- Merging Electron Transfer with 1,2-Metalate Rearrangement: Deoxygenative Arylation of Aromatic Amides with Arylboronic Esters
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Amides are essentially inert carboxyl derivatives in many types of chemical transformations. In particular, deoxygenative C?C bond formation of amides to synthetically important amines is a long-standing challenge for synthetic chemists due to the inertness of the resonance-stabilized amide C=O bond. Herein, it is disclosed that by merging electron-transfer-induced activation with 1,2-metalate rearrangement, a wide range of aromatic amides react smoothly with arylboron reagents, affording a series of biologically relevant diarylmethylamines as deoxygenative C?C bond cross-coupling products. With its simplicity and versatility, this reaction shows great promise in the synthesis of amines from amides, which may open up new avenues in retrosynthetic planning and find widespread use in academia and industry.
- Jiao, Jiwen,Wang, Xiaoming
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supporting information
p. 17088 - 17093
(2021/06/28)
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- Dehydrogenative Aromatization and Sulfonylation of Pyrrolidines: Orthogonal Reactivity in Photoredox Catalysis
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Oxidative dehydrogenative aromatization and selective sulfonylation reactions of N-heterocycles under visible-light photoredox catalysis were established. The mild reaction conditions make this approach an appealing and versatile strategy to functionalize/oxidize pyrrolidines whereby arylsulfonyl chlorides were identified to be both catalyst regeneration and sulfonylation reagents.
- Muralirajan, Krishnamoorthy,Kancherla, Rajesh,Rueping, Magnus
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supporting information
p. 14787 - 14791
(2018/10/20)
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- Hydrogen-free reductive amination using iron pentacarbonyl as a reducing agent
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We developed solvent-free reductive amination without an external hydrogen source using iron pentacarbonyl as a reducing agent. Neither a catalyst nor any other additives were employed. Various types of substrates are suitable for the reaction, including
- Afanasyev, Oleg I.,Usanov, Dmitry L.,Chusov, Denis
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supporting information
p. 10164 - 10166
(2017/12/26)
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- Tertiary amine synthesis: Via reductive coupling of amides with Grignard reagents
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A new iridium catalyzed reductive coupling reaction of Grignard reagents and tertiary amides affording functionalised tertiary amine products via an efficient and technically-simple one-pot, two-stage experimental protocol, is reported. The reaction-which can be carried out on gram-scale using as little as 1 mol% Vaska's complex [IrCl(CO)(PPh3)2] and TMDS as the terminal reductant for the initial reductive activation step-tolerates a broad range of tertiary amides from (hetero)aromatic to aliphatic (branched, unbranched and formyl) and a wide variety of alkyl (linear, branched), vinyl, alkynyl and (hetero)aryl Grignard reagents. The new methodology has been applied directly to bioactive molecule synthesis and the high chemoselectivity of the reductive coupling of amide has been exploited in late stage functionalization of drug molecules. This reductive functionalisation of tertiary amides provides a new and practical solution to tertiary amine synthesis.
- Xie, Lan-Gui,Dixon, Darren J.
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p. 7492 - 7497
(2017/10/30)
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- Skin
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PROBLEM TO BE SOLVED: To provide a skin care preparation suitable for a cosmetic (provided that quasi drugs are included) or the like, for detail, a skin care preparation having whitening effects, particularly preventive or improving effects against pigme
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Paragraph 0066
(2018/03/23)
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- Skin care
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PROBLEM TO BE SOLVED: To provide a skin care preparation suitable for a cosmetic (provided that quasi drugs are included) or the like, for detail, a skin care preparation having whitening effects, particularly preventive or improving effects against pigme
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Paragraph 0065; 0067
(2017/10/05)
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- MELANIN PRODUCTION INHIBITOR
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Disclosed is a melanin production inhibitor which has an excellent inhibitory activity on the production of melanin and is highly safe. The melanin production inhibitor is represented by general formula (1) (excluding clotrimazole) and/or a pharmacologically acceptable salt thereof. In the formula, A1, A2 and A3 are independently selected from a hydrogen atom, an aryl group which may have a substituent, and an aromatic heterocyclic group which may have a substituent. At least one of A1, A2 and A3 is selected from the aryl group and the aromatic heterocyclic group, the total number of carbon atoms contained in A1, A2 and A3 is 6 to 50 and, when at least two of A1, A2 and A3 represent the aryl groups or the aromatic heterocyclic groups, the adjacent two aryl or aromatic heterocyclic groups may be bound to each other via an alkyl chain or an alkenyl chain to form a ring; m represents an integer of 0 to 2; X represents a hetero atom, a hydrogen atom, or a carbon atom; R1 and R2 are independently selected from a hydrogen atom and an oxo group. When one of R1 and R2 is an oxo group, the other is not present. R3 is selected from a hydrogen atom, and a C1-8 hydrocarbon group in which one or some of hydrogen atoms or carbon atoms may be substituted by a hetero atom or hetero atoms. The number of R3's present in the compound corresponds to X and, when two or more R3's are present, the R3's are independently present and the adjacent two R3's may be bound to each other to form, together with X, a ring, and the terminal of R3 may be bound to a carbon atom to which A1, A2 and A3 are bound, thereby forming a ring.
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Paragraph 0287- 0291
(2015/12/17)
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- MELANIN PRODUCTION INHIBITOR
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Disclosed is a melanin production inhibitor which has an excellent inhibitory activity on the production of melanin and is highly safe. The melanin production inhibitor comprises a compound represented by general formula (1) (excluding clotrimazole), and/or a pharmacologically acceptable salt thereof. In the formula, A1, A2 and A3 are independently selected from a hydrogen atom, an aryl group which may have a substituent, and an aromatic heterocyclic group which may have a substituent, wherein at least one of A1, A2 and A3 is selected from the aryl group and the aromatic heterocyclic group, the total number of carbon atoms contained in A1, A2 and A3 is 6 to 50 and, when at least two of A1, A2 and A3 represent the aryl groups or the aromatic heterocyclic groups, the adjacent two aryl or aromatic heterocyclic groups may be bound to each other via an alkyl chain or an alkenyl chain to form a ring; m represents an integer of 0 to 2; X represents a hetero atom, a hydrogen atom, or a carbon atom; R1 and R2 are independently selected from a hydrogen atom and an oxo group, wherein when one of R1 and R2 is an oxo group, the other is not present; and R3 is selected from a hydrogen atom, and a C1-8 hydrocarbon group in which one or some of hydrogen atoms or carbon atoms may be substituted by a hetero atom or hetero atoms, wherein the number of R3's present in the compound corresponds to the number of X's and, when two or more R3's are present, the R3's are independently present and the adjacent two R3's may be bound to each other to form, together with X, a ring, and the terminal of R3 may be bound to a carbon atom to which A1, A2 and A3 are bound, thereby forming a ring.
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- Three-component synthesis of α-branched amines under barbier-like conditions
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(Chemical Equation Presented) An array of α-branched amines has been prepared by using an expedient three-component Mannich-type reaction among organic halides, aldehyde derivatives, and amines. The experimental procedure, which is characterized by its simplicity, employs zinc dust for the in situ generation of organozinc reagents. We show that this Barbier-like protocol constitutes a useful entry to diarylmethylamines, 1,2-diarylethylamines, α- or β-amino esters, benzylamines, and β-arylethylamines.
- Le Gall, Erwan,Haurena, Caroline,Sengmany, Stephane,Martens, Thierry,Troupel, Michel
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supporting information; experimental part
p. 7971 - 7973
(2010/02/28)
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- Synthesis of tertiary sec-alkylamines by the addition of grignard reagents to N,N-dialkylformamides mediated by Ti(OiPr)4 and Me3SiCl
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A number of tertiary sec-alkylamines (22 examples, 29-80% yield) have been prepared according to a simple one-pot procedure by the addition of Grignard reagents to N,N-dialkylformamides in the presence of Ti(OiPr)4 and Me3SiCl. Wiley-VCH Verlag GmbH & Co. KGaA, 2008.
- Tomashenko, Olesya,Sokolov, Viktor,Tomashevskiy, Alexander,Buchholz, Herwig A.,Welz-Biermann, Urs,Chaplinski, Vladimir,De Meijere, Armin
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experimental part
p. 5107 - 5111
(2009/06/17)
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- Selective and catalytic arylation of N-phenylpyrrolidine: sp3 C-H bond functionalization in the absence of a directing group
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We herein describe our studies on arylation of N-phenylpyrrolidine, which led to the development of a new transformation for the direct and selective arylation of sp3 C-H bonds in the absence of a directing group. In this method, Ru(H)2(CO)(PCy3)3 4 was used as the catalyst, and preliminary mechanistic studies suggested that Ru(Ph)(I)(CO)(PCy3)2 5 is the key intermediate of the catalytic cycle. A large kinetic isotope effect (kH/kD = 5.4) was observed, which supports the proposal that C-H bond metalation is the slow step. Preliminary examination of the substrate scope showed that in addition to N-phenylpyrrolidine, N-methyl- and N-benzylpyrrolidine, as well as N-benzoylpyrrolidine, were arylated under the reaction conditions. Copyright
- Sezen, Bengue,Sames, Dalibor
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p. 5284 - 5285
(2007/10/03)
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- Aminoalkylation with aldehydes mediated by solid lithium perchlorate
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The solid LiClO4-mediated one-pot reaction of aldehydes with secondary amines and C nucleophiles afforded the corresponding aminoalkylation products in high yields. Unlike the previous reported procedure, the aminoalkylation of aldehyde was achieved in the presence of only 0.5 equivalents of solid lithium perchlorate in dichloromethane as the solvent with good to high yields at room temperature. Springer-Verlag 2003.
- Saidi, Mohammad R.,Nazari, Mohammad
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p. 309 - 312
(2007/10/03)
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- Efficient and chemoselective deoxygenation of amine N-oxides using polymethylhydrosiloxane
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Deoxygenation of aromatic and aliphatic amine N-oxides to the corresponding amines is achieved under mild conditions. The reagent combination employed for this transformation is polymethylhydrosiloxane (PMHS) in the presence of either tetrakis (triphenylphosphine) palladium (0) [Pd(PPh3)4], titanium (IV) isopropoxide [Ti(i-PrO)4] or palladium on carbon (Pd/C).
- Chandrasekhar,Reddy, Ch. Raji,Rao, R. Jagadeeshwar,Rao, J. Madhusudana
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p. 349 - 351
(2007/10/03)
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- Kinetics and Mechanism of Reactions of Benzhydryl Chlorides with Anilines
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Nucleophilic substitution reactions of substituted benzhydryl chlorides with anilines in acetonitrile and methanol are investigated.The reactions are found to proceed by the attack of nucleophile on the preformed carbocation, I, within the ion pair.The cr
- Chang, Saemin,Koh, Han Joong,Lee, Bon-Su,Lee, Ikchoon
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p. 7760 - 7768
(2007/10/03)
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- A Novel Deselenation in the Reaction of Selenoamides with Organolithium Reagents
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The reaction of selenoamides with organolithium reagents proceeds in a carbophilic manner, and more interestingly, the presence of excess lithium reagents causes a novel deselenation reaction from the carbophilic adducts.
- Sekiguchi, Masahito,Ogawa, Akiya,Fujiwara, Shin-Ichi,Ryu, Ilhyong,Kambe, Nobuaki,Sonoda, Noboru
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p. 2053 - 2056
(2007/10/02)
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