Selective production of linear α-olefins <i>via</i> catalytic deoxygenation of fatty acids and derivatives

Chatterjee, Anamitra; Eliasson, Sondre H. Hopen; Jensen, Vidar R.

doi:10.1039/c7cy02580g

Cited by 33 publications

(20 citation statements)

References 170 publications

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“…The synthetic significance of this transformation is further enhanced when it is applicable to α-hydroxy acids and α-amino acids to produce enol ethers and enamides, which are important intermediates for synthesis 13 , 14 and privileged structures in bioactive compounds 15 , 16 . Reported methods for the transformation of aliphatic carboxylic acids into alkenes include transition-metal-catalyzed decarbonylative dehydration 17 – 22 , decarboxylative oxidation using Pb(IV) 23 , and enzymatic processes 24 , 25 . These methods require either harsh reaction conditions or toxic reagents, or lack generality for synthetic utility.…”

Section: Introductionmentioning

confidence: 99%

Irradiation-induced palladium-catalyzed decarboxylative desaturation enabled by a dual ligand system

Cheng¹,

Shang²,

Fu³

2018

Nat Commun

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Generation of alkenes through decarboxyolefination of alkane carboxylates has significant synthetic value in view of the easy availability of a variety of carboxylic acids and the synthetic versatility of alkenes. Herein we report that palladium catalysts under irradiation with blue LEDs (440 nm) catalyze decarboxylative desaturation of a variety of aliphatic carboxylates to generate aliphatic alkenes, styrenes, enol ethers, enamides, and peptide enamides under mild conditions. The selection of a dual phosphine ligand system is the key enabler for the successful development of this reaction. The Pd-catalyzed decarboxylative desaturation is utilized to achieve a three-step divergent synthesis of Chondriamide A and Chondriamide C in overall 68% yield from simple starting materials. Mechanistic studies suggest that, distinct from palladium catalysis under thermal condition, irradiation-induced palladium catalysis involves irradiation-induced single-electron transfer and dynamic ligand-dissociation/association process to allow two phosphine ligand to work synergistically.

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Section: Introductionmentioning

confidence: 99%

Irradiation-induced palladium-catalyzed decarboxylative desaturation enabled by a dual ligand system

Cheng¹,

Shang²,

Fu³

2018

Nat Commun

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show abstract

“…5D ). 42,43 This terminal alkene can then either be isomerized to form internal alkenes, further cracked to smaller alkene products, or undergo complex condensation to heavy oligomerization products. Taken together, this hybrid approach to hydrocarbon production serves as a proof-of-concept platform to demonstrate the production of olefins from glucose using both cellular and heterogeneous catalysis.…”

Section: Resultsmentioning

confidence: 99%

A Hybrid Cellular-Heterogeneous Catalyst Strategy for the Production of Olefins from Glucose

Wang

Song

Hara³

et al. 2020

Preprint

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Living systems provide a promising approach to chemical synthesis, having been optimized by evolution to convert renewable carbon sources such as glucose to an enormous range of small molecules. However, a large number of synthetic structures can still be difficult to obtain solely from cells, such as unsubstituted hydrocarbons. In this work, we demonstrate the use of a hybrid cellular-heterogeneous catalytic strategy to produce olefins from glucose, using a selective hydrolase to generate an activated intermediate that is readily deoxygenated. Using a new family of iterative thiolase enzymes, we have genetically engineered a microbial strain that produces 4.3 ± 0.4 g L−1 of fatty acid from glucose with 86% captured as 3-hydroxyoctanoic and 3-hydroxydecanoic acids. This 3-hydroxy substituent serves as a leaving group enabling heterogeneous tandem decarboxylation-dehydration routes to olefinic products on Lewis acidic catalysts without the additional redox input required for enzymatic or chemical deoxygenation of simple fatty acids.

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“…88 Chatterjee and Jensen reported the synthesis of Pd NPs capped with phosphine ligands to catalyse the deoxygenation of fatty acids to alkenes via anhydride intermediates (Scheme 7). 89,90 While the PPh 3 -modified Pd catalyst performed poorly, the use of bidentate Xantphos-like ligands, 91 such as DPEphos, resulted in good yields and excellent selectivity towards terminal alkenes. 89 Inspired by these results, we computationally addressed the deoxygenation of pentanoic anhydride as a model substrate on phosphinedecorated Pd(111) surfaces to unravel the underlying reaction pathway.…”

Section: View Article Onlinementioning

confidence: 99%

Reaction mechanisms at the homogeneous–heterogeneous frontier: insights from first-principles studies on ligand-decorated metal nanoparticles

Ortuño

López

2019

Catal. Sci. Technol.

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Selective production of linear α-olefins via catalytic deoxygenation of fatty acids and derivatives

Abstract: Various homogeneous, heterogeneous, and enzyme catalysis strategies for the selective synthesis of linear α-olefins from fatty acids and their derivatives are reviewed.

Cited by 33 publications

References 170 publications

Irradiation-induced palladium-catalyzed decarboxylative desaturation enabled by a dual ligand system

Irradiation-induced palladium-catalyzed decarboxylative desaturation enabled by a dual ligand system

A Hybrid Cellular-Heterogeneous Catalyst Strategy for the Production of Olefins from Glucose

Reaction mechanisms at the homogeneous–heterogeneous frontier: insights from first-principles studies on ligand-decorated metal nanoparticles

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