264882-01-1Relevant articles and documents
Blue Light-Emitting Diode-Mediated in Situ Generation of Pyridinium and Isoquinolinium Ylides from Aryl Diazoesters: Their Application in the Synthesis of Diverse Dihydroindolizine
Guha, Souvik,Maiti, Debajit,Prabakar, Tejas,Sar, Saibal,Sen, Subhabrata
, p. 11736 - 11747 (2021)
Blue light-emitting diode-mediated environmentally sustainable three component reactions among pyridine/isoquinoline 1/2, aryl diazoesters 3, and acrylic ester/3-alkenyl oxindoles 5/6 provide various dihydroindolizines 7 to 9 in excellent yield. The principle of the strategy is photolytic generation of nitrogen ylides from N-heteroarenes and aryl diazoesters and their subsequent [3 + 2] cycloaddition reaction with dipolarophiles. Detailed mechanistic analysis of the transformation through control experiments establishes this strategy as the foundation for the photolytic multicomponent reaction.
2-azabicyclo [3.2.0] compound as well as synthesis method and application
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Paragraph 0107; 0111; 0118; 0129-0131; 0134, (2021/07/17)
The invention discloses a 2-azabicyclo [3.2.0] compound as well as a synthesis method and an application. The 2-azabicyclo [3.2.0] compound comprises a compound with a structure as shown in a formula I and pharmaceutically acceptable salts thereof, wherein R is a substituted or unsubstituted benzene ring, a C1-8 aliphatic group or trifluoromethyl, R1 and R2 are respectively a substituted or unsubstituted benzene ring, a hydrogen atom or a C1-8 aliphatic group, R3 is a substituted or unsubstituted benzene ring, a hydrogen atom, a C1-8 aliphatic group or a heterocyclic substituent, R4 is a heterocyclic substituent or a substituted or unsubstituted benzene ring, R5 is a C1-8 fatty group, a benzyl group or -COOR6, and R6 is a C1-4 fatty group or a benzyl group. The invention belongs to the technical field of pharmaceutical chemicals, and after the prepared 2-azabicyclo [3.2.0] compound acts on an animal body, anti-sedation and anti-hypnosis effects can be achieved by adjusting the intracerebral level of histamine.
Dirhodium(II)/Xantphos-Catalyzed Relay Carbene Insertion and Allylic Alkylation Process: Reaction Development and Mechanistic Insights
Liang, Xinyi,Lu, Bin,Peng, Qian,Wang, Xiaoming,Wang, Zijian,Zhang, Jinyu
supporting information, p. 11799 - 11810 (2021/08/16)
Although dirhodium-catalyzed multicomponent reactions of diazo compounds, nucleophiles and electrophiles have achieved great advance in organic synthesis, the introduction of allylic moiety as the third component via allylic metal intermediate remains a formidable challenge in this area. Herein, an attractive three-component reaction of readily accessible amines, diazo compounds, and allylic compounds enabled by a novel dirhodium(II)/Xantphos catalysis is disclosed, affording various architecturally complex and functionally diverse α-quaternary α-amino acid derivatives in good yields with high atom and step economy. Mechanistic studies indicate that the transformation is achieved through a relay dirhodium(II)-catalyzed carbene insertion and allylic alkylation process, in which the catalytic properties of dirhodium are effectively modified by the coordination with Xantphos, leading to good activity in the catalytic allylic alkylation process.
Visible-light-promoted selective: O -alkylation of 2-pyridones with α-aryldiazoacetates
Yang, Jingya,Wang, Ganggang,Zhou, Hongyan,Li, Zhifeng,Ma, Ben,Song, Menghui,Sun, Rongxia,Huo, Congde
supporting information, p. 394 - 398 (2021/01/29)
A visible-light-promoted O-H insertion reaction between 2-pyridones and α-aryldiazoacetates has been developed. Upon visible light irradiation, the reaction proceeds smoothly under mild and catalyst-free conditions. A wide scope of 2-pyridones and α-aryldiazoacetates are well tolerated, and various O-alkylated 2-pyridones are obtained with perfect selectivity and good functional group tolerance. A photoinduced radical process is probably responsible for the excellent selectivity. This journal is
Divergent Synthesis of Aziridine and Imidazolidine Frameworks under Blue LED Irradiation
Cheng, Xiao,Cai, Bao-Gui,Mao, Hui,Lu, Juan,Li, Lei,Wang, Kun,Xuan, Jun
supporting information, p. 4109 - 4114 (2021/05/26)
We develop a visible light-promoted divergent cycloaddition of α-diazo esters with hexahydro-1,3,5-triazines, leading to a series of aziridine and imidazolidine frameworks in average good yield, by simply changing the reaction media used. It is noteworthy that the reaction occurs under sole visible light irradiation without the need for exogenous photoredox catalysts. More significantly, a reasonable reaction mechanism was proposed on the basis of the control experiments and density functional theory calculation results.
Visible light and base promoted O-H insertion/cyclization of para-quinone methides with aryl diazoacetates: An approach to 2,3-dihydrobenzofuran derivatives
Zhou, Shuangjing,Cai, Baogui,Hu, Chuxia,Cheng, Xu,Li, Lei,Xuan, Jun
supporting information, p. 2577 - 2581 (2021/03/22)
A visible light and base promoted O-H insertion/cyclization of para-quinone methides with aryl diazoacetates is developed. This one-pot two step reaction offers a mild and efficient approach for the synthesis of biologically important 2,3-dihydrobenzofuran derivatives in good yields and moderate diastereoselectivities.
Rhodium(I)-Catalyzed Enantioselective C(sp3)—H Functionalization via Carbene-Induced Asymmetric Intermolecular C—H Insertion?
Liu, Bo,Xu, Ming-Hua
supporting information, p. 1911 - 1915 (2021/05/31)
Transition-metal-catalyzed C—H insertion of metal-carbene represents an excellent and powerful approach for C—H functionalization. However, despite remarkable advances in metal-carbene chemistry, transition metal catalysts that are capable of enantioselective intermolecular carbene C—H insertion are mainly constrained to dirhodium(II) and iridium(III)-based complexes. Herein, we disclose a new version of asymmetric carbene C—H insertion reaction with rhodium(I) catalyst. A highly enantioselective rhodium(I) complex-catalyzed C(sp3)—H functionalization of 1,4-cyclohexadienes with α-aryl-α-diazoacetates was successfully developed. By using chiral bicyclo[2.2.2]-octadiene as ligand, rhodium(I)-carbene-induced asymmetric intermolecular C—H insertion proceeds smoothly at room temperature, allowing access to a diverse variety of α-aryl-α-cyclohexadienyl acetates and gem-diaryl-containing acetates in good yields with good to excellent enantioselectivities (up to 99% ee). Furthermore, the synthetic utility of the reaction was highlighted by facile synthesis of a novel cannabinoid CB1 receptor ligand. This method may offer a new opportunity for the development of therapeutically exploitable cannabinoid receptor type ligands in medicinal chemistry.
Photolytic amino etherification reactions of aryl diazoacetates with N-heterocycles and a stoichiometric amount of dioxane/tetrahydropyran in aqueous medium: Synthesis of 1,4-dioxepane/1,4,7-dioxazonan-6-one systems
Das, Ranajit,Maiti, Debajit,Sen, Subhabrata
, p. 8533 - 8544 (2021/11/17)
Herein we have reported a blue LED mediated reaction of aryl diazoacetate with a stoichiometric amount of 1,4-dioxane/tetrahydropyran (THP) and various heterocycles like indoles, pyrroles, phthalimides, thiazolidinediones and hydantoins in water. During the reaction, various aryl diazoacetates were converted to oxonium ylides by reacting with 1,4-dioxane and THP. These ylides generated in aqueous medium (under metal- and base-free conditions) were then used for the amino etherification of the aforementioned heterocycles in excellent yield. The ylides underwent a [1,2] shift to afford substituted 1,4-dioxepanes. Phthalimide products were also converted to 1,4,7-dioxazonan-6-ones. Reaction kinetics, Hammett's plot and DFT calculations (solvent phase) rationalize the ylide formation and subsequent reactions with the nucleophiles. The reaction was also demonstrated at the multigram scale. This amino etherification reaction of aryl diazoacetates in aqueous medium demonstrated a sustainable process of converting toxic 1,4-dioxane in functionalizing heterocycles. This journal is
Visible Light-Promoted Sulfoxonium Ylides Synthesis from Aryl Diazoacetates and Sulfoxides
Lu, Juan,Li, Lei,He, Xiang-Kui,Xu, Guo-Yong,Xuan, Jun
supporting information, p. 1646 - 1650 (2021/05/28)
A visible light-promoted reaction of donor/acceptor diazoalkanes with sulfoxides towards the synthesis of synthetically useful sulfoxonium ylides was reported. The reaction occurred under sole visible light irradiation without the need of any transition-metals or additives, affording the corresponding sulfoxonium ylides in moderate to good yields. The success of late-stage modification of natural isolates or drug candidates, scale-up reaction and transformation of sulfoxonium ylides to other useful molecules further rendered the approach valuable.
Pd-Catalyzed Decarboxylative Olefination: Stereoselective Synthesis of Polysubstituted Butadienes and Macrocyclic P-glycoprotein Inhibitors
Chen, Xiangyang,Hao, Jiping,Houk, K. N.,Li, Yingzi,Lou, Liguang,Quan, Haitian,Song, Bichao,Wang, Lu,Xia, Yuanzhi,Xie, Peipei,Xu, Zhongliang,Yang, Weibo
, p. 9982 - 9992 (2020/06/27)
The efficient and stereoselective synthesis of polysubstituted butadienes, especially the multifunctional butadienes, represents a great challenge in organic synthesis. Herein, we wish to report a distinctive Pd(0) carbene-initiated decarboxylative olefination approach that enables the direct coupling of diazo esters with vinylethylene carbonates (VECs), vinyl oxazolidinones, or vinyl benzoxazinones to afford alcohol-, amine-, or aniline-containing 1,3-dienes in moderate to high yields and with excellent stereoselectivity. This protocol features operational simplicity, mild reaction conditions, a broad substrate scope, and gram-scalability. Notably, a structurally unique allylic Pd(II) intermediate was isolated and characterized. DFT calculation and control experiments demonstrated that a rare Pd(0) carbene intermediate could be involved in this reaction. Moreover, the polysubstituted butadienes as novel building blocks were unprecedentedly assembled into macrocycles, which efficiently inhibited the P-glycoprotein and dramatically reversed multidrug resistance in cancer cells by 190-fold.