1437
(2007/10/03)
-
- AROMATIC HETEROANNULATION VIA ORTHO LITHIATION-CYCLIZATION OF N-ACYL-2-BROMOBENZAMIDES
-
N-acyl-2-bromobenzamides participate in metal-halogen exchange with n-BuLi to form N-acyl-2-lithiobenzamides, which undergo cyclization to afford 3-alkylidenephtalimides.
- Hendi, Mukta S.,Natalie, Kenneth J. Jr.,Hendi, Shivakumar B.,Campbell, James A.,Greenwood, Thomas D.,Wolfe, James F.
-
p. 275 - 278
(2007/10/02)
-
- Novel Lactam Synthesis by Use of a Combination System of Carbonylation and Nitrogenation
-
An amide unit was constructed from aryl halide and titanium-isocyanate complex prepared from TiCl4 under atmospheric pressure of molecular nitrogen and carbon monoxide in the presence of a palladium catalyst.With this combination system of carbonylation and nitrogenation, isoindolinone and quinazolinone derivatives were synthesized from o-halophenyl alkyl ketone in one step.The reaction proceeds through the oxidative addition of enol lactone, generated by palladium-catalyzed carbonylation to o-halophenyl alkyl ketone, to titanium-isocyanate complex.
- Uozumi, Yasuhiro,Kawasaki, Naofumi,Mori, Eiko,Mori, Miwako,Shibasaki, Masakatsu
-
p. 3725 - 3727
(2007/10/02)
-
- A Novel Diphenyl Phosphorazidate Catalysed Reaction of 3-Aryl-3,4-dihydro-1-oxo-1H-2-benzopyran-4-carboxylic Acids
-
Reaction of 3-(3',4'-dimethoxyphenyl)-(I) and 3-phenyl-(II)-3,4-dihydro-1-oxo-1H-2-benzopyran-4-carboxylic acids with diphenyl phosphorazidate takes an unusual course to form 2,3-dihydro-3-arylmethylene-1H-isoindole-1-ones (III and IV), the formation of w
- Dikshit, Dinesh K.
-
-