- IrIII-Catalyzed Selective ortho-Monoiodination of Benzoic Acids with Unbiased C?H Bonds
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An iridium-catalyzed selective ortho-monoiodination of benzoic acids with two equivalent C?H bonds is presented. A wide range of electron-rich and electron-poor substrates undergo the reaction under mild conditions, with >20:1 mono/di selectivity. Importantly, the C?H iodination occurs selectively ortho to the carboxylic acid moiety in substrates bearing competing coordinating directing groups. The reaction is performed at room temperature and no inert atmosphere or exclusion of moisture is required. Mechanistic investigations revealed a substrate-dependent reversible C?H activation/protodemetalation step, a substrate-dependent turnover-limiting step, and the crucial role of the AgI additive in the deactivation of the iodination product towards further reaction.
- Weis, Erik,Johansson, Magnus J.,Martín-Matute, Belén
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supporting information
p. 10185 - 10190
(2020/07/31)
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- Base- and Additive-Free Ir-Catalyzed ortho-Iodination of Benzoic Acids: Scope and Mechanistic Investigations
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A protocol for the C-H activation/iodination of benzoic acids catalyzed by a simple iridium complex has been developed. The method described in this paper allows the ortho-selective iodination of a variety of benzoic acids under extraordinarily mild conditions in the absence of any additive or base in 1,1,1,3,3,3-hexafluoroisopropanol as the solvent. The iridium catalyst used tolerates air and moisture, and selectively gives ortho-iodobenzoic acids with high conversions. Mechanistic investigations revealed that an Ir(III)/Ir(V) catalytic cycle operates, and that the unique properties of HFIP enables the C-H iodination using the carboxylic moiety as a directing group.
- Erbing, Elis,Sanz-Marco, Amparo,Vázquez-Romero, Ana,Malmberg, Jesper,Johansson, Magnus J.,Gómez-Bengoa, Enrique,Martín-Matute, Belén
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p. 920 - 925
(2018/02/14)
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- 2-Iodo-N-isopropyl-5-methoxybenzamide as a highly reactive and environmentally benign catalyst for alcohol oxidation
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Several N-isopropyliodobenzamides were evaluated as catalysts for the oxidation of benzhydrol to benzophenone in the presence of Oxone (2KHSO5·KHSO4·K2SO4) as a co-oxidant at room temperature. A study on the substituent effect of the benzene ring of N-isopropyl-2-iodobenzamide on the oxidation revealed that its reactivity increased in the following order of substitution: 5-NO2 2Me, 3-OMe 5-OAc 5-Cl H, 4-OMe 5-Me 5-OMe. The oxidation of various benzylic and aliphatic alcohols using a catalytic amount of the most reactive 5-methoxy derivative successfully resulted in moderate to excellent yields of the corresponding carbonyl compounds. The high reactivity of the 5-methoxy derivative at room temperature is a result of the rapid generation of the pentavalent species from the trivalent species during the reaction. 5-Methoxy-2-iodobenzamide would be an efficient and environmentally benign catalyst for the oxidation of alcohols, especially benzylic alcohols.
- Yakura, Takayuki,Fujiwara, Tomoya,Yamada, Akihiro,Nambu, Hisanori
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supporting information
p. 971 - 978
(2019/11/11)
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- Stereoretentive Intramolecular Glycosyl Cross-Coupling: Development, Scope, and Kinetic Isotope Effect Study
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A series of cyclic C-glycosides were synthesized using the palladium-catalyzed stereoretentive intramolecular glycosylation of aryl iodides by employing a bulky phosphine ligand. A variety of functional groups are tolerated in the reaction, and enantioenr
- Yi, Duk,Zhu, Feng,Walczak, Maciej A.
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supporting information
p. 4627 - 4631
(2018/08/07)
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- PYRROLE COMPOUNDS, A PROCESS FOR THEIR PREPARATION AND PHARMACEUTICAL COMPOSITIONS CONTAINING THEM
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Compounds of formula (I): wherein A1, A2, Ra, Rb, Rc, Rd, R3, R4, R5 and T are as defined in the description. Medicinal products containing the same which are useful in treating pathologies involving a deficit in apoptosis, such as cancer, auto-immune diseases, and diseases of the immune system.
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Paragraph 0419
(2015/02/19)
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- Lewis Acid Catalyzed Formal Intramolecular [3 + 3] Cross-Cycloaddition of Cyclopropane 1,1-Diesters for Construction of Benzobicyclo[2.2.2]octane Skeletons
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A novel Lewis acid catalyzed formal intramolecular [3 + 3] cross-cycloaddition (IMCC) of cyclopropane 1,1-diesters has been successfully developed. This supplies an efficient and conceptually new strategy for construction of bridged bicyclo[2.2.2]octane skeletons. This [3 + 3]IMCC could be run up to gram scale and from easily prepared starting materials. This [3 + 3]IMCC, together with our previously reported [3 + 2]IMCC strategy, can afford either the bicyclo[2.2.2]octane or bicyclo[3.2.1]octane skeletons from the similar starting materials by regulating the substituents on vinyl group.
- Ma, Weiwei,Fang, Jie,Ren, Jun,Wang, Zhongwen
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supporting information
p. 4180 - 4183
(2015/09/15)
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- Direct carbocyclizations of benzoic acids: Catalyst-controlled synthesis of cyclic ketones and the development of tandem aHH (acyl Heck-Heck) reactions
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The formation of exo-methylene indanones and indenones from simple ortho-allyl benzoic acid derivatives has been developed. Selective formation of the indanone or indenone products in these reactions is controlled by choice of ancillary ligand. This new process has a low environmental footprint as the products are formed in high yields using low catalyst loadings, while the only stoichiometric chemical waste generated from the reactants in the transformation is acetic acid. The conversion of the active cyclization catalyst into the Hermman-Beller palladacycle was exploited in a one-pot tandem acyl Heck-Heck (aHH) reaction, and utilized in the synthesis of donepezil. Carboxylic acids in aHH: Simple ortho-allyl benzoic acid derivatives have been utilized in an acyl Heck (aH) reaction to selectively form indanones and indenones. The conversion of the active cyclization catalyst into the Hermman-Beller palladacycle was exploited in a one-pot tandem acyl Heck-Heck (aHH) reaction to form two sp 2-sp2 bonds of (E)-trisubstituted olefins.
- Miles, Kelsey C.,Le, Chi,Stambuli, James P.
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supporting information
p. 11336 - 11339
(2014/10/16)
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- Palladium-catalyzed insertion of N-tosylhydrazones for the synthesis of isoindolines
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Isoindolines are synthesized by palladium-catalyzed coupling reaction of N-(2-iodobenzyl) anilines with α,β-unsaturated N-tosylhydrazones. The reaction has several potential advantages: (1) toleration of a wide range of functional groups, (2) easy to handle and with mild conditions, (3) enriches the isoindoline family, (4) two new bonds form in one step.
- Zhou, Ping-Xin,Luo, Jian-Yi,Zhao, Lian-Biao,Ye, Yu-Ying,Liang, Yong-Min
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supporting information
p. 3254 - 3256
(2013/05/08)
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- Amination of benzoxazoles and 1,3,4-oxadiazoles using 2,2,6,6- tetramethylpiperidine-N-oxoammonium tetrafluoroborate as an organic oxidant
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No transition metals are necessary to convert benzoxazoles and 1,3,4-oxadiazoles into the corresponding pharmacologically interesting 2-aminated heterocycles by formal direct C(2)-amination using tetramethylpiperidine-N-oxoammonium tetrafluoroborate (TEMPO+BF 4-) as an oxidant (see scheme; TEMP=2,2,6,6- tetramethylpiperidine; TfOH=trifluoromethanesulfonic acid).
- Wertz, Sebastian,Kodama, Shintaro,Studer, Armido
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supporting information; experimental part
p. 11511 - 11515
(2012/01/11)
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- PdII-catalyzed monoselective ortho halogenation of C-H bonds assisted by counter cations: A complementary method to directed ortho lithiation
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(Chemical Equation Presented) When the counterion counts: The yield and selectivity of the title transformation of benzoic acid derivatives were improved greatly by using tetraalkyl ammonium salts as additives (see scheme; monoselectivity: 5:1-18:1). These effects are attributed to the influence of counter cations. The halogenated products are versatile intermediates for the construction of substituted aromatic compounds. DMF=N,N-dimethylformamide.
- Mei, Tian-Sheng,Giri, Ramesh,Maugel, Nathan,Yu, Jin-Quan
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supporting information; experimental part
p. 5215 - 5219
(2009/04/11)
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- PROCESS FOR PRODUCTION OF IODINE COMPOUNDS AND PROCESS FOR PRODUCTION OF HIGH-PURITY 5-IODO-2-METHYLBENZOIC ACID
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Provided is a production method for an iodine compound in which iodine is reacted with a substrate in the presence of a porous material having a pore diameter of 500 nm or less or in the presence of the above porous material and an oxidizing agent and a production process for high purity 5-iodo-2-methylbenzoic acid comprising an iodination reaction step carried out by the above-mentioned, a crystal precipitation and separation step in which a product is precipitated by adding water or cooling and then separated and a purification step in which crystal separated is recrystallized using an organic solvent. According to the production method for an iodine compound described above, iodine can be introduced into various substrates at a high selectivity. Since expensive metals and specific reagents do not have to be used, it can readily be carried out in an industrially scale, and the product having a high purity can be obtained. Further, the process comprising the iodination reaction, separation and purification steps described above makes it possible to readily obtain at a high yield, 5-iodo-2-methylbenzoic acid having a high purity which is useful in uses for functional chemical products such as medicines. The process of the present invention comprising iodination reaction, separation and purification steps is characterized by that it is simple in terms of a procedure and that the purification load is smaller, and it is very advantageous in industrially carrying out.
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Page/Page column 8
(2008/06/13)
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- Immobilized Iodosobenzoate Catalysts for the Cleavage of Reactive Phosphates
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Titanium dioxide and nylon covalently supported iodosobenzoate reagents 11 and 19 have been prepared by the procedures outlined in Schemes I and II.Both 11 and 19 are good catalysts for the cleavage of p-nitrophenyl diphenyl phosphate (PNPDPP) under heter
- Moss, Robert A.,Chung, Yong-Chan
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p. 2064 - 2069
(2007/10/02)
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- Dibenz[b,f]oxepin derivatives
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Dibenz[b,f]oxepins of the formula STR1 wherein R, R1, R2, R3 and R4 are as hereinafter described. The foregoing compounds exhibit strong central depressant and neuroleptic properties, and are useful, for example
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- 10,11-Dihydro-dibenzo(b,f)thiepin derivatives
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Dibenzothiepin derivatives of the general formula STR1 wherein m, n, R1, R2, R3 and X are as hereinafter set forth, And salts thereof as well as processes for their manufacture are disclosed. The end products are useful as central-depressant and neuroleptic agents.
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