@article{61335, abstract = {{Amidines are a ubiquitous class of bioactive compounds found in a wide variety of natural products; thus, efficient strategies for their preparation are in great demand. Herein, a novel protocol is reported for the synthesis of amidines based on PIII/PVO redox catalysis. This two‐step, one‐pot approach involves the activation of amides via PIII/PVO catalyzed in situ formation of imidoyl chloride intermediates which are directly converted upon reaction with amines into the corresponding amidines. Instead of traditionally used toxic and corrosive chloride sources, hexachloroacetone (HCA) is successfully employed as a halide source. The reaction proceeds with low catalyst loading (2 mol%) in BuOAc as the solvent. Under the optimized conditions, 20 amidines are prepared in yields up to 99%. A feasible mechanism is proposed based on experimental results. The synthetic potential of this method is evaluated in the preparation of the tyrosine kinase inhibitor (TKI) Erlotinib.}}, author = {{Medvaric, Viktorija and Paradies, Jan and Werner, Thomas}}, issn = {{1615-4150}}, journal = {{Advanced Synthesis and Catalysis}}, keywords = {{T2, T, CSSD}}, publisher = {{Wiley}}, title = {{{Synthesis of Amidines Via P(III)/P(V)=O Redox Catalyzed In Situ Formation of Imidoyl Chlorides From Amides}}}, doi = {{10.1002/adsc.70059}}, year = {{2025}}, } @article{61336, author = {{Zhou, Rundong and Medvaric, Viktorija and Werner, Thomas and Paradies, Jan}}, issn = {{0002-7863}}, journal = {{Journal of the American Chemical Society}}, keywords = {{T2, CSSD}}, publisher = {{American Chemical Society (ACS)}}, title = {{{Metal-Free Reduction of Nitrous Oxide via PIII/PV═O Cycling: Mechanistic Insights and Catalytic Performance}}}, doi = {{10.1021/jacs.5c06190}}, year = {{2025}}, } @article{62090, abstract = {{The selective N-formylation and N-methylation of amines with carbon dioxide (CO2) catalyzed by methyltriphenylphosphonium methylcarbonate and tuned by polymethylhydrosiloxane or trimethoxysilane as reducing agents is reported.}}, author = {{Ren, Changyue and Terazzi, Constanza and Werner, Thomas}}, issn = {{1463-9262}}, journal = {{Green Chemistry}}, keywords = {{T1, T2, CSSD}}, number = {{1}}, pages = {{439--447}}, publisher = {{Royal Society of Chemistry (RSC)}}, title = {{{Tuneable reduction of CO2 – organocatalyzed selective formylation and methylation of amines}}}, doi = {{10.1039/d3gc03993e}}, volume = {{26}}, year = {{2024}}, } @article{62091, author = {{Ren, Changyue and Spannenberg, Anke and Werner, Thomas}}, issn = {{2168-0485}}, journal = {{ACS Sustainable Chemistry & Engineering}}, keywords = {{T1, T2, CSSD}}, number = {{29}}, pages = {{10969--10977}}, publisher = {{American Chemical Society (ACS)}}, title = {{{Phosphonium-Salt-Catalyzed N-Methylation and N-Formylation of Amines with CO2}}}, doi = {{10.1021/acssuschemeng.4c03464}}, volume = {{12}}, year = {{2024}}, } @article{62088, author = {{Tönjes, Jan and Medvarić, Viktorija and Werner, Thomas}}, issn = {{0022-3263}}, journal = {{The Journal of Organic Chemistry}}, keywords = {{T2, CSSD}}, number = {{15}}, pages = {{10729--10735}}, publisher = {{American Chemical Society (ACS)}}, title = {{{Synthesis of Trisubstituted Furans from Activated Alkenes by P(III)/P(V) Redox Cycling Catalysis}}}, doi = {{10.1021/acs.joc.4c00985}}, volume = {{89}}, year = {{2024}}, } @article{62095, author = {{Tönjes, Jan and Kell, Lukas and Werner, Thomas}}, issn = {{1523-7060}}, journal = {{Organic Letters}}, keywords = {{T2, CSSD}}, number = {{51}}, pages = {{9114--9118}}, publisher = {{American Chemical Society (ACS)}}, title = {{{Organocatalytic Stereospecific Appel Reaction}}}, doi = {{10.1021/acs.orglett.3c03463}}, volume = {{25}}, year = {{2023}}, } @article{37940, author = {{Ren, Changyue and Spannenberg, Anke and Werner, Thomas}}, issn = {{2193-5807}}, journal = {{Asian Journal of Organic Chemistry}}, keywords = {{T1, T2, CSSD}}, number = {{9}}, publisher = {{Wiley}}, title = {{{Synthesis of Bifunctional Phosphonium Salts Bearing Perfluorinated Side Chains and Their Application in the Synthesis of Cyclic Carbonates from Epoxides and CO 2}}}, doi = {{10.1002/ajoc.202200156}}, volume = {{11}}, year = {{2022}}, } @article{37946, abstract = {{AbstractThe facile synthesis of highly functionalized building blocks with potential biological activity is of great interest to medicinal chemistry. The benzoxepinone core structures commonly exhibit biological activity. Thus, a short and efficient synthetic route towards benzoxepine containing scaffold, which enables late stage modification was developed. Namely, base-free catalytic Wittig reactions enabled the synthesis of bromobenzoxepinones from readily available starting materials. Subsequent, Suzuki–Miyaura and Stille reactions proved to be suitable methods to access a variety of benzoxepinone diaryl derivatives by late stage modification in only three steps. This three-step reaction sequence is suitable for high throughput applications and gives facile access to highly complex molecular structures, which are suitable for further functionalization. The antiproliferative properties of selected arylbenzoxepinones­ were tested in vitro on monolayer tumor cell line A549. Notably, in this initial screening, these compounds were found to be active in the micromolar range.}}, author = {{Werner, Thomas and Grandane, Aiga and Pudnika, Linda and Domraceva, Ilona and Zalubovskis, Raivis}}, issn = {{0039-7881}}, journal = {{Synthesis}}, keywords = {{T2, T4, CSSD}}, number = {{19}}, pages = {{3545--3554}}, publisher = {{Georg Thieme Verlag KG}}, title = {{{Base-Free Catalytic Wittig-/Cross-Coupling Reaction Sequence as Short Synthetic Strategy for the Preparation of Highly Functionalized Arylbenzoxepinones}}}, doi = {{10.1055/a-1509-6078}}, volume = {{53}}, year = {{2021}}, } @article{37945, abstract = {{

PMHS proved to be a suitable terminal reductant for P(iii)/P(v) redox cycling with a methyl-substituted phosphetane as catalyst and BuOAc as solvent. The formation of water by silanol condensation was identified as main pathway of siloxane formation.

}}, author = {{Tönjes, Jan and Longwitz, Lars and Werner, Thomas}}, issn = {{1463-9262}}, journal = {{Green Chemistry}}, keywords = {{T2, CSSD}}, number = {{13}}, pages = {{4852--4857}}, publisher = {{Royal Society of Chemistry (RSC)}}, title = {{{Poly(methylhydrosiloxane) as a reductant in the catalytic base-free Wittig reaction}}}, doi = {{10.1039/d1gc00953b}}, volume = {{23}}, year = {{2021}}, } @article{62101, abstract = {{AbstractThe carbon–carbon double bond of unsaturated carbonyl compounds was readily reduced by using a phosphetane oxide catalyst in the presence of a simple organosilane as the terminal reductant and water as the hydrogen source. Quantitative hydrogenation was observed when 1.0 mol % of a methyl‐substituted phosphetane oxide was employed as the catalyst. The procedure is highly selective towards activated double bonds, tolerating a variety of functional groups that are usually prone to reduction. In total, 25 alkenes and two alkynes were hydrogenated to the corresponding alkanes in excellent yields of up to 99 %. Notably, less active poly(methylhydrosiloxane) could also be utilized as the terminal reductant. Mechanistic investigations revealed the phosphane as the catalyst resting state and a protonation/deprotonation sequence as the crucial step in the catalytic cycle.}}, author = {{Longwitz, Lars and Werner, Thomas}}, issn = {{0044-8249}}, journal = {{Angewandte Chemie}}, keywords = {{T2, T4}}, number = {{7}}, pages = {{2782--2785}}, publisher = {{Wiley}}, title = {{{Reduction of Activated Alkenes by PIII/PV Redox Cycling Catalysis}}}, doi = {{10.1002/ange.201912991}}, volume = {{132}}, year = {{2020}}, } @article{62102, abstract = {{AbstractThe carbon–carbon double bond of unsaturated carbonyl compounds was readily reduced by using a phosphetane oxide catalyst in the presence of a simple organosilane as the terminal reductant and water as the hydrogen source. Quantitative hydrogenation was observed when 1.0 mol % of a methyl‐substituted phosphetane oxide was employed as the catalyst. The procedure is highly selective towards activated double bonds, tolerating a variety of functional groups that are usually prone to reduction. In total, 25 alkenes and two alkynes were hydrogenated to the corresponding alkanes in excellent yields of up to 99 %. Notably, less active poly(methylhydrosiloxane) could also be utilized as the terminal reductant. Mechanistic investigations revealed the phosphane as the catalyst resting state and a protonation/deprotonation sequence as the crucial step in the catalytic cycle.}}, author = {{Longwitz, Lars and Werner, Thomas}}, issn = {{1433-7851}}, journal = {{Angewandte Chemie International Edition}}, keywords = {{T2, T4, CSSD}}, number = {{7}}, pages = {{2760--2763}}, publisher = {{Wiley}}, title = {{{Reduction of Activated Alkenes by PIII/PV Redox Cycling Catalysis}}}, doi = {{10.1002/anie.201912991}}, volume = {{59}}, year = {{2020}}, } @article{37953, author = {{Hu, Yuya and Peglow, Sandra and Longwitz, Lars and Frank, Marcus and Epping, Jan Dirk and Brüser, Volker and Werner, Thomas}}, issn = {{1864-5631}}, journal = {{ChemSusChem}}, keywords = {{T2, T1, CSSD}}, number = {{7}}, pages = {{1825--1833}}, publisher = {{Wiley}}, title = {{{Plasma‐Assisted Immobilization of a Phosphonium Salt and Its Use as a Catalyst in the Valorization of CO 2}}}, doi = {{10.1002/cssc.201903384}}, volume = {{13}}, year = {{2020}}, } @article{37952, author = {{Grandane, Aiga and Nocentini, Alessio and Werner, Thomas and Zalubovskis, Raivis and Supuran, Claudiu T.}}, issn = {{0968-0896}}, journal = {{Bioorganic and Medicinal Chemistry}}, keywords = {{T4, T2, CSSD}}, number = {{11}}, publisher = {{Elsevier BV}}, title = {{{Benzoxepinones: A new isoform-selective class of tumor associated carbonic anhydrase inhibitors}}}, doi = {{10.1016/j.bmc.2020.115496}}, volume = {{28}}, year = {{2020}}, } @article{37958, author = {{Longwitz, Lars and Spannenberg, Anke and Werner, Thomas}}, issn = {{2155-5435}}, journal = {{ACS Catalysis}}, keywords = {{T2, CSSD}}, number = {{10}}, pages = {{9237--9244}}, publisher = {{American Chemical Society (ACS)}}, title = {{{Phosphetane Oxides as Redox Cycling Catalysts in the Catalytic Wittig Reaction at Room Temperature}}}, doi = {{10.1021/acscatal.9b02456}}, volume = {{9}}, year = {{2019}}, } @article{37962, author = {{Longwitz, Lars and Jopp, Stefan and Werner, Thomas}}, issn = {{0022-3263}}, journal = {{The Journal of Organic Chemistry}}, keywords = {{T2, CSSD}}, number = {{12}}, pages = {{7863--7870}}, publisher = {{American Chemical Society (ACS)}}, title = {{{Organocatalytic Chlorination of Alcohols by P(III)/P(V) Redox Cycling}}}, doi = {{10.1021/acs.joc.9b00741}}, volume = {{84}}, year = {{2019}}, } @article{37959, abstract = {{Catalytic nucleophilic substitution of alcohols makes organic synthesis greener}}, author = {{Longwitz, Lars and Werner, Thomas}}, issn = {{0036-8075}}, journal = {{Science}}, keywords = {{T2, CSSD}}, number = {{6456}}, pages = {{866--867}}, publisher = {{American Association for the Advancement of Science (AAAS)}}, title = {{{The Mitsunobu reaction, reimagined}}}, doi = {{10.1126/science.aay6635}}, volume = {{365}}, year = {{2019}}, } @article{37966, abstract = {{Abstract Numerous organic transformations are based on the use of stoichiometric amounts of phosphorus reagents. The formation of phosphane oxides from phosphanes is usually the thermodynamic driving force for these reactions. The stoichiometric amounts of phosphane oxide which are formed as by-products often significantly hamper the product purification. Organophosphorus catalysis based on P(III)/P(V) redox cycling aims to address these problems. Herein we present our recent advances in developing catalytic Wittig-type reactions. More specifically, we reported our results on catalytic Wittig reactions based on readily available Bu3P=O as pre-catalyst as well as the first microwave-assisted version of this reaction and the first enantioselective catalytic Wittig reaction utilizing chiral phosphane catalysts. Further developments led to the implementation of catalytic base-free Wittig reactions yielding highly functionalized alkylidene and arylidene succinates.}}, author = {{Longwitz, Lars and Werner, Thomas}}, issn = {{1365-3075}}, journal = {{Pure and Applied Chemistry}}, keywords = {{T2, CSSD}}, number = {{1}}, pages = {{95--102}}, publisher = {{Walter de Gruyter GmbH}}, title = {{{Recent advances in catalytic Wittig-type reactions based on P(III)/P(V) redox cycling}}}, doi = {{10.1515/pac-2018-0920}}, volume = {{91}}, year = {{2019}}, } @article{37965, author = {{Grandane, Aiga and Longwitz, Lars and Roolf, Catrin and Spannenberg, Anke and Murua Escobar, Hugo and Junghanss, Christian and Suna, Edgars and Werner, Thomas}}, issn = {{0022-3263}}, journal = {{The Journal of Organic Chemistry}}, keywords = {{T2, T4, CSSD}}, number = {{3}}, pages = {{1320--1329}}, publisher = {{American Chemical Society (ACS)}}, title = {{{Intramolecular Base-Free Catalytic Wittig Reaction: Synthesis of Benzoxepinones}}}, doi = {{10.1021/acs.joc.8b02789}}, volume = {{84}}, year = {{2019}}, } @article{37967, author = {{Steinbauer, Johannes and Kubis, Christoph and Ludwig, Ralf and Werner, Thomas}}, issn = {{2168-0485}}, journal = {{ACS Sustainable Chemistry and Engineering}}, keywords = {{T1, T2, CSSD}}, number = {{8}}, pages = {{10778--10788}}, publisher = {{American Chemical Society (ACS)}}, title = {{{Mechanistic Study on the Addition of CO2 to Epoxides Catalyzed by Ammonium and Phosphonium Salts: A Combined Spectroscopic and Kinetic Approach}}}, doi = {{10.1021/acssuschemeng.8b02093}}, volume = {{6}}, year = {{2018}}, } @article{37973, abstract = {{

An immobilized bifunctional phosphonium salt catalyst efficiently catalyzed the synthesis of cyclic carbonates under mild conditions, and was reused up to 15 times.

}}, author = {{Steinbauer, J. and Longwitz, L. and Frank, M. and Epping, J. and Kragl, U. and Werner, Thomas}}, issn = {{1463-9262}}, journal = {{Green Chemistry}}, keywords = {{T1, T2, CSSD}}, number = {{18}}, pages = {{4435--4445}}, publisher = {{Royal Society of Chemistry (RSC)}}, title = {{{Immobilized bifunctional phosphonium salts as recyclable organocatalysts in the cycloaddition of CO2 and epoxides}}}, doi = {{10.1039/c7gc01782k}}, volume = {{19}}, year = {{2017}}, }