Expanding the Synthetic Toolbox through Metal–Enzyme Cascade Reactions

Chemical Reviews, Journal Year: 2023, Volume and Issue: 123(9), P. 5297 - 5346

Published: Jan. 10, 2023

The combination of metal-, photo-, enzyme-, and/or organocatalysis provides multiple synthetic solutions, especially when the creation chiral centers is involved. Historically, enzymes and transition metal species have been exploited simultaneously through dynamic kinetic resolutions racemates. However, more recently, linear cascades appeared as elegant solutions for preparation valuable organic molecules combining bioprocesses metal-catalyzed transformations. Many advantages are derived from this symbiosis, although there still bottlenecks to be addressed including successful coexistence both catalyst types, need compatible reaction media mild conditions, or minimization cross-reactivities. Therefore, here also provided by means coimmobilization, compartmentalization strategies, flow chemistry, etc. A comprehensive review presented focusing on period 2015 early 2022, which has divided into two main sections that comprise first use metals independent catalysts but working in an orchestral sequential manner, later their application bionanohybrid materials coimmobilization adequate supports. Each part classified different subheadings, based catalyzed catalyst, while development nonasymmetric stereoselective processes was considered section.

Language: Английский

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Strategies and Lessons Learned from Total Synthesis of Taxol

Chemical Reviews, Journal Year: 2023, Volume and Issue: 123(8), P. 4934 - 4971

Published: March 14, 2023

Taxol (paclitaxel), the most well-known taxane diterpenoid, is best-selling natural-source anticancer drug ever produced and one of common prescriptions in treatment breast, lung, ovarian cancers, saving countless lives around world. Structurally, possesses a highly oxygenated [6–8–6–4] core bearing 11 stereocenters, seven which are contiguous chiral centers. Moreover, extremely strained bicyclo[5.3.1] undecane ring system with bridgehead double bond unique structural feature. All these features make challenging synthetic target. Tremendous efforts from more than 60 research groups world have already culminated ten total syntheses three formal syntheses, as well model studies Taxol. This review intended to provide long-overdue appraisal great achievements reported last few decades. In doing so, we summarize development synthesis toward 1994 2022, including evolution strategy for accessing this complex molecular scaffold key lessons learned such endeavors. Finally, briefly discuss future area.

Language: Английский

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Enantioselective Reductive Divinylation of Unactivated Alkenes by Nickel-Catalyzed Cyclization Coupling Reaction

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(33), P. 12961 - 12967

Published: Aug. 12, 2021

Catalytic asymmetric dicarbofunctionalization of tethered alkenes has emerged as a promising tool for producing chiral cyclic molecules; however, it typically relies on aryl-tethered to form benzene-fused compounds. Herein, we report an enantioselective cross-electrophile divinylation reaction nonaromatic substrates, 2-bromo-1,6-dienes. The approach thus offers route new architectures, which are key structural motifs found in various biologically active proceeds under mild conditions, and the use t-Bu-pmrox 3,5-difluoro-pyrox ligands resulted formation divinylated products with high chemo-, regio-, enantioselectivity. method is applicable incorporation hetero- carbocycles into complex molecules.

Language: Английский

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Electrophilic Aminating Agents in Total Synthesis

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(49), P. 25640 - 25666

Published: May 4, 2021

Classical amination methods involve the reaction of a nitrogen nucleophile with an electrophilic carbon center; however, in recent years, umpoled strategies have gained traction where source acts as electrophile. A wide range aminating agents are now available, and these underpin powerful C-N bond-forming processes. In this Review, we highlight strategic use total synthesis.

Language: Английский

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Heck Migratory Insertion Catalyzed by a Single Pt Atom Site

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(44), P. 24126 - 24135

Published: Oct. 23, 2023

Single-atom catalysts (SACs) have generated excitement for their potential to downsize metal particles the atomic limit with engineerable local environments and improved catalytic reactivities selectivities. However, successes been limited small-molecule transformations little progress toward targeting complex-building reactions, such as metal-catalyzed cross-coupling. Using a supercritical carbon-dioxide-assisted protocol, we report heterogeneous single-atom Pt-catalyzed Heck reaction, which provides first C–C bond-forming migratory insertion on SACs. Our quantum mechanical computations establish reaction mechanism involve novel C-rich coordination site (i.e., PtC4) that demonstrates an unexpected base effect. Notably, was found transiently modulate environment allow into M–C species, process high steric impediment no previous example The studies showcase how SACs can introduce structures remained underexplored in catalyst design. These findings offer immense transferring vast highly versatile manifold of migratory-insertion-based protocols

Language: Английский

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Applications of bio-resource based sustainable heterogeneous Pd-Nanocatalyst for Cross-Coupling and Michael addition reactions

Chemical Engineering Journal, Journal Year: 2024, Volume and Issue: 483, P. 149271 - 149271

Published: Feb. 3, 2024

The development of efficient and cost-effective catalysts from renewable sources is crucial for sustainable chemistry. Herein, we developed a bio-heterogeneous Pd-nanocatalyst (PdNc@PA) by incorporating palladium nanoparticles into biodegradable kenaf-cellulose modified with poly(amidoxime) ligands. catalyst has demonstrated remarkable stability exceptional catalytic performance in range cross-coupling including Mizoroki-Heck, Suzuki-Miyaura, Tamejiro-Hiyama reactions inactivated aryl chlorides resulting high yields the desired coupling products. Additionally, PdNc@PA was also found to be effective Michael addition producing N, S, O-alkylated products yields. Furthermore, robustness recoverability allowing it reused across successive cycles without significant loss activity. incorporation resources offers an environmentally conscious alternative traditional synthetic approaches. This research highlights potential utilizing materials as supports, which could significantly diminish environmental impact waste production. Moreover, this study demonstrates versatility proficient reusable diverse array organic reactions. These discoveries provide encouraging pathway towards economically viable suitable industrial applications.

Language: Английский

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Synthesis and Contemporary Applications of Platinum Group Metals Complexes with Acyclic Diaminocarbene Ligands (Review)

Russian Journal of Inorganic Chemistry, Journal Year: 2022, Volume and Issue: 67(1), P. 48 - 90

Published: Jan. 1, 2022

Language: Английский

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Mechanistic Insights into the Stereocontrolling Non-Covalent π Interactions in Pd-Catalyzed Redox-Relay Heck Arylation Reaction

Chemical Communications, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

DFT calculations revealed a series of non-covalent π interactions that are responsible for the high enantioselectivity palladium-catalyzed redox-relay Heck arylation 1,1-disubstituted homoallylic alcohols.

Language: Английский

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Intermolecular Enantioselective Dearomative Oxidative Heck Reaction of Indoles

Acta Chimica Sinica, Journal Year: 2024, Volume and Issue: 82(1), P. 1 - 1

Published: Jan. 1, 2024

Transition-metal-catalyzed asymmetric dearomatization reaction represents a straightforward method to access chiral cyclic compounds.In recent years, enantioselective dearomative Heck reactions of indoles, benzofurans, pyrroles, furans, and naphthalenes have been successfully developed.Nevertheless, current reports are mainly limited the intramolecular reaction, intermolecular still underdeveloped.In consideration relatively mild conditions in oxidative we envisioned that its induction might be possible due commonly-proposed cationic rather than neutral mechanism for reaction.In present work, an palladium-catalyzed indoles with arylboronic acids has developed.By employing Pd(OAc)2 as catalyst precursor, pyridineoxazoline ligand, oxygen oxidant, benzoquinone (BQ) co-oxidant, series indolines bearing C2-substituted quaternary stereocenter were afforded moderate good yields ee values.A general procedure this is described following: To dried Schlenk tube charged (4.5 mg, 10 mol%) ligand L9 (15.1 20 under O2 atmosphere. 2 mL N-methylpyrrolidone (NMP) solvent was then introduced via syringe sealed using Teflon cap.The mixture stirred at 60 ℃ 30 min order form complex.After cooling room temperature, indole substrates 1 (0.2 mmol), aryl boronic (0.6 co-oxidant BQ (4.3 added system atmosphere.The resulting 80 12 h.When completed [monitored by thin-layer chromatography (TLC)], water extracted ethyl acetate.The combined organic phases over anhydrous Na2SO4 concentrated reduced pressure.The residue purified flash column on silica gel [V(ethyl acetate)∶V(petroleum ether)＝1∶ 15] afford products 2.

Language: Английский

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Discovery of a nitroaromatic nannocystin with potent in vivo anticancer activity against colorectal cancer by targeting AKT1

Acta Pharmacologica Sinica, Journal Year: 2024, Volume and Issue: 45(5), P. 1044 - 1059

Published: Feb. 7, 2024

Language: Английский

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