Metathesis of renewable polyene feedstocks – Indirect evidences of the formation of catalytically active ruthenium allylidene species

Kovács, E.; Sághy, Péter; Turczel, Gábor; Tóth, Imre; Lendvay, György; Domján, Attila; Anastas, Paul T.; Tuba, Róbert

doi:10.1016/j.jorganchem.2017.04.018

Cited by 7 publications

(7 citation statements)

References 26 publications

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“…This is not surprising as CPD is relatively unstable, it can spontaneously dimerize to DCPD via Diels‐Alder (DA) reaction ,. In addition, the conjugated electron system is expected to reduce activity in metathesis reactions via the formation of less or non‐reactive η 4 ‐allylidene (vinylcarbene) species (Scheme ) …”

Section: Introductionmentioning

confidence: 99%

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One‐pot Synthesis of 1,3‐Butadiene and 1,6‐Hexanediol Derivatives from Cyclopentadiene (CPD) via Tandem Olefin Metathesis Reactions

et al. 2018

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A novel tandem reaction of cyclopentadiene leading to high value linear chemicals via ruthenium catalyzed ring opening cross metathesis (ROCM), followed by cross metathesis (CM) is reported. The ROCM of cyclopentadiene (CPD) with ethylene using commercially available 2 nd gen. Grubbs metathesis catalysts (1-G2) gives 1,3-butadiene (BD) and 1,4-pentadiene (2) (and 1,4-cyclohexadiene (3)) with reasonable yields (up to 24 % (BD) and 67 % (2 + 3) at 73% CPD conversion) at 1-5 mol % catalyst loading in toluene solution (5 V% CPD, 10 bar, RT) in an equilibrium reaction. The ROCM of CPD with cis-butene diol diacetate (4) using 1.00 -0.05 mol % of 3 rd gen. Grubbs (1-G3) or 2 nd gen. Hoveyda-Grubbs (1-HG2) catalysts loading gives hexa-2,4-diene-1,6-diyl diacetate (5), which is a precursor of 1,6hexanediol (an intermediate in polyurethane, polyester and polyol synthesis) and hepta-2,5-diene-1,7-diyl diacetate (6) in good yield (up to 68 % or TON: 1180). Thus, convenient and selective synthetic procedures are revealed by ROCM of CPD with ethylene and 4 leading to BD and 1,6-hexanediol precursor, respectively, as key components of commercial intermediates of high-performance materials.

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Section: Introductionmentioning

confidence: 99%

“…However, the use of cross‐coupling agents containing electron withdrawing groups (i. e. like acrylonitrile) “shut down” the secondary metathesis step of the cascade reactions via the formation of an electron deficient, less nucleophile conjugated intermediate …”

Section: Introductionmentioning

confidence: 99%

One‐pot Synthesis of 1,3‐Butadiene and 1,6‐Hexanediol Derivatives from Cyclopentadiene (CPD) via Tandem Olefin Metathesis Reactions

et al. 2018

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“…It is possible to explain the overall process by means of systems chemistry. Through the change in the aromaticity (AR%) [ 142 ] and carbonylicity (CA%) values [computed at B3LYP/6-31G(d,p)//PCM(water)] it is possible to understand how the electron distribution follows the energetic changes in the triplet excited as well as the ground state during the photochemical process. DNI-Glu ( 62 ) is composed of an aromatic ring and a carbonyl group ( Figure 24 ), characterized by values of AR% and CA%.…”

Section: Discussionmentioning

confidence: 99%

Amide Activation in Ground and Excited States

et al. 2018

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Not all amide bonds are created equally. The purpose of the present paper is the reinterpretation of the amide group by means of two concepts: amidicity and carbonylicity. These concepts are meant to provide a new viewpoint in defining the stability and reactivity of amides. With the help of simple quantum-chemical calculations, practicing chemists can easily predict the outcome of a desired process. The main benefit of the concepts is their simplicity. They provide intuitive, but quasi-thermodynamic data, making them a practical rule of thumb for routine use. In the current paper we demonstrate the performance of our methods to describe the chemical character of an amide bond strength and the way of its activation methods. Examples include transamidation, acyl transfer and amide reductions. Also, the method is highly capable for simple interpretation of mechanisms for biological processes, such as protein splicing and drug mechanisms. Finally, we demonstrate how these methods can provide information about photo-activation of amides, through the examples of two caged neurotransmitter derivatives.

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“…Although the yield of the metathesis reaction is low (11%), this reaction is highly relevant as it demonstrates the applicability of metathesis reactions in the synthesis of conjugated double bond systems. [44][45][46][47] Scheme 8. Synthesis of pheromone of Cydia pomonella (20)…”

Section: Scheme 7 Three Different Routes To E-9-decenyl-acetate (14) the Pheromone Of Platynota Stultanamentioning

confidence: 99%

Synthesis of Semiochemicals via Olefin Metathesis

Turczel

Kovács

Merza

et al. 2018

ACS Sustainable Chem. Eng.

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Semiochemicals are substances or mixtures that carry messages and are used for communication between individuals of the same or different species. Semiochemicals that are used in pest control are called biopesticides. Conventional pesticides, which are generally synthetically derived and unnatural, inactivate or kill the pests, whereas biopesticides are naturally occurring compounds that attract insects to a trap or interfere with their reproduction.There are several advantages to biopesticides. Compared to conventional pesticides, biochemical-based pesticides are often less toxic and therefore pose a significantly lower impact 2 on human health and the environment. Moreover, the biopesticides are pest selective and as such, do not negatively impact other organisms such as insects, mammals or birds. Other advantages of biopesticides include high potency, meaning that smaller amounts of biopesticide are required, less resistance by target organisms, and the ability to biodegrade more quickly than conventional pesticides. [1][2][3] Although the biochemical-based pesticides are very promising materials, their production is often cumbersome and their application is often limited. So far, most of the biopesticides are synthesized by multistep, classical organic reactions which are not economical and pose high environmental impact. However, in recent decades, many efforts have been done to implement cost-effective and safer chemical procedures for the widespread application of biochemical-based pesticides. The purpose of this perspective is to draw the attention of the green chemistry community to the applicability of olefin metathesis reactions in environmental benign and cost-effective biopesticide synthesis. In this article, we review seminal work on the total synthesis of biopesticides using olefin metathesis as a key reaction step, and in doing so, we hope to inspire new ideas for forthcoming olefin metathesis based biopesticide development.

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Metathesis of renewable polyene feedstocks – Indirect evidences of the formation of catalytically active ruthenium allylidene species

Cited by 7 publications

References 26 publications

One‐pot Synthesis of 1,3‐Butadiene and 1,6‐Hexanediol Derivatives from Cyclopentadiene (CPD) via Tandem Olefin Metathesis Reactions

One‐pot Synthesis of 1,3‐Butadiene and 1,6‐Hexanediol Derivatives from Cyclopentadiene (CPD) via Tandem Olefin Metathesis Reactions

Amide Activation in Ground and Excited States

Synthesis of Semiochemicals via Olefin Metathesis

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