18859-19-3Relevant academic research and scientific papers
Selective Construction of C?C and C=C Bonds by Manganese Catalyzed Coupling of Alcohols with Phosphorus Ylides
Liu, Xin,Werner, Thomas
supporting information, p. 1096 - 1104 (2020/12/31)
Herein, we report the manganese catalyzed coupling of alcohols with phosphorus ylides. The selectivity in the coupling of primary alcohols with phosphorus ylides to form carbon-carbon single (C?C) and carbon-carbon double (C=C) bonds can be controlled by the ligands. In the conversion of more challenging secondary alcohols with phosphorus ylides the selectivity towards the formation of C?C vs. C=C bonds can be controlled by the reaction conditions, namely the amount of base. The scope and limitations of the coupling reactions were thoroughly evaluated by the conversion of 21 alcohols and 15 ylides. Notably, compared to existing methods, which are based on precious metal complexes as catalysts, the present catalytic system is based on earth abundant manganese catalysts. The reaction can also be performed in a sequential one-pot reaction generating the phosphorus ylide in situ followed manganese catalyzed C?C and C=C bond formation. Mechanistic studies suggest that the C?C bond was generated via a borrowing hydrogen pathway and the C=C bond formation followed an acceptorless dehydrogenative coupling pathway. (Figure presented.).
Development of a triazinedione-based dehydrative condensing reagent containing 4-(dimethylamino)pyridine as an acyl transfer catalyst
Liu, Jie,Fujita, Hikaru,Kitamura, Masanori,Shimada, Daichi,Kunishima, Munetaka
supporting information, p. 4712 - 4719 (2021/06/11)
A new triazinedione-based reagent, (N,N′-dialkyl)triazinedione-4-(dimethylamino)pyridine (ATD-DMAP) was developed for the operationally simple dehydrative condensation of carboxylic acids. This reagent comprises an ATD core and DMAP as the leaving group, which is liberated into the reaction system to accelerate acyl transfer reactions. Upon adding ATD-DMAP to a mixture of carboxylic acids and alcohols in the presence of an amine base, the corresponding esters were formed rapidly at room temperature. Moreover, dehydrative condensation between carboxylic acids and amines using ATD-DMAP proceeded in high yield.
Efficiency Enhancement of a Photocatalytic Decarbonylation of an Aminocyclopropenone by Benzothiophene Substitution
Mishiro, Kenji,Nomura, Mitsuki,Furuyama, Taniyuki,Kunishima, Munetaka
, p. 3625 - 3636 (2021/03/03)
To improve the efficiency of the photocatalytic decarbonylation of cyclopropenones, the effects of substituents on cyclopropenone were explored. A benzothiophene-substituted aminocyclopropenone exhibited significantly improved decarbonylation efficiency t
METHOD FOR PRODUCING AMIDE COMPOUND
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Paragraph 0030; 0033-0037; 0042-0043, (2021/09/17)
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
Nickel-catalyzed: C-alkylation of thioamide, amides and esters by primary alcohols through a hydrogen autotransfer strategy
Yang, Peng,Wang, Xiuhua,Ma, Yu,Sun, Yaxin,Zhang, Li,Yue, Jieyu,Fu, Kaiyue,Zhou, Jianrong Steve,Tang, Bo
supporting information, p. 14083 - 14086 (2020/11/20)
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
Clickable coupling of carboxylic acids and amines at room temperature mediated by SO2F2: A significant breakthrough for the construction of amides and peptide linkages
Wang, Shi-Meng,Zhao, Chuang,Zhang, Xu,Qin, Hua-Li
, p. 4087 - 4101 (2019/04/30)
The construction of amide bonds and peptide linkages is one of the most fundamental transformations in all life processes and organic synthesis. The synthesis of structurally ubiquitous amide motifs is essential in the assembly of numerous important molecules such as peptides, proteins, alkaloids, pharmaceutical agents, polymers, ligands and agrochemicals. A method of SO2F2-mediated direct clickable coupling of carboxylic acids with amines was developed for the synthesis of a broad scope of amides in a simple, mild, highly efficient, robust and practical manner (>110 examples, >90% yields in most cases). The direct click reactions of acids and amines on a gram scale are also demonstrated using an extremely easy work-up and purification process of washing with 1 M aqueous HCl to provide the desired amides in greater than 99% purity and excellent yields.
Development of Triazinone-Based Condensing Reagents for Amide Formation
Yamada, Kohei,Kota, Mika,Takahashi, Kensuke,Fujita, Hikaru,Kitamura, Masanori,Kunishima, Munetaka
, p. 15042 - 15051 (2019/11/19)
Novel triazinone-based condensing reagents have been developed. The palladium-catalyzed O-N allylic rearrangement of 2-(allyloxy)-4,6-dichloro-1,3,5-triazine and subsequent regioselective substitution using alcohols and an amine afforded chlorotriazinones, which can be readily converted using N-methylmorpholine into the corresponding condensing reagents. The condensation of carboxylic acids and amines using these reagents proceeded to afford the desired amides in good yields. In comparison with 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride, the newly synthesized triazinone-based condensing reagents exhibited higher reactivity.
Phototriggered Active Alkyne Generation from Cyclopropenones with Visible Light-Responsive Photocatalysts
Mishiro, Kenji,Kimura, Takeshi,Furuyama, Taniyuki,Kunishima, Munetaka
supporting information, p. 4101 - 4105 (2019/06/17)
A photocatalytic active alkyne generation reaction was developed using cyclopropenone as a starting reagent. Visible light-responsive photocatalysts induced cyclopropenone decarbonylation. The resulting highly reactive alkyne could be used directly, witho
Selective hydrogenation of α,β-unsaturated carbonyl compounds on silica-supported copper nanoparticles
Mendes-Burak, Jorge,Ghaffari, Behnaz,Copéret, Christophe
supporting information, p. 179 - 181 (2019/01/04)
Silica-supported copper nanoparticles prepared via surface organometallic chemistry are highly efficient for the selective hydrogenation of various α,β-unsaturated carbonyl compounds yielding the corresponding saturated esters, ketones, and aldehydes in the absence of additives. High conversions and selectivities (>99%) are obtained for most substrates upon hydrogenation at 100-150 °C and under 25 bar of H2.
Chemoselective α,β-Dehydrogenation of Saturated Amides
Teskey, Christopher J.,Adler, Pauline,Gon?alves, Carlos R.,Maulide, Nuno
supporting information, p. 447 - 451 (2019/01/04)
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.
