Chemical Communications, Journal Year: 2023, Volume and Issue: 59(46), P. 7088 - 7091
Published: Jan. 1, 2023
The difficulty in isolating cyclic enamines emanating from their intrinsic instability has impeded exploration cycloaddition reactions. Here, we achieved a metal-free domino reaction providing quinoline and isoquinoline-derived amidines by the of azides with situ generated via dearomatization.
Language: Английский
Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(4), P. 2358 - 2363
Published: Jan. 17, 2024
Dearomatization of pyridines is a well-established synthetic approach to access piperidines. Although remarkably powerful, existing dearomatization processes have been limited the hydrogenation or addition carbon-based nucleophiles activated pyridiniums. Here, we show that arenophile-mediated dearomatizations can be applied directly introduce heteroatom functionalities without prior substrate activation. The arenophile platform in combination with olefin oxidation chemistry provides dihydropyridine cis-diols and epoxides. These previously elusive compounds are now readily accessible used for downstream preparation diversely functionalized
Language: Английский
Citations
14
Chemical Society Reviews, Journal Year: 2024, Volume and Issue: 53(12), P. 6600 - 6624
Published: Jan. 1, 2024
Dearomatization has emerged as a powerful tool for rapid construction of 3D molecular architectures from simple, abundant, and planar (hetero)arenes. The field evolved beyond simple dearomatization driven by new synthetic technology development. With the renaissance photocatalysis expansion activation mode, last few years have witnessed impressive developments in innovative photochemical methodologies, enabling skeletal modifications dearomatized structures. They offer truly efficient useful tools facile highly complex structures, which are viable natural product synthesis drug discovery. In this review, we aim to provide mechanistically insightful overview on these innovations based degree alteration, categorized into dearomative functionalization editing, highlight their utilities.
Language: Английский
Citations
13
Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(21), P. 11781 - 11788
Published: May 19, 2023
Dihydropyridines are versatile building blocks for the synthesis of pyridines, tetrahydropyridines, and piperidines. Addition nucleophiles to activated pyridinium salts allows 1,2-, 1,4-, or 1,6-dihydropyridines; however, this process often leads a mixture constitutional isomers. Catalyst-controlled regioselective addition pyridiniums has potential solve problem. Herein, we report that boron-based can be accomplished by choice Rh catalyst.
Language: Английский
Citations
22
Synthesis, Journal Year: 2023, Volume and Issue: 56(01), P. 55 - 70
Published: Jan. 17, 2023
Abstract Despite its challenges, the skeletal editing of mono-azaarenes (pyridines, quinolines, and isoquinolines) has shown unparalleled synthetic utility in construction complex molecules that are difficult to access by conventional methods. In this short review, we summarize three most recently developed strategies for deconstruction azaarene cores, with a focus on their generality, limitations, mechanistic aspects. Also, application strategy total synthesis some important natural products is discussed. 1 Introduction 2 Skeletal Editing Mono-Azaarenes through Zincke-like Reactions 3 Mono-azaarenes Aza-Buchner 4 via Photoinduced Radical or Energy-Transfer Processes 5 Conclusion
Language: Английский
Citations
20
Coordination Chemistry Reviews, Journal Year: 2024, Volume and Issue: 520, P. 216136 - 216136
Published: Aug. 14, 2024
Language: Английский
Citations
7
Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(41)
Published: May 28, 2024
Dearomative construction of multiply-fused 2D/3D frameworks, composed aromatic two-dimensional (2D) rings and saturated three-dimensional (3D) rings, from readily available quinolines has greatly contributed to drug discovery. However, dearomative cycloadditions in the presence photocatalysts usually afford 5,6,7,8-tetrahydroquinoline (THQ)-based polycycles, access 1,2,3,4-THQ-based structures remains limited. Herein, we present a chemo-, regio-, diastereo-, enantioselective transformation into 6-6-4-membered without any catalyst, through combination nucleophilic addition borate-mediated [2+2] photocycloaddition. Detailed mechanistic studies revealed that photoexcited borate complex, generated quinoline, organolithium, HB(pin), accelerates cycloaddition suppresses rearomatization occurs conventional Based on our analysis, also developed further photoinduced affording other types frameworks isoquinoline phenanthrene.
Language: Английский
Citations
6
Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(26), P. 14221 - 14226
Published: June 22, 2023
Piperidines are frequently found in natural products and of importance to the pharmaceutical industry. A generally useful asymmetric route enantiomerically enriched 3-substituted piperidines remains elusive. Here we report a cross-coupling approach enantioenriched 3-piperidines from pyridine- sp2-hybridized boronic acids. The key step involves Rh-catalyzed reductive Heck reaction aryl, heteroaryl, or vinyl acids phenyl pyridine-1(2H)-carboxylate provide tetrahydropyridines high yield excellent enantioselectivity with wide functional group tolerance. three-step process involving i) partial reduction pyridine, ii) carbometalation, then iii) another provides access variety 3-piperidines, including clinically used materials such as Preclamol Niraparib.
Language: Английский
Citations
15
Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 63(8)
Published: Nov. 21, 2023
Abstract An arylation protocol for pyridines is described, via the ring‐opened Zincke intermediate. Treatment of with triflic anhydride and a secondary amine produces an azahexatriene species, which undergoes regioselective Pd‐catalyzed at putative C4 position. Recyclization then provides pyridine products. Alternatively, metal‐free diaryliodonium salt selective meta ‐position, affording regiodivergent approach to biaryls from common
Language: Английский
Citations
14
Organic Letters, Journal Year: 2023, Volume and Issue: 25(2), P. 400 - 404
Published: Jan. 10, 2023
The identification of the beneficial pharmacokinetic properties aza-spirocycles has led to routine incorporation these highly rigid and three-dimensional structures in pharmaceuticals. Herein, we report an operationally simple synthesis spirocyclic dihydropyridines via electrophile-induced dearomative semi-pinacol rearrangement 4-(1'-hydroxycyclobutyl)pyridines. various points for diversification spirocyclization precursors, as well synthetic utility amine ketone functionalities products, provide potential rapidly assemble medicinally relevant spirocycles.
Language: Английский
Citations
12
Organic Letters, Journal Year: 2023, Volume and Issue: 25(28), P. 5366 - 5371
Published: July 11, 2023
A multicomponent dearomative difluoroalkylation of isoquinolines has been developed with difluorinated silyl enol ethers serving as poor nucleophiles without an additional transition-metal or organic catalyst. The sequential oxidative rearomatization under different alkaline conditions provides a controllable formal C-H and difluoromethylation method for peroxide metal oxidant. series including pharmaceutical, phenanthridine, quinolines, were suitable substrates to construct gem-difluorinated heterocycles. inexpensive starting materials, mild reaction conditions, simple operation also show practical environmentally benign advantages.
Language: Английский
Citations
11