Transition-metal-catalyzed C–H bond alkylation using olefins: recent advances and mechanistic aspects

Chemical Society Reviews, Год журнала: 2022, Номер 51(17), С. 7358 - 7426

Опубликована: Янв. 1, 2022

Transition metal catalysis has contributed immensely to C-C bond formation reactions over the last few decades, and alkylation is no exception. The superiority of such methodologies traditional evident from minimal reaction steps, shorter times, atom economy while also allowing control regio- stereo-selectivity. In particular, hydrocarbonation alkenes grabbed increased attention due its fundamental ability effectively selectively synthesise a wide range industrially pharmaceutically relevant moieties. This review attempts provide scientific viewpoint systematic analysis recent developments in transition-metal-catalyzed various C-H bonds using simple activated olefins. key features mechanistic studies involved these transformations are described briefly.

Язык: Английский

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Transition-metal catalyzed C–H activation as a means of synthesizing complex natural products

Chemical Society Reviews, Год журнала: 2023, Номер 52(21), С. 7461 - 7503

Опубликована: Янв. 1, 2023

Over the past few decades, advent of C–H activation has led to a rethink among chemists about synthetic strategies employed for multi-step transformations.

Язык: Английский

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A π-conjugated covalent organic framework enables interlocked nickel/photoredox catalysis for light-harvesting cross-coupling reactions

Chemical Science, Год журнала: 2023, Номер 14(32), С. 8624 - 8634

Опубликована: Янв. 1, 2023

Covalent organic frameworks (COFs) are an outstanding platform for heterogeneous photocatalysis. Herein, we synthesized a pyrene-based two-dimensional C[double bond, length as m-dash]C linked π-conjugated COF via Knoevenagel condensation and anchored Ni(ii)-centers through bipyridine moieties. Instead of traditional dual metallaphotoredox catalysis, the mono-metal decorated Ni@Bpy-sp2c-COF interlocked catalysis mediated by light transition metal. Under irradiation, enhanced energy electron transfer in backbone, delineated photoluminescence, electrochemical, control experiments, expedited excitation Ni centers to efficiently catalyze diverse photocatalytic C-X (X = B, C, N, O, P, S) cross-coupling reactions with efficiencies orders magnitude higher than homogeneous controls. The catalyst tolerated range coupling partners various steric electronic properties, delivering products up 99% yields. Some were performed on gram scale applied diversify pharmaceuticals complex molecules demonstrate synthetic utility.

Язык: Английский

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Dual Ligand Enabled Nondirected C–H Chalcogenation of Arenes and Heteroarenes

Journal of the American Chemical Society, Год журнала: 2022, Номер 144(27), С. 12032 - 12042

Опубликована: Июнь 27, 2022

Chalcogenide motifs are present as principal moieties in a vast array of natural products and complex molecules. Till date, the construction these chalcogen has been restricted to either use directing groups or employment large excess electronically activated arenes, typically employed cosolvent. Despite being highly effective, methods have their own limitations step economy deployment an amount arenes. Herein, we report evolution catalytic system employing arene-limited, nondirected thioarylation arenes heteroarenes using complimentary dual-ligand approach. The reaction is controlled by combination steric electronic factors, utilization suitable ligand enables generation on spectrum that generated classical methods. ligands remains imperative protocol with theoretical calculations pointing towards monoprotected amino acid crucial concerted metalation deprotonation (CMD) mechanism characteristic [5,6]-palladacyclic transition state, while pyridine moiety assists active catalyst species formation product release. Combined experimental computational mechanistic investigations point toward C–H activation both regio- rate-determining. Interestingly, oxidative addition diphenyl disulfide substrate found be unlikely, alternative transmetalation-like involving Pd–Ag heterometallic proposed operative.

Язык: Английский

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Binaphthyl Scaffold: A Class of Versatile Structure in Asymmetric C–H Functionalization

ACS Catalysis, Год журнала: 2022, Номер 12(15), С. 9359 - 9396

Опубликована: Июль 18, 2022

Over the past decades, transition metal-catalyzed enantioselective C–H functionalization has emerged as a straightforward and powerful tool for rapid access to chiral molecules. The enormous advances achieved in this emerging area largely rely on development of ligands that can enable both high levels enantiocontrol efficiency. Chiral bearing binaphthyl scaffolds have been proven be versatile asymmetric due their availability, unique stereochemical features, ease fine-tuning steric electronic properties. In Review, we summarized advance applications basis scaffold functionalization.

Язык: Английский

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Visible light metallaphotoredox catalysis in the late-stage functionalization of pharmaceutically potent compounds

Organic Chemistry Frontiers, Год журнала: 2022, Номер 10(1), С. 216 - 236

Опубликована: Ноя. 8, 2022

The late stage functionalization (LSF) is a distinctive approach for accelerating the discovery of structure–activity relationships (SARs) and optimising ADME (absorption, distribution, metabolism, excretion) profiles.

Язык: Английский

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Dual-Ligand Catalyst for the Nondirected C–H Olefination of Heteroarenes

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(14), С. 8198 - 8208

Опубликована: Март 28, 2023

Pd(II)-catalyzed nondirected C-H functionalization of heteroarenes is a significant challenge for the following reasons: poor reactivity electron-deficient heterocycles and unproductive coordination Lewis basic nitrogen atoms. Existing methodologies using palladium catalysis often employ large excess heterocycle substrates to overcome these hurdles. Despite recent advances in arenes that allow them be used as limiting reagents, reaction conditions are incompatible with heteroarenes. Herein we report dual-ligand catalyst enables olefination without substrate. In general, use 1-2 equiv was sufficient obtain synthetically useful yields. The rationalized by synergy between two types ligands: bidentate pyridine-pyridone ligand promotes cleavage; monodentate substrate acts second form cationic Pd(II) complex has high affinity arenes. proposed cooperation supported combination X-ray, kinetics, control experiments.

Язык: Английский

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Distal meta-alkenylation of formal amines enabled by catalytic use of hydrogen-bonding anionic ligands

Chem, Год журнала: 2023, Номер 9(4), С. 989 - 1003

Опубликована: Янв. 24, 2023

Язык: Английский

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Controlling Reactivity and Selectivity in the Nondirected C–H Activation of Arenes with Palladium

Accounts of Chemical Research, Год журнала: 2023, Номер 56(18), С. 2459 - 2472

Опубликована: Авг. 24, 2023

ConspectusAromatic structures are widespread motifs throughout organic chemistry, and C-H activation has been recognized as a major tool for enabling their sustainable efficient functionalization. Through activation, arenes can be modified without the need prefunctionalization, leading to inherent atom- step-economic advantages over traditional methods. However, development of synthetically useful methods, several hurdles have overcome. The strength bonds necessitates sufficiently reactive catalysts, while presence multiple within substrate poses challenges in terms site-selectivity. Traditionally these addressed by control. By attaching different directing groups (DGs), reactivity respective arene was significantly enhanced DG guided metal close proximity specific bonds, resulting high introduction removal add additional steps synthetic sequence, scope reaction is limited class. complementary nondirected methods that applied broad range necessity carry functional group coordinates Pd (referred simple arenes) therefore highly desirable. intrinsically lower such substrates absence selectivity-determining pose significant solved only catalysts. Consequently, field especially with respect Pd-catalyzed remained comparatively underdeveloped when we initiated our research program 2017. At time, state-of-the-art required used large excess, precluding its use late-stage Since organopalladium species among most versatile intermediates, realized developing system, which effectively selectively activate limiting reagent, would powerful chemistry. This account summarizes groups' toward application catalytic systems offering this desired focuses explicitly on functionalization reactions arenes, where employed reagent. After an state before 2017 associated challenges, experimental mechanistic details about first arene-limited, palladium will discussed. enabled identification combination two ligands, N-heterocycle amino acid-derived ligand. Afterward discuss expansion dual-ligand approach further arene-limited transformations. Finally, describe methodologies originated from observations made during studies, namely, deuteration selective olefination method uses noncovalent interactions induce meta selectivity.

Язык: Английский

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Visible-Light-Induced Redox-Neutral Difunctionalization of Alkenes and Alkynes

Chemical Communications, Год журнала: 2024, Номер 60(72), С. 9659 - 9691

Опубликована: Янв. 1, 2024

The twelve principles of green chemistry illuminate the pathway in direction sustainable and eco-friendly synthesis, marking a fundamental shift synthetic organic paradigms. In this realm, harnessing power visible light for difunctionalization various skeletons without employing any external oxidant or reductant, specifically termed as redox-neutral difunctionalization, has attracted tremendous interest from chemists due to its low cost, easy availability environmentally friendly nature contrast traditional metal-catalyzed difunctionalizations. This review presents an overview recent updates on visible-light-induced reactions with literature coverage up May 2024.

Язык: Английский

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