Joseph S M Samec

Joseph S M Samec
Stockholm University | SU · Department of Organic Chemistry

Professor

About

109
Publications
11,375
Reads
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4,134
Citations
Additional affiliations
May 2017 - present
Stockholm University
Position
  • Professor
July 2015 - April 2017
Stockholm University
Position
  • Professor (Associate)
August 2009 - June 2015
Uppsala University
Position
  • Professor (Associate)

Publications

Publications (109)
Article
We report a stereoinvertive deoxygenation of trans-3-arylglycidates as an alternative route to access thermodynamically less stable (Z)-cinnamate esters by using nickel triflate and triphenylphosphine. Broad functional-group tolerance was observed, with trans-3-arylglycidates containing methyl, methoxy, halo, or nitro groups affording the correspon...
Article
Thermosetting polymeric materials have advantageous properties and are therefore used in numerous applications. In this study, we hypothesized and ultimately showed that thermosets could be derived from comparably sustainable sub‐components. A two‐step procedure to produce a thermoset comprising Kraft lignin (KL) and the cross‐linker adipic acid (A...
Article
Full-text available
Despite the increased use of hemp fiber, negligible attention has been given to upgrade the hemp hurd, which constitutes up to 70 wt % of the hemp stalk and is currently considered a low-value byproduct. In this work, valorization of hemp hurd was performed by reductive catalytic fractionation (RCF) in the presence of a metal catalyst. We found an...
Article
The novel Cr-loaded MCM-22 zeolite (Cr/MCM-22) was successfully synthesized, fully characterized, and applied as a heterogeneous catalyst for the transformation of biomass-derived materials (glucose, sucrose, cellulose, starch, agricultural residues, and other municipal wastes) into levulinic acid via hydrothermolysis. The novel Cr/MCM-22 gives hig...
Article
Full-text available
Lignin is an aromatic polymer that constitutes up to 30 wt% of woody biomass and is considered the largest source of renewable aromatics. Valorization of the lignin stream is pivotal for making biorefining sustainable. Monomeric units in lignin are bound via C–O and C–C bonds. The majority of existing methods for the production of valuable compound...
Article
Reductive catalytic fractionation (RCF) is a promising approach to fractionate lignocellulose and convert lignin to a narrow product slate. To guide research towards commercialization, cost and sustainability must be considered....
Article
Full-text available
Lignin is an abundant polymeric renewable material and thus a promising candidate for incorporation in various commercial thermoplastic polymers. One challenge is to increase the dispersibility of amphiphilic lignin in lipophilic thermoplastic polymers We altered Kraft lignin using widely available and renewable fatty acids, such as oleic acid, yie...
Article
Full-text available
By extracting lignin, pulp production can be increased without heavy investments in a new recovery boiler, the typical bottleneck of a pulp mill. The extraction is performed by using 0.20 and 0.15 weight equivalents of CO 2 and H 2 SO 4 respectively. Herein, we describe lignin esterification with fatty acids using benign reagents to generate a lign...
Article
Full-text available
A novel catalyst based on nickel supported on a folded sheet material (FSM) was synthesized and fully characterized. The resulting Ni-FSM-16 catalyst showed a high reactivity and selectivity in decarboxylation of plant-based carboxylic acids to yield the corresponding linear alkenes and alkanes in up to 75% yield and less than 5% of undesired crack...
Article
The Cover Feature shows a “Green Chemist” contemplating how to achieve the synthesis of α‐sulfenylated carbonyl compounds in a sustainable manner. To do this, he is trying to weigh in the atom economy and the E‐factor of the reaction, as well as the solvents used and possible safety issues. However, achieving a good balance between all these factor...
Article
Organosolv pulping performed in a high-pressure Soxhlet extractor using carbon dioxide as a mild and recyclable acid is described. The system reached a liquid to wood ratio of 6.6 yielding...
Article
Full-text available
α‐Sulfenylated carbonyl compounds are important both as active pharmaceutical ingredients and as intermediates in organic synthesis. Owing to their relevance in synthetic organic chemistry, this Minireview focuses on assessing the most relevant synthetic procedures based on green chemistry metrics. The Minireview starts with the traditional routes...
Article
Full-text available
The valorisation of the plant biopolymer lignin is now recognised as essential to enabling the economic viability of the lignocellulosic biorefining industry. In this context, the “lignin-first” biorefining approach, in which lignin valorisation is considered in the design phase, has demonstrated the fullest utilisation of lignocellulose. We define...
Article
In this Editorial, Guest Editors Run‐Cang Sun, Joseph S. M. Samec, and Arthur J. Ragauskas introduce the Special Issue of ChemSusChem on Lignin Valorization: From Theory to Practice. The significance of and enormous challenges for the utilization of lignin are reviewed, and the contents of the Special Issue with highly interesting contributions fro...
Article
Full-text available
Organosolv pulping releases reactive monomers from both lignin and hemicellulose via the cleavage of weak C–O bonds. These monomers recombine to form undesired polymers through the formation of recalcitrant C–C bonds. Different strategies have been developed to prevent this process by stabilising the reactive monomers (i.e., lignin‐first approaches...
Article
Substitution of fossil energy sources for bio-based ones will require development of efficient processes that can convert inedible and preferably low-value fractions that currently are not used into high-value products. It is desirable that such processes are developed so that both current logistics and infrastructure can be used. Bark, which is th...
Article
Full-text available
Current pulping technologies only valorize the cellulosic fiber giving total yields from biomass below 50 %. Catalytic fractionation enables valorization of both cellulose, lignin, and, optionally, also the hemicellulose. The process consists of two operations occurring in one pot: (1) solvolysis to separate lignin and hemicellulose from cellulose,...
Article
The Suzuki–Miyaura reaction is one of the most powerful tools for the formation of carbon–carbon bonds in organic synthesis. The utilization of alcohols in this powerful reaction is a challenging task. This short review covers progress in the transition-metal-catalyzed Suzuki­–Miyaura-type cross-coupling reaction of π-activated alcohol, such as ary...
Article
The direct intramolecular stereospecific substitution of the hydroxyl group in enantiomerically enriched secondary benzylic, allylic, propargylic, and alkyl alcohols was successfully accomplished by phosphinic acid catalysis. The hydroxyl group was displaced by O-, S-, and N-centered nucleophiles to provide enantioenriched five-membered tetrahydrof...
Article
Die stereospezifische Substitution von nicht‐derivatisierten und nicht‐allylischen enantiomerenangereicherten Alkoholen, bei der lediglich Wasser als Beiprodukt anfällt, würde die Verwendung von leicht verfügbaren Alkoholen als Substrat für nachhaltige Transformationen ermöglichen. Die schlechte Abgangsgruppenfähigkeit der OH‐Gruppe hat jedoch die...
Article
The stereospecific substitution of non‐derivatized and non‐allylic enantioenriched alcohols with only water as a by‐product would enable the use of readily available alcohols as substrates for green and sustainable transformations. However, the poor leaving group ability of the OH group has hampered the development of such a process. Denton and co‐...
Article
Full-text available
Optically pure alcohols are abundant in nature and attractive as feedstock for organic synthesis but challenging for further transformation using atom efficient and sustainable methodologies, particularly when there is a desire to conserve the chirality. Usually, substitution of the OH group of stereogenic alcohols with conservation of chirality re...
Article
Chiral α-sulfenylated ketones are versatile building blocks, although there are still several limitations with their prep-aration. Here we report a new two-step procedure, consisting in a Pd-catalyzed hydrothiolation of propargylic alco-hols followed by an enantioselective Rh-isomerization of allylic alcohols. The isomerization reaction is the key...
Article
A nickel-catalyzed C(sp3)-C(sp2) Suzuki cross-coupling of arylboronic acids and (hetero)naphthyl alcohols has been developed. A Ni(dppp)Cl2 complex showed the highest efficiency and broadest substrate scope. High functional group tolerance has been achieved where 35 compounds could be generated in good to excellent yields, including both primary an...
Article
We have studied the interaction of lignin fragments obtained from catalytic fractionation with a heterogeneous palladium catalyst. By studying the adsorption of verified substrate and product molecules on the palladium surface, understanding of what governs adsorption and desorption dynamics of both substrates and products has been obtained. In add...
Article
Full-text available
The idea of using biaryl structures to generate synthetic building block such as spirolactones is attractive because biaryl structures are abundant in biomass waste streams. However, the inertness of aromatic rings of biaryls makes it challenging to transform them into functionalized structures. In this work, we developed a photoinduced dearomatiza...
Article
Invited for this month's cover is the group of Joseph S. M. Samec at Stockholm University together with Duangamol Tungasmita from Chulalongkorn University. The image shows cobalt‐based heterogeneous catalyst on nitrogen‐doped carbon support outperforming the noble‐metal‐based competitors. The Communication itself is available at 10.1002/cssc.201802...
Article
The Front Cover shows a “Lignin‐First approach” where birch wood is fractionated and simultaneously the lignin is reductively depolymerized. For the first time, a heterogeneous cobalt catalyst is used instead of noble metal‐based catalysts. The cobalt was immobilized on a nitrogen doped carbon support to form Co‐phen/C. Noteworthy, the catalytic sy...
Article
Herein, we present a catalytic reductive fractionation of lignocellulose using a heterogeneous cobalt catalyst and formic acid or formate as a hydrogen donor. The catalytic reductive fractionation of untreated birch wood yield monophenolic compounds in up to 34 wt% yield of total lignin, and this corresponds to 76% of the theoretical maximum yield....
Article
The interaction of fragments derived from lignin depolymerization with a heterogeneous palladium catalyst in methanol--water solution is studied by means of experimental and theoretical methodologies. Quantum chemistry calculations and molecular dynamics simulations based on the ReaxFF approach are combined effectively to obtain an atomic level cha...
Article
A series of phenolic bio‐oil components were selectively hydrodearomatized by palladium on carbon into the corresponding ketones or alcohols in excellent yields using polymethylhydrosiloxane and water as reducing agent. The selectivity of the reaction was governed by the water concentration where selectivity to alcohol was favoured at higher water...
Article
In a recent Joule article, Rinaldi and co-workers report a convergent lignin-first approach that uses a part of the cellulose of the woody biomass as a source of hydrogen equivalents in the hydrodeoxygenation of the lignin from a catalytic fractionation to produce aromatic or aliphatic biofuels.
Article
Black liquor (BL) from the kraft pulping process has been treated at elevated temperatures (380 °C) in a batch reactor to give high yields of a bio oil comprising monomeric phenolic compounds that were soluble in organic solvents and mineral oil and a water fraction with inorganic salts. The metal content in the product was <20 ppm after a simple e...
Article
A reductive fractionation process for the valorization of Quercus suber bark towards hydrocarbons in gasoline and diesel ranges and optionally 4-ethylguaiacol has been developed. The procedure involves three steps: 1) tandem hydrogen-free Pd/C-catalyzed transfer hydrogenolysis of lignin where the carbohydrates serve as an inherent hydrogen donor un...
Article
Non-activated phenols have been employed as nucleophiles in the allylation of non-derivatized allylic alcohols to generate allylated phenolic ethers with water as the only by-product. A Pd[BiPhePhos] catalyst was found to be reactive to give the O-allylated phenols in good to excellent yields in the presence of molecular sieves. The reactions are c...
Article
Pd[κ²-BiPhePhos][η³-C3H5][OTf] is reported as an efficient catalyst in the Tsuji–Trost reaction of non-derivatized allylic alcohols. Both inter- and intramolecular stereospecific allylic substitutions with various types of nucleophiles (C-, S-, N-, and O-centered) were successfully transformed. The desired products were obtained in high yield and h...
Article
Palladium-catalyzed allylic substitution of non-derivatized enantioenriched allylic alcohols with a variety of uncharged N-, S-, C- and O-centered nucleophiles using a bidentate BiPhePhos ligand is described. A remarkable effect of the counter ion (X) of the XPd[kappa-2-BiPhePhos][eta-3-C3H5] was observed. When ClPd[kappa-2-BiPhePhos][eta-3-C3H5] (...
Article
Full-text available
A reductive lignocellulose fractionation in a flow-through system in which pulping and transfer hydrogenolysis steps were separated in time and space has been developed. Without the hydrogenolysis step or addition of trapping agents to the pulping, it is possible to obtain partially depolymerized lignin (21 wt% monophenolic compounds) that is prone...
Article
Biobased diepoxy synthons derived from isoeugenol, eugenol or resorcinol (DGE-isoEu, DGE-Eu and DGER, respectively) have been used as epoxy monomers in replacement of the diglycidyl ether of bisphenol A (DGEBA). Their curing with six different biobased anhydride hardeners leads to fully biobased epoxy thermosets. These materials exhibit interesting...
Article
This review discusses the challenges within the research area of modern biomass fractionation and valorization. The current pulping industry focuses on pulp production and the resulting cellulose fiber. The hemicellulose and lignin are handled as low value streams for process heat and regeneration of process chemicals. The paper and pulp industry h...
Poster
Full-text available
Current processes for the fractionation of lignocellulosic biomass focus on the carbohydrate part, more precisely, cellulosic fibers. The other fractions (hemicellulose and lignin) that constitute approximately half of lignocellulose are treated as waste or used for energy production. The transformation of lignocellulose beyond paper pulp to fine c...
Article
The Cover depicts our research as the final task of Ulysses. The golden bow represents the gold catalyst IPrAuNTf2, also present in the golden flasks, which operates the initial cyclization. Just as Ulysses had to shoot the arrow through the axes, here the two Pd axes are atop a black Pd/C mound to symbolize the regio- and chemoselectivity of the t...
Article
Full-text available
A mild Pd/C-catalyzed hydrogenolysis of the C–O bond of model compounds representing the dibenzodioxocin motif in lignin using polymethylhydrosiloxane (PMHS) and water as hydrogen source was developed. The efficiency of the reaction is highly dependent on both water concentration and the addition of a base. The results from mechanistic studies show...
Article
The pulping industry could become a biorefinery if the lignin and hemicellulose components of the lignocellulose are valorized. Conversion of lignin into well-defined aromatic chemicals is still a major challenge. Lignin depolymerization reactions often occur in parallel with irreversible condensation reactions of the formed fragments. Here, we des...
Article
Density functional theory (DFT) calculations, combined with a constrained minima hopping algorithm (global minimum search while preserving the molecular identity), have been performed to investigate important reaction intermediates for the heterogeneously catalyzed β−O−4’ bond cleavage in lignin derivatives. More specifically, we have studied the a...
Article
A novel lignin-based synthon, diglycidylether of iso-eugenol (DGE-isoEu) is used as a prepolymer for the preparation of thermosetting resins. DGE-isoEu is synthesized in a two-step procedure with a satisfactory yield from bio-based iso-Eugenol (isoEu, 2-Methoxy-4-(1-propenyl)phenol) catalytically fragmented from lignin in an organosolv process. DGE...
Article
Precipitated kraft lignin from black liquor was converted into green diesel in three steps. A mild Ni-catalyzed transfer hydrogenation/hydrogenolysis using 2-propanol generated a lignin residue in which the ethers, carbonyls, and olefins were reduced. An organocatalyzed esterification of the lignin residue with an in situ prepared tall oil fatty ac...
Article
An intramolecular substitution of the OH group in enantioenriched alcohols is achieved by acid/base bifunctional catalysis.
Article
Current processes for the fractionation of lignocellulosic biomass focus on the production of high-quality cellulosic fibers for paper, board, and viscose production. The other fractions that constitute a major part of lignocellulose are treated as waste or used for energy production. The transformation of lignocellulose beyond paper pulp to a comm...
Article
The Pd-catalyzed bis-allylation of aromatic and aliphatic amines followed by a one-pot Grubbs-catalyzed ring-closing metathesis and a FeCl3-promoted aromatization provides an efficient route to 1,3-disubstituted pyrroles.
Article
A brief overview of the development of direct substitution of the hydroxyl (OH) group of alcohols in our research group is presented. By applying a Bronsted acid, an intramolecular substitution of the OH group in stereogenic alcohols with chirality transfer was achieved. Noteworthy, the intramolecular substitution has a wide scope in respect to bot...
Article
An atom efficient route to pyrroles substituted in the β-position has been achieved in four high yielding steps by a combination of Pd-, Ru-, and Fe-catalysis with only water and ethene as side-products. The reaction is general and gives pyrroles substituted in the β-position with linear and branched alkyl-, benzyl-, or aryl groups in overall good...
Article
A key factor for a successful aerobic oxidation process is the addition of catalytic amounts of glucose to inhibit deactivation of the Pd-C catalyst.
Article
Full-text available
A Pd/C catalyzed redox neutral CO bond cleavage of 2-aryloxy-1-arylethanols has been developed. The reactions are carried out at 80 °C, in air, using a green solvent system to yield the aryl ketones in near quantitative yields. Addition of catalytic amounts of a hydrogen source to the reaction mixture activates the catalyst to proceed through a lo...
Article
The hydroxyl group of enantioenriched benzyl-, propargyl-, allyl-, and alkyl alcohols has been intramolecularly displaced by uncharged O-, N-, and S-centered nucleophiles to yield enantioenriched tetrahydrofuran, pyrrolidine, and tetrahy-drothiophene derivatives with phosphinic acid catalysis. The 5-membered heterocyclic products are generated in g...
Article
A mild and chemoselective oxidation of the α-alcohol in β-O-4′-ethanoaryl and β-O-4′-glycerolaryl ethers has been developed. The benzylic alcohols were selectively dehydrogenated to the corresponding ketones in 60–93 % yield. A one-pot selective route to aryl ethyl ketones was performed. The catalytic system comprises recyclable heterogeneous palla...
Article
An atom-efficient synthesis of keto thioethers was devised via tandem gold/palladium catalysis. The reaction proceeds through a regioselective thiol attack at the β-position of the alcohol, followed by an alkyl, aryl, or benzyl 1,2-shift. Both acyclic and cyclic systems were studied, in the latter case leading to the ring expansion of cyclic substr...
Article
A tandem organosolv pulping and Pd-catalysed transfer hydrogenolysis depolymerisation and deoxygenation has been developed. The tandem process generated 2-methoxy-4-(prop-1-enyl)phenol in 23 % yield (92 % theoretical monomer yield) starting from pine wood and 2,6-dimethoxy-4-(prop-1-enyl)phenol in 49 % yield (92 % theoretical monomer yield) startin...
Article
An efficient and highly atom-economical tandem Pd/Au-catalyzed route to α-sulfenylated carbonyl compounds from terminal propargylic alcohols and thiols has been developed. This one-step procedure has a wide substrate scope with respect to substituents at the α-position of the alcohol. Both aromatic and aliphatic thiols generated the α-sulfenylated...
Article
A mild and robust heterogeneous palladium-catalyzed CO bond cleavage of 2-aryloxy-1-arylethanols using formic acid as reducing agent in air was developed. The cleaved products were isolated in 92–98 % yield; and by slightly varying the reaction conditions, a ketone, an alcohol, or an alkane can be generated in near-quantitative yield. This reaction...
Article
Gold(I)-chloride-catalyzed synthesis of α-sulfenylated carbonyl compounds from propargylic alcohols and aryl thiols showed a wide substrate scope with respect to both propargylic alcohols and aryl thiols. Primary and secondary aromatic propargylic alcohols generated α-sulfenylated aldehydes and ketones in 60-97 % yield. Secondary aliphatic propargy...