Photochemical synthesis in inorganic chemistry

Reviews in Inorganic Chemistry, Journal Year: 2024, Volume and Issue: 44(3), P. 323 - 337

Published: Feb. 16, 2024

Abstract In the last few decades, photochemistry has great influence on all type of synthetic processes. While photochemical synthesis is emerging field in inorganic chemistry as it impart various magnificent properties to materials that are used for nano-sized giant supramolecular structures. There many based approaches like electron, atom, energy transfer depending upon need product where one can switch pathway. A variety compounds have been synthesized dienes, nitrides, indoles, gold nano-particles and structures using route. Photochemical applications artificial photosynthesis fluorophores.

Language: Английский

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An Experimental and Theoretical Investigation into [2π + 2π] Cycloaddition Reactions Catalyzed by a Cationic Cobalt(I) Complex Containing a Strong-Field PC_NHCP Pincer Ligand

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: April 24, 2025

In the past decade, metal-catalyzed [2π + 2π] cycloaddition reactions have gained significant momentum for synthesis of substituted cyclobutanes and bicyclo[3.2.0]-heptanes. To date, earth-abundant metals that contain redox non-innocent (radical)-type ligands are most commonly used in these reactions, whereby ligand plays a crucial role stabilizing oxidation spin-state metal center. Classical π-accepting ligands, however, inactive transformations. Here, we report efficient catalyzed by cobalt(I) complex containing traditional but innocent PCNHCP pincer ligand. Mechanistic computational investigations revealed classical Co(I)-Co(III) cycle on singlet spin manifold, where oxidative cyclization is rate-limiting step. Overall, herein developed methodology exhibits wide substrate scope low catalyst loadings (<1 mol %) compatible with variety functional groups while occurring under mild conditions (40-60 °C, N2) short reaction times.

Language: Английский

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Synthesis of bicyclo[3.2.0]heptane lactones via a ligand-enabled Pd-catalyzed C(sp³)–H activation cascade

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

Published: Jan. 1, 2025

Bicyclo[3.2.0]heptane lactones represent an important scaffold in bioactive molecules. Herein, we report a diastereoselective synthetic disconnection to access bicyclo[3.2.0]heptane from bicyclo[1.1.1]pentane carboxylic acids, which proceeds through palladium-catalyzed C-H activation and C-C cleavage processes. By using two different classes of ligands, MPAA pyridone-amine, either all-syn arylated or non-arylated ones can be synthesized. The lactone products were converted into multiple substituted cyclobutane, γ-lactone, oxobicyclo[3.2.0]heptane derivatives showcase the versatility this method.

Language: Английский

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Recent Advances in Nonprecious Metal Catalysis

Organic Process Research & Development, Journal Year: 2024, Volume and Issue: 28(4), P. 937 - 948

Published: March 21, 2024

Significant emphasis has been placed on the development of nonprecious metal alternatives to precious-metal-catalyzed reactions due lower cost and greater sustainability they can achieve. This review is part a series describing advances in nonprecious-metal-catalyzed transformations published between March June 2023 that are relevant pharmaceutical process chemistry.

Language: Английский

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DFT Struggles to Predict the Energy Landscape for Iron Pyridine Diimine-Catalyzed [2 + 2] Cycloaddition of Alkenes: Insights into the Problem and Alternative Solutions

The Journal of Physical Chemistry A, Journal Year: 2024, Volume and Issue: 128(20), P. 4114 - 4127

Published: April 24, 2024

In recent years, noninnocent pyridine diimine (PDI) complexes featuring first-row transition metals have emerged as prominent catalysts, demonstrating efficacy in a diverse range of vital organometallic transformations. However, the inherent complexity fundamental reactivity paradigm these systems arises from presence ligand and multispin feasibility 3d metals. While density functional theory (DFT) has been widely used to unravel mechanistic insights, its limitations single-reference method can potentially misrepresent spin-state energetics, compromising our understanding intricate systems. this study, we employ extensive high-level ab initio state averaged-complete active space self-consistent field/N-electron valence perturbation (SA-CASSCF/NEVPT2) calculations combination with DFT investigate an iron-PDI-catalyzed [2 + 2] cycloaddition reaction alkenes. The transformation proceeds through two major steps: oxidative cyclization reductive elimination. Contrary predictions calculations, which suggest two-state identify elimination turnover-limiting step, SA-CASSCF/NEVPT2-corrected results unequivocally establish single-state scenario step. SA-CASSCF/NEVPT2-based insights into electronic ground states electron distribution elucidate intriguing interactions between PDI iron center, revealing highly multiconfigurational nature species providing precise depiction metal–ligand cooperativity throughout transformation. A comparative assessment several recognized functionals against data indicates that single-point energy using modern MN15 on TPSSh geometries offer most reliable methodology, scenarios where SA-CASSCF/NEVPT2 computational cost is consideration.

Language: Английский

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The Atmosphere Matters: The Effect of “Inert” Gas on the Catalytic Outcomes in Cobalt-Mediated Alkyne and Olefin Hydroboration

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(13), P. 8770 - 8782

Published: June 17, 2023

We present a highly efficient cobalt-mediated hydroboration reaction of alkynes and alkenes enabled by π-acidic redox-active pyrimidinediimine (PPymDI) core. The entry point in the catalytic cycle is on cobalt dinitrogen complex rather than hydride species, which are commonly postulated hydroelementation reactions. Stoichiometric studies have demonstrated that both hydrides complexes can be generated from same precursors under conditions, with sole difference being atmosphere (argon vs N2). Nevertheless, while PPymDI-based active (TOF = 1100 h–1 at t1/2, RT), analogue displays only modest conversions slow rates. Under optimized wide range vinyl alkyl organoboron derivatives obtained high efficiency. Mechanistic suggest that, due to increased π-acidity PPymDI core, initial formation Co-π-complexes preferred, followed oxidative addition borane, turnover-limiting step. This sequence steps supported Hammett analysis, shows proceeds more rapidly for electron-rich substrates. electronic structure all relevant species was investigated detail computational, crystallographic, spectroscopic means, revealing ligand involvement redox processes.

Language: Английский

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Diazines and Triazines as Building Blocks in Ligands for Metal-Mediated Catalytic Transformations

ACS Organic & Inorganic Au, Journal Year: 2023, Volume and Issue: 4(1), P. 41 - 58

Published: Oct. 23, 2023

Pyridine is a ubiquitous building block for the design of very diverse ligand platforms, many which have become indispensable catalytic transformations. Nevertheless, isosteric pyrazine, pyrimidine, and triazine congeners enjoyed thus far less privileged role in design. In this review, several applications such fragments new catalysts are presented. significant number cases described, diazine- triazine-based ligands either outperform their pyridine or offer alternative pathways enable reactivities. The potential opportunities unlocked by using these blocks discussed, origin enhanced activity highlighted where mechanistic studies available.

Language: Английский

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Synthesis of polysubstituted fused pyrrolidines via [2 + 2]/[2 + 3] cycloaddition of azomethine ylides

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(15), P. 4149 - 4155

Published: Jan. 1, 2024

A general approach via [2 + 2]/[2 3] cycloaddition is elaborated for the preparation of densely substituted 3-azabicyclo[3.2.0]heptanes in good yields with excellent diastereoselectivities.

Language: Английский

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Theoretical Insights into the Mechanism and Origin of Solvent-Dependent Selectivity in the Cyclization of Propargyl Alcohols for the Divergent Synthesis of N-Heterocycles

The Journal of Physical Chemistry A, Journal Year: 2024, Volume and Issue: 128(32), P. 6729 - 6738

Published: Aug. 7, 2024

This study elucidates the mechanisms and principles governing chemoselectivity in synthesizing two distinct N-heterocycles, benzimidazole thiazine benzothiazole imidazole, through BF

Language: Английский

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