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Martín‐Matute, BelénORCID iD iconorcid.org/0000-0002-7898-317x
Alternative names
Publications (10 of 96) Show all publications
Bermejo-López, A., Kong, W.-J., Tortajada, P. J., Posevins, D., Martín‐Matute, B. & Bäckvall, J.-E. (2023). Iron-Catalyzed Borylation of Propargylic Acetates for the Synthesis of Multisubstituted Allenylboronates. Chemistry - A European Journal, 29(3), Article ID e202203130.
Open this publication in new window or tab >>Iron-Catalyzed Borylation of Propargylic Acetates for the Synthesis of Multisubstituted Allenylboronates
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2023 (English)In: Chemistry - A European Journal, ISSN 0947-6539, E-ISSN 1521-3765, Vol. 29, no 3, article id e202203130Article in journal (Refereed) Published
Abstract [en]

A novel iron-catalyzed borylation of propargylic acetates leading to allenylboronates has been developed. The method allows the preparation of a variety of di-, tri- and tetrasubstituted allenylboronates at room temperature with good functional group compatibility. Stereochemical studies show that an anti-SN2’ displacement of acetate by boron occurs; this also allows transfer of chirality to yield enantiomerically enriched allenylboronates. The synthetic utility of this protocol was further substantiated by transformations of the obtained allenylboronates including oxidation and propargylation. 

Keywords
Allenes, allenylboronates, borylation, iron, propargyl esters
National Category
Chemical Sciences
Identifiers
urn:nbn:se:su:diva-213118 (URN)10.1002/chem.202203130 (DOI)000888153700001 ()36250587 (PubMedID)2-s2.0-85143203381 (Scopus ID)
Available from: 2022-12-20 Created: 2022-12-20 Last updated: 2023-02-23Bibliographically approved
Sanz-Marco, A., Saavedra, B., Erbing, E., Malmberg, J., Johansson, M. J. & Martín‐Matute, B. (2023). Selective C–H Iodination of Weinreb Amides and Benzamides through Iridium Catalysis in Solution and under Mechanochemical Conditions. Organic Letters
Open this publication in new window or tab >>Selective C–H Iodination of Weinreb Amides and Benzamides through Iridium Catalysis in Solution and under Mechanochemical Conditions
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2023 (English)In: Organic Letters, ISSN 1523-7060, E-ISSN 1523-7052Article in journal (Refereed) Epub ahead of print
Abstract [en]

The acid mediated ortho-iodination of Weinreb amides using a readily available catalyst is described. The selective ortho-iodination of Weinreb amides, challenging substrates in directed C–H activations, and also of benzamides is achieved. The process works under mild conditions and tolerates air and moisture, having a great potential for industrial applications. The methodology can be applied under mechanochemical conditions maintaining the reaction outcome and selectivity. 

National Category
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-226916 (URN)10.1021/acs.orglett.3c03190 (DOI)001158867000001 ()37931032 (PubMedID)2-s2.0-85178172376 (Scopus ID)
Available from: 2024-02-29 Created: 2024-02-29 Last updated: 2024-02-29
Saavedra Guillem, B., Bermejo-López, A., Raeder, M. & Martín‐Matute, B. (2023). Selective quantitative N-functionalization of unprotected α-amino acids using NHC-Ir(III) catalyst. STAR Protocols, 4(2), Article ID 102147.
Open this publication in new window or tab >>Selective quantitative N-functionalization of unprotected α-amino acids using NHC-Ir(III) catalyst
2023 (English)In: STAR Protocols, ISSN 2666-1667, Vol. 4, no 2, article id 102147Article in journal (Refereed) Published
Abstract [en]

Unnatural amino acids are valuable building blocks with numerous applications. Here, we present a quantitative technique for accessing mono-N-functionalized amino acids directly from unprotected substrates using alcohols as alkylating agents and an NHC-Ir(III) catalyst. We detail specific steps for catalyst preparation and application, as well as for catalyst recycling. The protocol excludes a few amino acids (l-cysteine, l-lysine, and l-arginine) and secondary alcohols.

National Category
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-222195 (URN)10.1016/j.xpro.2023.102147 (DOI)001068778500001 ()36920910 (PubMedID)2-s2.0-85150351704 (Scopus ID)
Available from: 2023-10-17 Created: 2023-10-17 Last updated: 2023-10-17Bibliographically approved
García-Vázquez, V., Carretero Cerdán, A., Sanz-Marco, A., Gómez-Bengoa, E. & Martín‐Matute, B. (2022). An Expedient Method for the Umpolung Coupling of Enols with Heteronucleophiles. Chemistry - A European Journal, 28(44), Article ID e202201000.
Open this publication in new window or tab >>An Expedient Method for the Umpolung Coupling of Enols with Heteronucleophiles
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2022 (English)In: Chemistry - A European Journal, ISSN 0947-6539, E-ISSN 1521-3765, Vol. 28, no 44, article id e202201000Article in journal (Refereed) Published
Abstract [en]

In this paper, we present an unprecedented and general umpolung protocol that allows the functionalization of silyl enol ethers and of 1,3-dicarbonyl compounds with a large range of heteroatom nucleophiles, including carboxylic acids, alcohols, primary and secondary amines, azide, thiols, and also anionic carbamates derived from CO2. The scope of the reaction also extends to carbon-based nucleophiles. The reaction relies on the use of 1-bromo-3,3-dimethyl-1,3-dihydro-1λ3[d][1,2]iodaoxole, which provides a key α-brominated carbonyl intermediate. The reaction mechanism has been studied experimentally and by DFT, and we propose formation of an unusual enolonium intermediate with a halogen-bonded bromide. 

Keywords
DFT, enol derivatives, hypervalent iodine(III), mechanistic insight, umpolung
National Category
Chemical Sciences
Identifiers
urn:nbn:se:su:diva-206871 (URN)10.1002/chem.202201000 (DOI)000812456000001 ()35638139 (PubMedID)2-s2.0-85132015643 (Scopus ID)
Available from: 2022-06-30 Created: 2022-06-30 Last updated: 2022-09-06Bibliographically approved
Valiente, A., Martínez-Pardo, P., Kaur, G., Johansson, M. J. & Martín‐Matute, B. (2022). Electrochemical Proton Reduction over Nickel Foam for Z-Stereoselective Semihydrogenation/deuteration of Functionalized Alkynes. ChemSusChem, 15(1), Article ID e202102221.
Open this publication in new window or tab >>Electrochemical Proton Reduction over Nickel Foam for Z-Stereoselective Semihydrogenation/deuteration of Functionalized Alkynes
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2022 (English)In: ChemSusChem, ISSN 1864-5631, E-ISSN 1864-564X, Vol. 15, no 1, article id e202102221Article in journal (Refereed) Published
Abstract [en]

Selective reduction strategies based on abundant-metal catalysts are very important in the production of chemicals. In this paper, a method for the electrochemical semihydrogenation and semideuteration of alkynes to form Z-alkenes was developed, using a simple nickel foam as catalyst and H3O+ or D3O+ as sources of hydrogen or deuterium. Good yields and excellent stereoselectivities (Z/E up to 20 : 1) were obtained under very mild reaction conditions. The reaction proceeded with terminal and nonterminal alkynes, and also with alkynes containing easily reducible functional groups, such as carbonyl groups, as well as aryl chlorides, bromides, and even iodides. The nickel-foam electrocatalyst could be recycled up to 14 times without any change in its catalytic properties. 

Keywords
alkynes, electrocatalysis, nickel foam, semideuteration, semihydrogenation
National Category
Chemical Sciences
Identifiers
urn:nbn:se:su:diva-200536 (URN)10.1002/cssc.202102221 (DOI)000730781300001 ()34738723 (PubMedID)
Available from: 2022-01-10 Created: 2022-01-10 Last updated: 2022-02-25Bibliographically approved
Weis, E., Johansson, M., Korsgren, P., Martín‐Matute, B. & Johansson, M. J. (2022). Merging Directed C-H Activations with High-throughput Experimentation: Development of Predictable Iridium-catalyzed C-H Aminations Applicable to Late-stage Functionalizations. JACS Au, 2(4), 906-916
Open this publication in new window or tab >>Merging Directed C-H Activations with High-throughput Experimentation: Development of Predictable Iridium-catalyzed C-H Aminations Applicable to Late-stage Functionalizations
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2022 (English)In: JACS Au, E-ISSN 2691-3704, Vol. 2, no 4, p. 906-916Article in journal (Refereed) Published
Abstract [en]

Herein, we report an iridium-catalyzed directed C–H amination methodology developed using a high-throughput experimentation (HTE)-based strategy, applicable for the needs of automated modern drug discovery. The informer library approach for investigating the accessible directing group chemical space, in combination with functional group tolerance screening and substrate scope investigations, allowed for the generation of reaction application guidelines to aid future users. Applicability to late-stage functionalization of complex drugs and natural products, in combination with multiple deprotection protocols leading to the desirable aniline matched pairs, serve to demonstrate the utility of the method for drug discovery. Finally, reaction miniaturization to a nanomolar range highlights the opportunities for more sustainable screening with decreased material consumption. 

Keywords
catalysis, C−H activation, C−H amination, C−H functionalization, high-throughput experimentation, HTE, iridium, late-stage functionalization, LSF
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-199213 (URN)10.1021/jacsau.2c00039 (DOI)000795545200013 ()2-s2.0-85129291143 (Scopus ID)
Funder
Swedish Foundation for Strategic ResearchSwedish Research CouncilMistra - The Swedish Foundation for Strategic Environmental ResearchGöran Gustafsson Foundation for Research in Natural Sciences and Medicine
Available from: 2021-11-29 Created: 2021-11-29 Last updated: 2022-07-27Bibliographically approved
Bermejo-López, A., Raeder, M., Martínez-Castro, E. & Martín‐Matute, B. (2022). Selective and quantitative functionalization of unprotected α-amino acids using a recyclable homogeneous catalyst. Chem, 8(12), 3302-3323
Open this publication in new window or tab >>Selective and quantitative functionalization of unprotected α-amino acids using a recyclable homogeneous catalyst
2022 (English)In: Chem, ISSN 2451-9308, E-ISSN 2451-9294, Vol. 8, no 12, p. 3302-3323Article in journal (Refereed) Published
Abstract [en]

A new Ir(III)-NHC catalyst is reported that shows remarkable activity in the N-alkylation of unprotected amino acids. The catalytic system gives excellent selectivity toward monoalkylated α-amino acids and a high degree of retention of stereochemistry. A wide range of unprotected nonnatural amino acids have been prepared. These compounds represent an array of building blocks that could be used for the direct synthesis of peptidomimetics. The synthesis of amino-acid-based surfactants is also reported. This catalytic method gives the amino acid products in quantitative yield; hence, tedious purifications by derivatization are therefore avoided. Furthermore, although the catalyst is a homogeneous metal complex, it can be recycled and reused for several runs. This also contributes to the efficiency and sustainability of the method.

National Category
Chemical Sciences
Identifiers
urn:nbn:se:su:diva-214572 (URN)10.1016/j.chempr.2022.08.017 (DOI)000901507200001 ()2-s2.0-85143972565 (Scopus ID)
Available from: 2023-02-06 Created: 2023-02-06 Last updated: 2024-05-24Bibliographically approved
García-Vázquez, V., Martínez-Pardo, P., Postole, A., Inge, A. K. & Martín‐Matute, B. (2022). Synthesis of α,γ-Chiral Trifluoromethylated Amines through the Stereospecific Isomerization of α-Chiral Allylic Amines. Organic Letters, 24(21), 3867-3871
Open this publication in new window or tab >>Synthesis of α,γ-Chiral Trifluoromethylated Amines through the Stereospecific Isomerization of α-Chiral Allylic Amines
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2022 (English)In: Organic Letters, ISSN 1523-7060, E-ISSN 1523-7052, Vol. 24, no 21, p. 3867-3871Article in journal (Refereed) Published
Abstract [en]

Chiral γ-branched aliphatic amines are present in a large number of pharmaceuticals and natural products. However, enantioselective methods to access these compounds are scarce and mainly rely on the use of designed chiral transition-metal complexes. Herein, we combined an organocatalytic method for the stereospecific isomerization of chiral allylic amines with a diastereoselective reduction of the chiral imine/enamine intermediates, leading to γ-trifluoromethylated aliphatic amines with two noncontiguous stereogenic centers, in excellent yields and high diastereo- and enantioselectivities. This approach has been used with primary amine substrates. This approach also provides a new synthetic pathway to chiral trifluoromethylated scaffolds, of importance in medicinal chemistry. Additionally, a gram-scale reaction demonstrates the applicability of this synthetic procedure. 

National Category
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-201578 (URN)10.1021/acs.orglett.2c01436 (DOI)000808582000022 ()35588010 (PubMedID)2-s2.0-85131271167 (Scopus ID)
Available from: 2022-01-28 Created: 2022-01-28 Last updated: 2023-02-14Bibliographically approved
Weis, E., Hayes, M. A., Johansson, M. J. & Martín-Matute, B. (2021). Iridium-catalyzed C−H methylation and d3-methylation of benzoic acids with application to late-stage functionalizations. iScience, 24(5), Article ID 102467.
Open this publication in new window or tab >>Iridium-catalyzed C−H methylation and d3-methylation of benzoic acids with application to late-stage functionalizations
2021 (English)In: iScience, E-ISSN 2589-0042 , Vol. 24, no 5, article id 102467Article in journal (Refereed) Published
Abstract [en]

Late-stage functionalization (LSF) has over the past years emerged as a powerful approach in the drug discovery process. At its best, it allows for rapid access to new analogues from a single drug-like molecule, bypassing the need for de novo synthesis. To be successful, methods able to tolerate the diverse functional groups present in drug-like molecules that perform under mild conditions are required. C−H methylation is of particular interest due to the magic methyl effect in medicinal chemistry. Herein we report an iridium-catalyzed carboxylate-directed ortho C−H methylation and d3-methylation of benzoic acids. The method uses commercially available reagents and precatalyst and requires no inert atmosphere or exclusion of moisture. Substrates bearing electron-rich and electron-poor groups were successfully methylated, including compounds with competing directing/coordinating groups. The method was also applied to the LSF of several marketed drugs, forming analogues with increased metabolic stability compared with the parent drug.

National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-194609 (URN)10.1016/j.isci.2021.102467 (DOI)
Available from: 2021-06-24 Created: 2021-06-24 Last updated: 2022-02-25Bibliographically approved
Weis, E., Johansson, M. J. & Martín‐Matute, B. (2021). Late-Stage Amination of Drug-Like Benzoic Acids: Access to Anilines and Drug Conjugates through Directed Iridium-Catalyzed C−H Activation. Chemistry - A European Journal, 27(72), 18188-18200
Open this publication in new window or tab >>Late-Stage Amination of Drug-Like Benzoic Acids: Access to Anilines and Drug Conjugates through Directed Iridium-Catalyzed C−H Activation
2021 (English)In: Chemistry - A European Journal, ISSN 0947-6539, E-ISSN 1521-3765, Vol. 27, no 72, p. 18188-18200Article in journal (Refereed) Published
Abstract [en]

The functionalization of C−H bonds, ubiquitous in drugs and drug-like molecules, represents an important synthetic strategy with the potential to streamline the drug-discovery process. Late-stage aromatic C−N bond–forming reactions are highly desirable, but despite their significance, accessing aminated analogues through direct and selective amination of C−H bonds remains a challenging goal. The method presented herein enables the amination of a wide array of benzoic acids with high selectivity. The robustness of the system is manifested by the large number of functional groups tolerated, which allowed the amination of a diverse array of marketed drugs and drug-like molecules. Furthermore, the introduction of a synthetic handle enabled expeditious access to targeted drug-delivery conjugates, PROTACs, and probes for chemical biology. This rapid access to valuable analogues, combined with operational simplicity and applicability to high-throughput experimentation has the potential to aid and considerably accelerate drug discovery. 

Keywords
amination, C- H activation, conjugation, high-throughput experimentation, iridium
National Category
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-199209 (URN)10.1002/chem.202103510 (DOI)000719728500001 ()34672032 (PubMedID)
Funder
Swedish Foundation for Strategic Research Swedish Research CouncilGöran Gustafsson Foundation for Research in Natural Sciences and MedicineMistra - The Swedish Foundation for Strategic Environmental Research
Available from: 2021-11-29 Created: 2021-11-29 Last updated: 2022-01-25Bibliographically approved
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ORCID iD: ORCID iD iconorcid.org/0000-0002-7898-317x

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