Eucalyptol as a Bio-Based Solvent for Buchwald-Hartwig Reaction on O,S,N-Heterocycles

Campos, Joana F.; Berteina‐Raboin, Sabine

doi:10.3390/catal9100840

Cited by 14 publications

(12 citation statements)

References 38 publications

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“…For this purpose, the reaction was first optimized using the compound 4a and aniline. The choice of the catalytic system, base, and temperature was based on our previous work [ 12 ]. Once again, toluene was used as a conventional solvent reference ( Table 8 , Entry 1).…”

Section: Resultsmentioning

confidence: 99%

“…Therefore it seemed relevant to compare it to other ether-type solvents deemed to be green. In order to continue to develop new and green methods to construct heterocyclic rings containing oxygen, sulfur, and nitrogen [ 10 , 11 , 12 , 13 , 14 ], we report here the use of eucalyptol (1,8-cineole), cyclopentyl methyl ether (CPME), and 2-methyltetrahydrofuran (2-MeTHF) as alternative solvents for metal-free click chemistry and Buchwald–Hartwig coupling ( Figure 1 ). 2-methyltetrahydrofuran (2-MeTHF) is already well known to generate fewer peroxides than when tetrahydrofuran (THF) is obtained from renewable corncobs and bagasse resources.…”

Section: Introductionmentioning

confidence: 99%

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Demonstration of Green Solvent Performance on O,S,N-Heterocycles Synthesis: Metal-Free Click Chemistry and Buchwald—Hartwig Coupling

et al. 2021

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Demonstration of Green Solvent Performance on O,S,N-Heterocycles Synthesis: Metal-Free Click Chemistry and Buchwald—Hartwig Coupling

et al. 2021

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“…Moderate to excellent yields were obtained (43–99%), in many cases better than the reported yields for the analogous reaction conducted in a conventional dipolar aprotic solvent. 289 …”

Section: Common Reactions In Dipolar Aprotic or Ethereal Solvents Rep...mentioning

confidence: 99%

Replacement of Less-Preferred Dipolar Aprotic and Ethereal Solvents in Synthetic Organic Chemistry with More Sustainable Alternatives

et al. 2022

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Dipolar aprotic and ethereal solvents comprise just over 40% of all organic solvents utilized in synthetic organic, medicinal, and process chemistry. Unfortunately, many of the common “go-to” solvents are considered to be “less-preferable” for a number of environmental, health, and safety (EHS) reasons such as toxicity, mutagenicity, carcinogenicity, or for practical handling reasons such as flammability and volatility. Recent legislative changes have initiated the implementation of restrictions on the use of many of the commonly employed dipolar aprotic solvents such as dimethylformamide (DMF) and N -methyl-2-pyrrolidinone (NMP), and for ethers such as 1,4-dioxane. Thus, with growing legislative, EHS, and societal pressures, the need to identify and implement the use of alternative solvents that are greener, safer, and more sustainable has never been greater. Within this review, the ubiquitous nature of dipolar aprotic and ethereal solvents is discussed with respect to the physicochemical properties that have made them so appealing to synthetic chemists. An overview of the current legislative restrictions being imposed on the use of dipolar aprotic and ethereal solvents is discussed. A variety of alternative, safer, and more sustainable solvents that have garnered attention over the past decade are then examined, and case studies and examples where less-preferable solvents have been successfully replaced with a safer and more sustainable alternative are highlighted. Finally, a general overview and guidance for solvent selection and replacement are included in the Supporting Information of this review.

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“…as the base at 110 • C in 1,8-cineole. For the starting materials as the substrate containing oxygen, sulfur and nitrogen, they selected five brominated products (i.e., 2-bromofluorene, 4-bromo-1,2-methylenedioxybenzene, 6-bromo-2-methylquinoline, 7-bromo-6-phenylthieno [2,3-b]pyrazine and 3-bromo-2-phenylthieno[3,2-b]pyridine) and several amine derivatives [145]. They were able to synthesize the desired compounds 49-71 in moderate to excellent yields (Figure 7).…”

Section: Buchwald-hartwig Coupling Reactionmentioning

confidence: 99%

Eucalyptol, an All-Purpose Product

Campos

Berteina‐Raboin

2022

Catalysts

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Eucalyptus plants have attracted the attention of researchers and environmentalists worldwide because they are a rapidly growing source of wood and a source of oil used for multiple purposes. The main and the most important oil component is 1,8-cineole (eucalyptol: 60%–85%). This review summarizes the literature reported to date involving the use of 1,8-cineole for the treatment of disorders. Additionally, we describe our efforts in the use of eucalyptol as a solvent for the synthesis of O,S,N-heterocycles. Solvents used in chemistry are a fundamental element of the environmental performance of processes in corporate and academic laboratories. Their influence on costs, safety and health cannot be neglected. Green solvents such as bio-based systems hold considerable additional promise to reduce the environmental impact of organic chemistry. The first section outlines the process leading to our discovery of an unprecedented solvent and its validation in the first coupling reactions. This section continues with the description of its properties and characteristics and its reuse as reported in the various studies conducted. The second section highlights the use of eucalyptol in a series of coupling reactions (i.e., Suzuki–Miyaura, Sonogashira–Hagihara, Buchwald–Hartwig, Migita–Kosugi–Stille, Hiyama and cyanation) that form O,S,N-heterocycles. We describe the optimization process applied to reach the ideal conditions. We also show that eucalyptol can be a good alternative to build heterocycles that contain oxygen, sulfur and nitrogen. These studies allowed us to demonstrate the viability and potential that bio solvents can have in synthesis laboratories.

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Eucalyptol as a Bio-Based Solvent for Buchwald-Hartwig Reaction on O,S,N-Heterocycles

Cited by 14 publications

References 38 publications

Demonstration of Green Solvent Performance on O,S,N-Heterocycles Synthesis: Metal-Free Click Chemistry and Buchwald—Hartwig Coupling

Demonstration of Green Solvent Performance on O,S,N-Heterocycles Synthesis: Metal-Free Click Chemistry and Buchwald—Hartwig Coupling

Replacement of Less-Preferred Dipolar Aprotic and Ethereal Solvents in Synthetic Organic Chemistry with More Sustainable Alternatives

Eucalyptol, an All-Purpose Product

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