Efficient synthesis of styrene derivatives through ethenolysis of renewable propenylbenzenes

Avendaño-Villarreal, Jesus A.; Granato, Artur V.; Delolo, Fábio G.; Santos, Eduardo N. dos

doi:10.1016/j.mcat.2021.111631

Cited by 6 publications

(7 citation statements)

References 38 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The ruthenium‐catalyzed ethenolysis of 1‐propenylbenzenes as a convenient access to functionalized styrenes has been studied in our recent work [46] . In the present work, we decided to integrate this process with the consecutive HAM of the styrenes formed in this reaction.…”

Section: Resultsmentioning

confidence: 99%

“…Anethole ( 1 a ) was chosen as a benchmark substrate and a commercial ruthenium complex M73SIPr (Figure 2) as the catalyst for the ethenolysis step. The ethenolysis of 1 a was performed under the conditions optimized in our previous work (Table 1, run 1) [46] . The reaction was completed in 2 hours to give 4‐vinylanisole ( 2 a ) in a nearly quantitative yield.…”

Section: Resultsmentioning

confidence: 99%

“…Established classical and modern methods for the synthesis of functionalized styrenes involve the use of stoichiometric amounts of reagents and, therefore, generate large amounts of waste [35–45] . An alternative and more attractive route to certain styrenes is the cross‐metathesis of 1‐propenylbenzenes with ethylene promoted by ruthenium catalysts (ethenolysis) [46] . Functionalized styrenes can be also obtained from 2‐propenylbenzenes through the tandem isomerization/ethenolysis process [47,48] …”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

2‐Arylpropylamines from 1‐Propenylbenzenes in a New One‐Pot Metathesis–Hydroaminomethylation Protocol

et al. 2023

Self Cite

View full text Add to dashboard Cite

2-Arylpropylamines are useful as active pharmaceutical ingredients (APIs) and as synthetic building blocks in fine chemistry. Herein we report a new and efficient methodology to transform naturally occurring 1-propenylbenzenes into 2-arylpropylamines employing a one-pot ethenolysis/hydroaminomethylation protocol. Four consecutive reactions must occur in the same reaction vessel and the careful selection of the reaction conditions was critical to obtain the desired products in high yields. The negative interference between the ethenolysis and the hydroaminomethylation (HAM) catalysts was circumvented by the appropriate adjustment on the molar ratio of the catalysts. As a result, nine 2-arylpropylamines were obtained in yields ranging in 75-93 %.

show abstract

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

2‐Arylpropylamines from 1‐Propenylbenzenes in a New One‐Pot Metathesis–Hydroaminomethylation Protocol

et al. 2023

Self Cite

View full text Add to dashboard Cite

show abstract

“…[50,51] A particular case of olefin metathesis -when the crosscoupling agent is ethylene -is called ethenolysis. [9,52] In case of linear mono-olefins, the complete ISOMET using ethylene (in excess) as cross-coupling agent theoretically ends up in propylene [53] as the only end product independently of the double bond's position and the length of the hydrocarbon chain (Scheme 2). ISOMET reactions using renewable-based ethylene [54,55] is an emerging approach to develop sustainable, environmentally benign chemical procedures.…”

Section: Catalytic Degradation Of Hydrocarbons To Propylene Via Isome...mentioning

confidence: 99%

Making Persistent Plastics Degradable

et al. 2023

View full text Add to dashboard Cite

The vastness of the scale of the plastic waste problem will require a variety of strategies and technologies to move toward sustainable and circular materials. One of these strategies to address the challenge of persistent fossil‐based plastics is new catalytic processes that are being developed to convert recalcitrant waste such as polyethylene to produce propylene, which can be an important precursor of high‐performance polymers that can be designed to biodegrade or to degrade on demand. Remarkably, this process also enables the production of biodegradable polymers using renewable raw materials. In this Perspective, current catalyst systems and strategies that enable the catalytic degradation of polyethylene to propylene are presented. In addition, concepts for using “green” propylene as a raw material to produce compostable polymers is also discussed.

show abstract

“…eugenol ( 1 ) to isoeugenol ( 2 )] and subsequent cross-metathesis reactions have been combined in orthogonal tandem catalytic sequences . As CM partners in such sequences mainly ethylene − and acrylates , have been used, the self-metathesis of either isolated or in situ generated isoeugenol to the respective stilbene − has also been investigated. Overall, however, literature reports on cross-metathesis reactions of isoeugenol ( 2 ) and other bio-based propenylbenzenes are scarce.…”

Section: Introductionmentioning

confidence: 99%

Methylene Capping Facilitates Cross-Metathesis Reactions of Enals: A Short Synthesis of 7-Methoxywutaifuranal from the Xylochemical Isoeugenol

et al. 2022

View full text Add to dashboard Cite

Four combinations of type-I olefins isoeugenol and 4-hydroxy-3-methoxystyrene with type-II olefins acrolein and crotonaldehyde were investigated in cross-metathesis (CM) reactions. While both type-I olefins are suitable CM partners for this transformation, we observed synthetically useful conversions only with type-II olefin crotonaldehyde. For economic reasons, isoeugenol, a cheap xylochemical available from renewable lignocellulose or from clove oil, is the preferred type-I CM partner. Nearly quantitative conversions to coniferyl aldehyde by the CM reaction of isoeugenol and crotonaldehyde can be obtained at ambient temperature without a solvent or at high substrate concentrations of 2 mol·L–1 with the second-generation Hoveyda–Grubbs catalyst. Under these conditions, the ratio of reactants can be reduced to 1:1.5 and catalyst loadings as low as 0.25 mol % are possible. The high reactivity of the isoeugenol/crotonaldehyde combination in olefin metathesis reactions was demonstrated by a short synthesis of the natural product 7-methoxywutaifuranal, which was obtained from isoeugenol in a 44% yield over five steps. We suggest that the superior performance of crotonaldehyde in the CM reactions investigated can be rationalized by “methylene capping”, i.e., the steric stabilization of the propagating Ru-alkylidene species.

show abstract

Efficient synthesis of styrene derivatives through ethenolysis of renewable propenylbenzenes

Cited by 6 publications

References 38 publications

2‐Arylpropylamines from 1‐Propenylbenzenes in a New One‐Pot Metathesis–Hydroaminomethylation Protocol

2‐Arylpropylamines from 1‐Propenylbenzenes in a New One‐Pot Metathesis–Hydroaminomethylation Protocol

Making Persistent Plastics Degradable

Methylene Capping Facilitates Cross-Metathesis Reactions of Enals: A Short Synthesis of 7-Methoxywutaifuranal from the Xylochemical Isoeugenol

Contact Info

Product

Resources

About