- Direct amidation of acid fluorides using germanium amides
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Amide functional groups are an essential linkage that are found in peptides, proteins, and pharmaceuticals and new methods are constantly being sought for their formation. Here, a new method for their preparation is presented where germanium amides Ph3GeNR2convert acid fluorides directly to amides. These germanium amides serve to abstract the fluorine atom of the acid fluoride and transfer their amide group -NR2to the carbonyl carbon, and so function as amidation reagents.
- Hayatifar, Ardalan,Elifritz, Emily A.,Bloom, Molly B.,Pixley, Kaitlyn M.,Fennell, Christopher J.,Weinert, Charles S.
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supporting information
p. 4490 - 4493
(2021/04/12)
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- METHOD FOR PRODUCING AMIDE COMPOUND
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PROBLEM TO BE SOLVED: To provide a method whereby, while using a catalyst that contains a transition metal and can be relatively easily synthesized, even with a small amount of the transition metal, an amide compound can be produce efficiently by the α-alkylation of the amide compound. SOLUTION: A method for producing an amide compound includes the step of: causing a primary alcohol compound and an amide compound to react with each other in a reaction liquid containing a transition metal nanoparticle (M-NPs) of at least one of a ruthenium nanoparticle or an iridium nanoparticle, and a base, to produce an amide compound. SELECTED DRAWING: None COPYRIGHT: (C)2021,JPOandINPIT
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Paragraph 0030; 0033-0041; 0046-0048
(2021/09/17)
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- Catalytic α-Hydroarylation of Acrylates and Acrylamides via an Interrupted Hydrodehalogenation Reaction
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The palladium-catalyzed, α-selective hydroarylation of acrylates and acrylamides is reported. Under optimized conditions, this method is highly tolerant of a wide range of substrates including those with base sensitive functional groups and/or multiple enolizable carbonyl groups. A detailed mechanistic study was undertaken, and the high selectivity of this transformation was shown to be enabled by the formation of a [PdII(Ar)(H)] intermediate, which performs selective hydride insertion into the β-position of α,β-unsaturated carbonyl compounds.
- Cherney, Emily C.,Engle, Keary M.,Gurak, John A.,Joe, Candice L.,Vasquez, Alena M.
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supporting information
p. 10477 - 10484
(2020/08/07)
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- Radical condensation between benzylic alcohols and acetamides to form 3-arylpropanamides
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A new radical condensation reaction is developed where benzylic alcohols and acetamides are coupled to generate 3-arylpropanamides with water as the only byproduct. The transformation is performed with potassium tert-butoxide as the only additive and gives rise to a variety of 3-arylpropanamides in good yields. The mechanism has been investigated experimentally with labelled substrates, trapping experiments and spectroscopic measurements. The findings indicate a radical pathway where potassium tert-butoxide is believed to serve a dual role as both base and radical initiator. The radical anion of the benzylic alcohol is proposed as the key intermediate, which undergoes coupling with the enolate of the amide to form the new C-C bond. Subsequent elimination to the corresponding cinnamamide and olefin reduction then affords the 3-arylpropanamides.
- Azizi, Kobra,Madsen, Robert
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p. 7800 - 7806
(2020/08/14)
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- NANO-ADHESIVE AND SURFACE PRIMER COMPOUND AND USE THEREOF
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A compound for self-assembly onto a mineral and/or metal oxides substrate, the compound comprising a catechol group attached to an end group through a spacer group. The compound include a structure of Formula (I):
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Paragraph 0267-0269
(2020/07/04)
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- method for alpha-alkylation of acetamides and thioacetamides under catalysis of nickel
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The invention discloses a method for alpha-alkylation of acetamide and thioacetamide under the catalysis of nickel. The method comprises the following steps: by taking a complex generated in situ by adivalent nickel salt and a phosphine ligand as a catalyst and primary alcohol as an alkylation reagent, performing alpha-alkylation reaction on acetamide or thioacetamide in an alkaline environment to prepare amide or thioamide. According to the alpha-alkylation reaction of acetamide and thioacetamide, the active catalyst can be generated in situ from a bivalent nickel salt and a phosphine ligand, so that the catalyst is prevented from being prepared in advance, the operation is simple and convenient, and experimental steps and cost are saved.
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-
Paragraph 0039; 0041; 0043-0048
(2020/12/05)
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- Nickel-catalyzed: C-alkylation of thioamide, amides and esters by primary alcohols through a hydrogen autotransfer strategy
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A simple catalyst of Ni(OAc)2 and P(t-Bu)3 enables selective C-alkylation of thioacetamides and primary acetamides with alcohols for the first time. Monoalkylation of thioamides, amides and t-butyl esters occurs in excellent yields (>95%). Mechanistic studies reveal that the reaction proceeds via a hydrogen autotransfer pathway. This journal is
- Yang, Peng,Wang, Xiuhua,Ma, Yu,Sun, Yaxin,Zhang, Li,Yue, Jieyu,Fu, Kaiyue,Zhou, Jianrong Steve,Tang, Bo
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supporting information
p. 14083 - 14086
(2020/11/20)
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- Efficient Organoruthenium Catalysts for α-Alkylation of Ketones and Amide with Alcohols: Synthesis of Quinolines via Hydrogen Borrowing Strategy and their Mechanistic Studies
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A new family of phosphine free organometallic ruthenium(II) catalysts (Ru1–Ru4) supported by bidentate NN Schiff base ligands (L1–L4 where L1=N,N-dimethyl-4-((2-phenyl-2-(pyridin-2-ylmethyl)hydrazineylidene)methyl) aniline, L2=N,N-diethyl-4-((2-phenyl-2-(pyridin-2-ylmethyl)hydrazineylidene)methyl)aniline, L3=N,N-dimethyl-4-((2-phenyl-2-(pyridin-2-yl)hydrazineylidene)methyl)- aniline and L4=N,N-diethyl-4-((2-phenyl-2-(pyridin-2-yl)hydrazineylidene)methyl) aniline) was prepared and characterized. These half-sandwich complexes acted as catalysts for C?C bond formation and exhibited excellent performance in the dehydrogenative coupling of ketones and amides. In the synthesis of C–C bonds, alcohols were utilized as the alkylating agent. A broad range of substrates, including sterically hindered ketones and alcohols, were well tolerated under the optimized conditions (TON up to 47000 and TOF up to 11750 h?1). This ruthenium (II) catalysts were also active towards the dehydrogenative cyclization of o-amino benzyl alcohol for the formation of quinolines derivatives. Various polysubstituted quinolines were synthesized in moderate to excellent yields (TON up to 71000 and TOF up to 11830 h?1). Control experiments were carried out and the ruthenium hydride intermediate was characterized to support the reaction mechanism and a probable reaction pathway of dehydrogenative coupling for the C?C bond formation has been proposed.
- Maji, Ankur,Singh, Anshu,Singh, Neetu,Ghosh, Kaushik
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p. 3108 - 3125
(2020/05/18)
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- One-Pot Controlled Reduction of Conjugated Amides by Sequential Double Hydrosilylation Catalyzed by an Iridium(III) Metallacycle
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A single and accessible cationic iridiumIII metallacycle effectively catalyzes the one-pot sequential double hydrosilylation of challenging α,β-unsaturated secondary and tertiary amides to afford, in a controlled and straightforward way, the co
- Agbossou-Niedercorn, Francine,Corre, Yann,Djukic, Jean-Pierre,Kalocsai, Dorottya,Michon, Christophe,Nagyházi, Márton,Rysak, Vincent,Trivelli, Xavier
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supporting information
p. 6212 - 6220
(2020/10/02)
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- High-Throughput Ligand Screening Enables the Enantioselective Conjugate Borylation of Cyclobutenones to Access Synthetically Versatile Tertiary Cyclobutylboronates
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Cyclobutane rings are important in medicinal chemistry, yet few enantioselective methods exist to access this scaffold. In particular, cyclobutylboronates are receiving increasing attention in the literature due to the synthetic versatility of alkylboronic esters and the increasing role of boronic acids in drug discovery. Herein, a conjugate borylation of α-alkyl,β-aryl/alkyl cyclobutenones is reported leading to the first synthesis of enantioenriched tertiary cyclobutylboronates. Cyclobutanones with two stereogenic centers are obtained in good to high yield, with high enantioselectivity and diastereoselectivity. Vital to this advance are the development of a novel approach to α,β unsymmetrically disubstituted cyclobutenone substrates and the use of a high-throughput chiral ligand screening platform. The synthetic utility of both the boronic ester and ketone functionalities is displayed, with remarkable chemoselectivity for either group being possible in this small ring scaffold.
- Clement, Helen A.,Boghi, Michele,McDonald, Rory M.,Bernier, Louise,Coe, Jotham W.,Farrell, William,Helal, Christopher J.,Reese, Matthew R.,Sach, Neal W.,Lee, Jack C.,Hall, Dennis G.
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supporting information
p. 18405 - 18409
(2019/11/16)
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- Bidentate Ru(II)-NC Complexes as Catalysts for α-Alkylation of Unactivated Amides and Esters
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Five Ru(II)-NC complexes were tested as catalysts for α-alkylation of unactivated amides using alcohols as alkylating agents, and complex {(C5H4N)-(C6H4)}RuCl(CO)(PPh3)2 (1) showed the highest activity. With 0.5 mol% catalyst loading, a series of α-alkylated amides were isolated at 80 °C within 6 hours. Furthermore, under similar conditions, complex 1 was also active for α-alkylation of unactivated esters with alcohols, and the reaction time was shortened to 1.5 hours. The catalytic performance of 1 is comparable to the best reported catalyst.
- Gong, Dawei,Hu, Bowen,Yang, Weiwei,Chen, Dafa
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p. 4841 - 4847
(2019/11/05)
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- Manganese-catalyzed direct C-C coupling of α-C-H bonds of amides and esters with alcohols: Via hydrogen autotransfer
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Herein we report an efficient manganese-catalyzed C-alkylation of unactivated amides and tert-butyl acetate using alcohols as alkylating agents. This elegant approach exhibits a broad substrate scope providing the C-C coupled products of amides via a hydrogen auto-transfer strategy using aryl, heteroaryl, and aliphatic alcohols.
- Rana, Jagannath,Gupta, Virendrakumar,Balaraman, Ekambaram
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supporting information
p. 7094 - 7099
(2019/06/06)
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- Iridium-Catalyzed Alkene-Selective Transfer Hydrogenation with 1,4-Dioxane as Hydrogen Donor
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The iridium-catalyzed transfer hydrogenation of alkenes using 1,4-dioxane as a hydrogen donor is described. The use of 1,2-bis(dicyclohexylphosphino)ethane (DCyPE), featuring bulky and highly electron-donating properties, led to high catalytic activity. A polystyrene-cross-linking bisphosphine PS-DPPBz produced a reusable heterogeneous catalyst. These homogeneous and heterogeneous protocols achieved chemoselective transfer hydrogenation of alkenes over other potentially reducible functional groups such as carbonyl, nitro, cyano, and imino groups in the same molecule.
- Zhang, Deliang,Iwai, Tomohiro,Sawamura, Masaya
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supporting information
p. 5867 - 5872
(2019/08/26)
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- Chemoselective α,β-Dehydrogenation of Saturated Amides
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We report a method for the selective α,β-dehydrogenation of amides in the presence of other carbonyl moieties under mild conditions. Our strategy relies on electrophilic activation coupled to in situ selective selenium-mediated dehydrogenation. The α,β-unsaturated products were obtained in moderate to excellent yields, and their synthetic versatility was demonstrated by a range of transformations. Mechanistic experiments suggest formation of an electrophilic SeIV species.
- Teskey, Christopher J.,Adler, Pauline,Gon?alves, Carlos R.,Maulide, Nuno
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supporting information
p. 447 - 451
(2019/01/04)
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- Palladium-Catalyzed Hydrocarbonylative C-N Coupling of Alkenes with Amides
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An efficient palladium-catalyzed hydrocarbonylative C-N coupling of alkenes with amides has been developed. The reaction was performed via hydrocarbonylation of alkenes, followed by acyl metathesis with amides. Both intermolecular and intramolecular react
- Zhou, Xibing,Zhang, Guoying,Gao, Bao,Huang, Hanmin
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supporting information
p. 2208 - 2212
(2018/04/30)
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- NCP ligand, [...] complex, synthesis method, intermediate and application
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The invention discloses an NCP ligand, iridium complex, synthetic method, intermediate and application thereof. The invention provides an NCP ligand and an NCP ligand iridium complex, wherein R1, R2, R3, R4, R5, R6 and R7 separately represent hydrogen atom or C1-C30 alkyl, R' and R'' independently represent C1-C30 alkyl. The invention provides the application of the NCP ligand iridium complex to the catalysis of alkane dehydrogenation reaction, olefin isomerization reaction, alcohol dehydrogenation reaction, ester alpha alkylation reaction, and amide alpha alkylation reaction. The NCP ligand provided by the invention contains dialkyl substituted phosphine, which has strong electron donating ability and can form a NCP ligand iridium complex by complexing with iridium. The NCP ligand iridium complex uses pyridine to replace a conventional alkyl phosphate electron donor, and has the advantages of good stability, high selectivity on alkane dehydrogenation reaction, mild reaction conditions, good catalytic effect, and industrial production prospect.
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-
Paragraph 0138; 0218-0221
(2018/07/30)
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- Sustainable Alkylation of Unactivated Esters and Amides with Alcohols Enabled by Manganese Catalysis
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The first example of manganese-catalyzed C-alkylation of the carboxylic acid derivatives is reported. The bench-stable homogeneous manganese complex enables the transformation of the renewable alcohol and carboxylic acid derivative feedstock to higher value esters and amides. The reaction operates via hydrogen autotransfer and ideally produces water as the only side product. Importantly, aliphatic-, benzylic-, and heterocyclic-containing alcohols can be used as alkylating reagents, eliminating the need for mutagenic alkyl halides.
- Jang, Yoon Kyung,Krückel, Tobias,Rueping, Magnus,El-Sepelgy, Osama
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supporting information
p. 7779 - 7783
(2018/12/14)
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- Manganese-Catalyzed α-Alkylation of Ketones, Esters, and Amides Using Alcohols
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Herein we report the manganese-catalyzed C-C bond-forming reactions via α-alkylation of ketones, amides, and esters, using primary alcohols. β-Alkylation of secondary alcohols by primary alcohols to obtain α-alkylated ketones is also reported. The reactions are catalyzed by a (iPr-PNP)Mn(H)(CO)2 pincer complex under mild conditions in the presence of (catalytic) base liberating water (and H2 in the case of secondary alcohol alkylation) as the sole byproduct.
- Chakraborty, Subrata,Daw, Prosenjit,Ben David, Yehoshoa,Milstein, David
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p. 10300 - 10305
(2018/10/20)
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- Ni-Catalyzed Α-Alkylation of Unactivated Amides and Esters with Alcohols by Hydrogen Auto-Transfer Strategy
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A transition-metal-catalyzed borrowing hydrogen/hydrogen auto-transfer strategy allows the utilization of feedstock alcohols as an alkylating partner, which avoids the formation of stoichiometric salt waste and enables a direct and benign approach for the construction of C-N and C?C bonds. In this study, a nickel-catalyzed α-alkylation of unactivated amides and ester (tert-butyl acetate) is carried out by using primary alcohols under mild conditions. This C?C bond-forming reaction is catalyzed by a new, molecularly defined nickel(II) NNN-pincer complex (0.1–1 mol %) and proceeds through hydrogen auto-transfer, thereby releasing water as the sole byproduct. In addition, N-alkylation of cyclic amides under Ni-catalytic conditions is demonstrated.
- Midya, Siba P.,Rana, Jagannath,Pitchaimani, Jayaraman,Nandakumar, Avanashiappan,Madhu, Vedichi,Balaraman, Ekambaram
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p. 3911 - 3916
(2018/11/23)
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- Amidation reaction of carboxylic acid with formamide derivative using SO3?pyridine
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The amidation reaction of carboxylic acid derivatives was developed using sulfur trioxide pyridine complex (SO3?py) as a commercially available and easily handled oxidant. This method could be applied to the reaction of various aromatic and aliphatic carboxylic acids, including optically active ones, with formamide derivatives to afford the corresponding amides in good to high yields.
- Kawano, Shota,Saito, Kodai,Yamada, Tohru
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supporting information
p. 584 - 586
(2018/04/12)
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- Rhodium-Catalyzed Asymmetric Synthesis of β-Branched Amides
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A general asymmetric route for the one-step synthesis of chiral β-branched amides is reported through the highly enantioselective isomerization of allylamines, followed by enamine exchange, and subsequent oxidation. The enamine exchange allows for a rapid and modular synthesis of various amides, including challenging β-diaryl and β-cyclic.
- Wu, Zhao,Laffoon, Joshua D.,Nguyen, Trang T.,McAlpin, Jacob D.,Hull, Kami L.
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supporting information
p. 1371 - 1375
(2017/01/24)
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- Hydrogen-transfer reduction of α,β-unsaturated carbonyl compounds catalyzed by naphthyridine-functionalized N-heterocyclic carbene complexes
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Substitution of silver complex of 2-chloro-7-(mesitylimidazolylidenylmethyl)naphthyridine (NpNHC) with palladium(II), rhodium(I) and iridium(I) metal precursors provided [Pd(C,N-NpNHC)(η3-allyl)](BF4) (5), RhCl(COD)(C-NpNHC) (6a) and IrCl(COD)(C-NpNHC) (6b), respectively. Abstraction of chloride from 6a and 6b with AgBF4 provided the chelation complexes [Rh(COD)(C,N-NpNHC)](BF4) (7a) and Ir(COD)(C,N-NpNHC)(BF4) (7b), respectively. All complexes were characterized using NMR and elemental analyses and the structural details of 5 and 6a were further confirmed using X-ray crystallography. In catalytic activity studies, complex 5 was found to be an effective catalyst in the hydrogen-transfer reduction of α,β-unsaturated carbonyl compounds into the corresponding saturated carbonyl compounds.
- Huang, Hsiao-Ching,Ramanathan, Mani,Liu, Yi-Hong,Peng, Shie-Ming,Liu, Shiuh-Tzung
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- General and Mild Cobalt-Catalyzed C-Alkylation of Unactivated Amides and Esters with Alcohols
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The borrowing hydrogen or hydrogen autotransfer methodology is an elegant and sustainable or green concept to construct carbon-carbon bonds. In this concept, alcohols, which can be obtained from barely used and indigestible biomass, such as lignocellulose, are employed as alkylating reagents. An especially challenging alkylation is that of unactivated esters and amides. Only noble metal catalysts based on iridium and ruthenium have been used to accomplish these reactions. Herein, we report on the first base metal-catalyzed α-alkylation of unactivated amides and esters by alcohols. Cobalt complexes stabilized with pincer ligands, recently developed in our laboratory, catalyze these reactions very efficiently. The precatalysts can be synthesized easily from commercially available starting materials on a multigram scale and are self-activating under the basic reaction conditions. This Co catalyst class is also able to mediate alkylation reactions of both esters and amides. In addition, we apply the methodology to synthesize ketones and to convert alcohols into aldehydes elongated by two carbon atoms.
- Deibl, Nicklas,Kempe, Rhett
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p. 10786 - 10789
(2016/09/09)
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- Rhodium-catalyzed oxidative amidation of allylic alcohols and aldehydes: Effective conversion of amines and anilines into amides
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The rhodium-catalyzed oxidative amidation of allylic alcohols and aldehydes is reported. In situ generated [(BINAP)Rh]BF4 catalyzes the one-pot isomerization/oxidative amidation of allylic alcohols or direct amidation of aldehydes using acetone or styrene as the hydrogen acceptor. The conditions are general, affording good to excellent yields with a wide array of amine and aniline nucleophiles, and chemoselective, other alcohols do not participate in the oxidation reaction. Utilization of biphasic conditions is critical, as they promote an equilibrium between the imine/enamine byproducts and the hemiaminal, which can undergo oxidation to the amide.
- Wu, Zhao,Hull, Kami L.
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p. 969 - 975
(2016/02/05)
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- A highly efficient catalytic α-alkylation of unactivated amides using primary alcohols
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The α-alkylation of unactivated amides with alcohols is described. Using a NCP-type pincer Ir complex as the precatalyst and KOtBu as the base, the reactions of secondary or tertiary acetamides with benzyl or nonbenzyl primary alcohols occur at 80 °C, furnishing the alkylation products in good yields. This method represents a practical and green means of α-alkylation of amides in a relatively mild, efficient, and selective manner with low catalyst loadings (0.5 mol %).
- Yao, Wubing,Ma, Xiaochen,Guo, Le,Jia, Xiangqing,Hu, Aiguo,Huang, Zheng
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supporting information
p. 2919 - 2921
(2016/06/13)
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- Ruthenium-catalyzed direct α-alkylation of amides using alcohols
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The highly efficient direct α-alkylation of unactivated amides has been accomplished using alcohols in the presence of the Ru-PNN catalyst (0.1 mol%) with a high turnover number. Using this approach, 2-oxindole was directly transformed into C3-alkylated 3-hydroxyindolin-2-one in one step without the use of any oxidant.
- Chaudhari, Moreshwar Bhagwan,Bisht, Girish Singh,Kumari, Pooja,Gnanaprakasam, Boopathy
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supporting information
p. 9215 - 9220
(2016/10/13)
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- MONONUCLEAR IRON COMPLEX AND ORGANIC SYNTHESIS REACTION USING SAME
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Provided is a mononuclear iron complex that comprises an iron-silicon bond that is represented by formula (1) and that exhibits excellent catalyst activity in each of a hydrosilylation reaction, a hydrogenation reaction, and reduction of a carbonyl compound. In formula (1), R1-R6 either independently represent an alkyl group, an aryl group, an aralkyl group or the like that may be substituted with a hydrogen atom or X, or represent a crosslinking substituent in which at least one pair comprising one of R1-R3 and one of R4-R6 is combined. X represents a halogen atom, an organoxy group, or the like. L represents a two-electron ligand other than CO. When a plurality of L are present, the plurality of L may be the same as or different from each other. When two L are present, the two L may be bonded to each other. n and m independently represent an integer of 1 to 3 with the stipulation that n+m equals 3 or 4.
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- MONONUCLEAR RUTHENIUM COMPLEX AND ORGANIC SYNTHESIS REACTION USING SAME
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Provided is a mononuclear ruthenium complex that comprises a ruthenium-silicon bond that is represented by formula (1) and that exhibits excellent catalyst activity in each of a hydrosilylation reaction, a hydrogenation reaction, and reduction of a carbon
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- Easy access to amides through aldehydic C-H bond functionalization catalyzed by heterogeneous Co-based catalysts
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A novel synthesis strategy for amides by oxidative amidation of aldehydes is developed using a heterogeneous Co-based catalyst. The Co composite was prepared by simple pyrolysis of a Co-containing MOF, to obtain well-dispersed Co nanoparticles enclosed by carbonized organic ligands. The catalysts were characterized by powder X-ray diffraction (PXRD), N2 physical adsorption, atomic absorption spectroscopy (AAS), transmission electron microscopy (TEM), scanning electronic microscopy (SEM), and X-ray photoelectron spectroscopy (XPS). The small Co nanoparticles embedded in the N-doped carbons were highly dispersed with an average size of ca. 7 nm. The Co@C-N materials exhibited significantly enhanced catalytic activity in the oxidative amidation of aldehydes in comparison to those of commercial sources. A series of amides can be easily obtained in good to excellent yields. It was found that the reaction proceeded via radicals under mild conditions, and the carbonyl group in the amide product was from the aldehyde. Moreover, the catalyst could be easily separated by using an external magnetic field and reused several times without significant loss in catalytic efficiency under the investigated conditions. (Chemical Equation Presented).
- Bai, Cuihua,Yao, Xianfang,Li, Yingwei
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p. 884 - 891
(2015/02/19)
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- Electrophilic trifluoromethylthiolation of carbonyl compounds
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A general method for the α-trifluoromethylthiolation of carbonyl compounds, without prefunctionalization, has been developed. Aldehydes, ketones, esters, amides, keto-esters, alkaloids, and steroids have been trifluoromethylthiolated with good yields. This work, proposing a new reagent for electrophilic trifluoromethylthiolation, provides a route towards the original synthesis of various trifluoromethylthiolated molecules for further applications.
- Alazet, Sebastien,Zimmer, Luc,Billard, Thierry
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supporting information
p. 8589 - 8593
(2014/07/21)
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- A novel method for the conversion of carboxylic acids to N,N-dimethylamides using N,N-dimethylacetamide as a dimethylamine source
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A simple, cost effective and environmentally benign method is reported for the preparation of N,N-dimethylamides from carboxylic acids. The versatility of the method is determined by synthesising a large number of N,N-dimethylamide derivatives. Carboxylic acids are heated at 160-165°C in N,N-dimethylacetamide solvent in the presence of1,1'-carbonyldiimidazole to afford the corresponding N,N-dimethylamides in good to excellent yields.
- Aavula, Sanjeev Kumar,Chikkulapally, Anil,Hanumanthappa,Jyothi, Indira,Vinod,Sulur, Kumar,Manjunatha,Sythana, Suresh Kumar
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p. 155 - 159
(2013/07/11)
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- Iridium-catalyzed selective α-alkylation of unactivated amides with primary alcohols
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The first α-alkylation of unactivated amides with primary alcohols is described. An effective and robust iridium pincer complex has been developed for selective α-alkylation of tertiary and secondary acetamides involving a borrowing hydrogen methodology. The method is compatible with alcohols bearing various functional groups. This presents a convenient and environmentally benign protocol for α-alkylation of amides.
- Guo, Le,Liu, Yinghua,Yao, Wubing,Leng, Xuebing,Huang, Zheng
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supporting information
p. 1144 - 1147
(2013/04/10)
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- Ruthenium hydride/nitrogen tridentate ligand-catalyzed α-alkylation of acetamides with primary alcohols
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The α-alkylation reaction of acetamides with primary alcohols to afford the corresponding amides was accomplished effectively using RuHCl(CO)(PPh3)3 as a catalyst, nitrogen tridentate ligand L1 as an additive, and KOtBu as a base. While the addition of bpy was effective only for benzylic alcohols, L1 affected the alkylation reaction when both benzylic and non-benzylic type alcohols were used.
- Kuwahara, Takashi,Fukuyama, Takahide,Ryu, Ilhyong
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p. 13702 - 13704
(2013/08/23)
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- Copper-catalyzed amidation of acids using formamides as the amine source
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Copper-catalyzed amidation of acids with formamides or acetamide for the selective synthesis of amides with the aid of 1,4-diazabicyclo[2.2.2]octane as the ligand and tert-butyl hydroperoxide as the oxidant is presented. This method is highly compatible with a wide range of acids, including alkyl acids, aryl acids, α,β-unsaturated acids, and amino acids. A general and direct route for the synthesis of amides is described. The reaction involves the copper-catalyzed amidation of acids, wherein various formamides and an acetamide are used as the amine source. Importantly, this method represents a new strategy for the direct use of acids in the synthesis of amides. DABCO = 1,4-diazabicyclo[2.2.2]octane, TBHP = tert-butyl hydroperoxide. Copyright
- Xie, Ye-Xiang,Song, Ren-Jie,Yang, Xu-Heng,Xiang, Jian-Nan,Li, Jin-Heng
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p. 5737 - 5742
(2013/09/12)
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- Simple one-pot synthesis of Rh-Fe3O4 heterodimer nanocrystals and their applications to a magnetically recyclable catalyst for efficient and selective reduction of nitroarenes and alkenes
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A simple synthesis of Rh-Fe3O4 heterodimer nanocrystals was achieved by controlled one-pot thermolysis. The nanocrystals exhibited excellent activities for the selective reduction of nitroarenes and alkenes. Furthermore the nanocrystal catalyst could be easily separated by a magnet, and recycled eight times without losing the catalytic activity.
- Jang, Youngjin,Kim, Seyoung,Jun, Samuel Woojoo,Kim, Byung Hyo,Hwang, Sunhwan,Song, In Kyu,Kim, B. Moon,Hyeon, Taeghwan
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supporting information; experimental part
p. 3601 - 3603
(2011/04/26)
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- Condensation of aromatic aldehydes with VyV-dimethylacetamide in presence of dialkyl carbonates as dehydrating agents
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Reactions of benzaldehydes with excess N,N- dimethylacetamide at 140 °C in the presence of diethyl carbonate as dehydrating agent and a base gave (E)-N,N- dimethylcinnamamides in good yields. If hydroxybenzal- dehydes are used as substrates the reaction is accompanied by alkylation. Springer-Verlag 2010.
- Weidlich, Tomas,Prokes, Lubomir,Ruzicka, Ales,Padelkova, Zdenka
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experimental part
p. 205 - 211
(2010/08/22)
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- Use of potassium β-trifluoroborato amides in suzuki-miyaura cross-coupling reactions
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(Chemical Equation Presented) Potassium β-trifluoroborato amides were prepared and used as successful partners in Suzuki-Miyaura reactions with various aryl chlorides, including electron-rich and electron-poor derivatives, as well as several heteroaryl ch
- Molander, Gary A.,Jean-Gerard, Ludivine
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supporting information; experimental part
p. 5446 - 5450
(2009/12/08)
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- Practical access to amines by platinum-catalyzed reduction of carboxamides with hydrosilanes: Synergy of dual Si-H groups leads to high efficiency and selectivity
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The synergetic effect of two Si-H groups leads to efficient reduction of carboxamides to amines by platinum catalysts under mild conditions. The rate of the reaction is dependent on the distance of two Si-H groups; 1,1,3,3-tetramethyldisiloxane (TMDS) and 1,2-bis(dimethylsilyl)benzene are found to be an effective reducing reagent. The reduction of amides having other reducible functional groups such as NO2, CO2R, CN, CdC, Cl, and Br moieties proceeds with these groups remaining intact, providing a reliable method for the access to functionalized amine derivatives. The platinum-catalyzed reduction of amides with polymethylhydrosiloxane (PMHS) also proceeds under mild conditions. The reaction is accompanied by automatic removal of both platinum and silicon wastes as insoluble silicone resin, and the product is obtained by simple extraction. A mechanism involving double oxidative addition of TMDS to a platinum center is discussed.
- Hanada, Shiori,Tsutsumi, Emi,Motoyama, Yukihiro,Nagashima, Hideo
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supporting information; experimental part
p. 15032 - 15040
(2010/01/29)
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- Hydrosilane reduction of tertiary carboxamides by iron carbonyl catalysts
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Fox in the carboxamide: Reduction of tertiary carboxamides to their corresponding amines is catalyzed by [Fe(CO)5] or [Fe 3(CO)12], using 1,1,3,3tetramethyldlsiloxane (TMDS) as the reducing agent. The reaction proceeds under either thermal or photochemical conditions. Unlike the hydrosilane reduction of amides using platinum or ruthenlum catalysts, TMDS preferentially reduces a nitro group, even in the presence of competing amides.
- Sunada, Yusuke,Kawakami, Hiroko,Imaoka, Tsuyoshi,Motoyama, Yukihiro,Nagashima, Hideo
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supporting information; experimental part
p. 9511 - 9514
(2010/03/24)
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- Palladium/phosphite-catalyzed 1,4-addition of arylboronic acids to acrylic acid derivatives
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(Chemical Equation Presented) 1,4-Addition of arylboronic acids to acrylic acid derivatives proceeds efficiently in the presence of a palladium catalyst system of Pd(OAc)2/(PhO)3P to produce the corresponding 3-arylpropionic acid derivatives. The use of the phosphite ligand is the key to conducting the addition smoothly with suppressing the competing Mizoroki-Heck-type oxidative coupling.
- Horiguchi, Hakaru,Tsurugi, Hayato,Satoh, Tetsuya,Miura, Masahiro
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p. 1590 - 1592
(2008/09/17)
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- One-pot amidation of olefins through Pd-catalyzed coupling of alkylboranes and carbamoyl chlorides
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(Chemical Equation Presented) A one-pot synthesis of C1- elongated amides starting from olefins and carbamoyl chlorides has been developed. Alkyl-boranes, generated by hydroboration of terminal olefins with 9-BBN-H, underwent smooth coupling with carbamoyl chlorides in the presence of palladium catalyst and Cs2CO3.
- Yasui, Yoshizumi,Tsuchida, Sayo,Miyabe, Hideto,Takemoto, Yoshiji
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p. 5898 - 5900
(2008/02/09)
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- Heck-type coupling vs. conjugate addition in phosphine-rhodium catalyzed reactions of aryl boronic acids with α,β-unsaturated carbonyl compounds: A systematic investigation
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The competition between Heck-type coupling and conjugate addition in phosphine-rhodium catalyzed reactions of aryl boronic acids with α,β-unsaturated carbonyls has been systematically investigated in a toluene-H2O biphasic system. Aside from the intrinsic nature of rhodium and the enolization of carbonyls, the phosphine supporting ligand on rhodium, the ratio of aryl boronic acid to α,β-unsaturated carbonyl and the pH value of the aqueous phase were found to affect the competition significantly. Highly selective rhodium-based catalyst systems have therefore been developed for both Heck-type coupling and conjugate addition by synergistically tuning the supporting ligand, the boronic acid to olefin ratio and other reaction conditions. Conjugate addition with selectivity >99% and Heck-type coupling with selectivity of up to 100%, 98% and 84% for acrylates, acrylamides and methyl vinyl ketone, respectively, could be achieved in the rhodium-catalyzed reactions of aryl boronic acids with α,β- unsaturated carbonyls using the corresponding optimized rhodium-based catalyst systems. The Royal Society of Chemistry.
- Zou, Gang,Guo, Jianping,Wang, Zhiyong,Huang, Wen,Tang, Jie
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p. 3055 - 3064
(2008/02/09)
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- Borrowing hydrogen: Indirect "Wittig" olefination for the formation of C-C bonds from alcohols
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The successful development of an indirect three-step domino sequence for the formation of C-C bonds from alcohol substrates is described. An iridium-catalysed dehydrogenation of alcohol 1 affords the intermediate aldehyde 2. The desired C-C bond can then be formed by a facile Wittig olefination, yielding the intermediate alkene 3. In the final step the alkene is hydrogenated to afford the indirect Wittig product, the alkane 4. The key to this process is the concept of borrowing hydrogen; hydrogen removed in the initial dehydrogenation step is simply borrowed by the iridium catalyst. Functioning as a hydrogen reservoir, the catalyst facilitates C-C bond formation before subsequently returning the borrowed hydrogen in the final step. Herein we present full details of our examination into both the substrate and reaction scope and the limitations of the catalytic cycle. Wiley-VCH Verlag GmbH & Co. KGaA, 2006.
- Black, Phillip J.,Edwards, Michael G.,Williams, Jonathan M. J.
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p. 4367 - 4378
(2007/10/03)
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- Aromatic chlorination of ω-phenylalkylamines and ω- phenylalkylamides in carbon tetrachloride and α,α,α- trifluorotoluene
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The aromatic halogenation of simple alkylbenzenes with chlorine proceeds smoothly in acetic acid but is much less efficient in less polar solvents. By contrast chlorination of ω-phenylalkylamines, such as 3-phenylpropylamine, occurs readily in either acetic acid, carbon tetrachloride or α,α,α-trifluorotoluene, and in the latter solvents gives high proportions of ortho-chlorinated products. These effects are attributable to the involvement of N-chloroamines as reaction intermediates, with intramolecular delivery of the chlorine electrophile. ω-Phenylalkylamides, such as 3-phenylpropionamide, also easily undergo aromatic chlorination in carbon tetrachloride and α,α,α-trifluorotoluene. These reactions generally show a first-order dependence on the substrate concentration, but not on the amount of chlorine. With carbon tetrachloride, very similar reaction rates are observed with chlorine concentrations ranging from 0.1-1.5 M. In α,α,α-trifluorotoluene, the rates reach a plateau at a chlorine concentration of approximately 0.2 M. These features indicate that the reactions proceed via the formation of intermediates which evidence suggests may be the corresponding O-chloroimidates. Irrespective of the mechanistic details, the reactions are remarkably rapid, being faster than analogous reactions in acetic acid and three to four orders of magnitude more rapid than reactions of simple alkylbenzenes in carbon tetrachloride. Therefore, chlorination of the amines and amides may be accomplished without the need for highly polar solvents, added catalysts or large excesses of chlorine, which are often employed for electrophilic aromatic substitutions. Although the use of carbon tetrachloride is becoming increasingly impractical due to environmental concerns, the trifluorotoluene is a suitable alternative. The Royal Society of Chemistry 2006.
- O'Connell, Jenny L.,Simpson, Jamie S.,Dumanski, Paul G.,Simpson, Gregory W.,Easton, Christopher J.
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p. 2716 - 2723
(2008/02/08)
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- Self-encapsulation of homogeneous catalyst species into polymer gel leading to a facile and efficient separation system of amine products in the Ru-catalyzed reduction of carboxamides with polymethylhydrosiloxane (PMHS)
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A practical procedure for production of amines is offered by the ruthenium-catalyzed reduction of carboxamides with polymethylhydrosiloxane, in which encapsulation of the catalyst species into the formed insoluble siloxane resins contributes to the separation of both metallic and siloxane residues from the product. Copyright
- Motoyama, Yukihiro,Mitsui, Kaoru,Ishida, Toshiki,Nagashima, Hideo
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p. 13150 - 13151
(2007/10/03)
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- Synthesis of quaternary alkylammonium sulfobetaines
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A series of quaternary alkylammonium sulfobetaines of general formula RN+(CH3)2(CH2)nSO 3-, where n = 2-4, have been synthesised by reacting the corresponding N,N-dimethylamines with either sodium 2-chloroethanesulfonate (n = 2), 1,3-propane-sultone (n = 3), or 1,4-butanesultone (n = 4). Full details of the preparation of the required N,N-dimethylamines are reported.
- Ward, Robert S.,Davies, Joanna,Hodges, Geoffrey,Roberts, David W.
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p. 2431 - 2439
(2007/10/03)
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- Cyclic imidate salts in acyclic stereochemistry: Diastereoselective syn-epoxidation of 2-alkyl-4-enamides to epoxyamides
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Reaction of 2-alkyl-4-enamides with I+ and aqueous sodium bicarbonate results in the diastereoselective formation of the corresponding iodohydrins with essentially no iodolactone by-product. The reaction appears to proceed through a cyclic imidate type intermediate. This methodology has been successfully employed for the synthesis of the epoxide intermediate of the orally active HIV-1 protease inhibitor MK-639 (indinavir sulfate).
- Maligres,Weissman,Upadhyay,Cianciosi,Reamer,Purick,Sager,Rossen,Eng,Askin,Volante,Reider
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p. 3327 - 3338
(2007/10/03)
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- A biomimetic approach to the synthesis of rocaglamide based on a photochemical [2 + 2] cycloaddition of a cinnamate unit to a flavone
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In attempting a biomimetic synthesis of rocaglamide, we have discovered the first examples of photochemically induced cycloaddition reactions involving a flavone system.
- Hailes,Raphael,Staunton
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p. 5313 - 5316
(2007/10/02)
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- Cyanide as an Efficient and Mild Catalyst in the Aminolysis of Esters
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Cyanide anion was found to be a versatile catalyst in the aminolysis of nonactivated esters.A comparative study on various catalysts, including (dimethylamino)pyridine, 2-hydroxypyridine, imidazole, and sodium cyanide, in the ammonolysis of ethyl (S)-1-ethyl-2-pyrrolidinecarboxylate (1) in methanol showed sodium cyanide to be the superior catalyst.Furthermore, the reaction was completely stereoconservative; i.e., less than 1percent racemization occurred.Cyanide ion also proved to be an efficient catalyst in the transesterification with the solvent.Comparative studies on 1, ethyl benzoate (4), ethyl 3-phenylpropionate (5), and ethyl phenoxyacetate (6) in aminolysis with ammonia, methylamine, and dimethylamine in methanol showed cyanide to be a general catalyst.The reactivity order for various esters was found to be MeNH2 > NH3 > Me2NH.
- Hoegberg, Thomas,Stroem, Peter,Ebner, Michael,Raemsby, Sten
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p. 2033 - 2036
(2007/10/02)
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- Methods for Indole Alkaloid Synthesis. A Specific Procedure for Introducing the 6,7 Double Bond into Aspidosperma-Type Alkaloids via Thiolactam Dehydrogenation
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Tetracyclic amides 6, 14, and 19 were converted into their corresponding thiolactam derivatives 7, 15, and 20 , respectively, by treatment with Lawesson's reagent.When these thiolactams were treated with p-toluenesulfinyl chloride/i-Pr2NEt/(0 deg C) followed by aqueous workup, the α,β-unsaturated thiolactams 8, 16, and 21 were isolated in good to excellent yields.S-Alkylation of the α,β-unsaturated thiolactams followed by reduction with NaBH4 gave the tetracyclic allylic tertiary amines 10, 17, and 22.Dealkylation could only be accomplished for the N-methyl system 22, and only in modest yield.The pentacyclic amide 28 was converted into the thiolactam 29 by treatment with Lawesson's reagent, followed by p-toluenesulfinyl chloride/i-Pr2NEt/65 deg C to give the α,β-unsaturated thiolactam 30 (92percent).Extension of this exceptionally mild dehydrogenation procedure to simple monocyclic thiolactams was not successful.A mechanistic rationale for this new procedure is described with an explanation for its unusual selectivity.
- Magnus, Philip,Pappalardo, Paul A.
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p. 212 - 217
(2007/10/02)
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