Article
Chemistry, Multidisciplinary
Johanne Ling, Antoine Bruneau-Voisine, Guillaume Journot, Gwilherm Evano
Summary: In this study, a general copper-catalyzed carbonylative cross-coupling between amines and alkyl iodides was reported. The reaction showed good efficiency and broad substrate scope, making it potentially valuable for industrial applications.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
James E. Baumann, Gojko Lalic
Summary: A new method for the differential dihydrofunctionalization of terminal alkynes has been developed, enabling the synthesis of allylic boronate esters through a reductive three-component coupling reaction. This transformation, promoted by a copper/palladium catalyst system, hydrofunctionalizes both pi-bonds of the alkyne. The method is compatible with a wide range of functional groups.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Yifan Wang, Yuanyuan Ping, Wangqing Kong
Summary: A cooperative Pd/Cu-catalyzed three-component cross-coupling reaction of alkynes, B 2 Pin 2 and alkenetethered aryl halides is reported. This reaction proceeds under mild conditions and shows broad substrate scope, providing a variety of heterocycles containing tetrasubstituted alkenylboronate moieties in synthetically useful yields with excellent chemoselectivity and regioselectivity. An enantioselective cascade cyclization/cross-coupling process has also been developed for the synthesis of enantiomerically enriched oxindole bearing a tetrasubstituted alkenylboronate moiety.
CHINESE CHEMICAL LETTERS
(2023)
Review
Chemistry, Multidisciplinary
Xinlan A. F. Cook, Antoine de Gombert, Janette McKnight, Loic R. E. Pantaine, Michael C. Willis
Summary: This review focuses on the methods developed for the challenging coupling of 2-pyridine nucleophiles with (hetero)aryl electrophiles, ranging from traditional cross-coupling processes to alternative nucleophilic reagents and novel main group approaches.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Physical
Eduam O. Boeira, Caroline B. Pla, Fabiano S. Rodembusch, Angelica Moro
Summary: In this study, the arylation of Troger's base was achieved through the Suzuki cross-coupling reaction using aqueous micellar catalysis. The developed reaction conditions allowed for the preparation of various Troger's base derivatives with low catalytic loading of Pd(OAc)(2) catalyst and under environmentally friendly aqueous conditions.
Article
Chemistry, Organic
Hua Yao, Xiaoyang Zhong, Bingqing Wang, Sen Lin, Zhaohua Yan
Summary: A novel and efficient approach for the amine-directed dehydrogenative C(sp(2))-C(sp(3)) coupling of arylamines with acetonitrile was developed using FeCl2 as the catalyst. The method provides a straightforward and green route to arylacetonitriles with good regioselectivity and excellent compatibility of functional groups and aromatic rings.
Article
Chemistry, Multidisciplinary
Christopher A. Wilhelmsen, Xuntong Zhang, Jesse A. Myhill, James P. Morken
Summary: Versatile beta tert-boryl amides were synthesized through conjunctive cross-coupling of alpha-substituted alkenyl boron ate complexes and carbamoyl chloride electrophiles. The use of a palladium catalyst in combination with MandyPhos enabled enantioselective synthesis. Additionally, the chemoselectivity of the reaction product was enhanced by the addition of water.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Felipe Verdugo, Ricardo Rodino, Martin Calvelo, Jose Luis Mascarenas, Fernando Lopez
Summary: The reactivity of carbonyl-tethered alkylidenecyclopropanes (ACPs) can be directed towards tandem cycloisomerization/cross-coupling processes by using Pd-0 catalysts with phosphorus-based monodentate ligands. This allows for the synthesis of a wide variety of highly functionalized cyclic alcohols and amines through the formation of key pi-allyl oxapalladacyclic intermediates which are trapped with external nucleophilic partners.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Dejiang Zhang, Liyuan Le, Renhua Qiu, Wai-Yeung Wong, Nobuaki Kambe
Summary: A strategy for the formation of antimony-carbon bond via nickel-catalyzed cross-coupling of halostibines was developed. This method has a wide substrate scope and is compatible with various functional groups. The successful synthesis of arylated stibine demonstrated the high synthetic potential of this transformation.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Saidkhodzha Nematulloev, Arunachalam Sagadevan, Badriah Alamer, Aleksander Shkurenko, Renwu Huang, Jun Yin, Chunwei Dong, Peng Yuan, Khursand E. Yorov, Azimet A. Karluk, Wasim J. Mir, Bashir E. Hasanov, Mohamed Nejib Hedhili, Naveen M. Halappa, Mohamed Eddaoudi, Omar F. Mohammed, Magnus Rueping, Osman M. Bakr
Summary: This study reports the synthesis of atomically precise copper hydride nanoclusters with a controlled defect, which were demonstrated to be highly selective catalysts for C-C cross-couplings. The work highlights the potential of defective nanoclusters as model systems for investigating individual defects, correlating defects with physicochemical properties, and rationally designing new nanoparticle catalysts.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Lukas Hoff, Gleb A. Chesnokov, Anthony Linden, Karl Gademann
Summary: This study presents a thorough mechanistic investigation of the Pd-catalyzed and Ag-mediated cross-coupling reaction between monosubstituted tetrazine and boronic acids. Through kinetic analyses, isolation of intermediates, and computational methods, insights into the mechanism were obtained. The study also demonstrated the experimental confirmation of a highly electron-deficient ligand and the impact of mechanistic understanding on the generality of the reaction scope through a data-driven workflow.
Article
Chemistry, Multidisciplinary
Sheng Feng, Yuyang Dong, Stephen L. Buchwald
Summary: In this study, an alternative method for the asymmetric hydroaminocarbonylation of olefins using dual copper hydride and palladium catalysis was described. This method enables the synthesis of enantioenriched amides using readily available carbamoyl chlorides as the carbamoylating reagent, and is applicable to various types of olefins with good yields and excellent enantioselectivities.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Physical
Chao Li, Liang Ling, Zheng Luo, Sha Wang, Xiaoyu Zhang, Xiaoming Zeng
Summary: In this study, we report a deoxygenative cross-coupling reaction between unactivated aryl esters and unsaturated amides, enabled by chromium catalysis. Mechanistic studies indicate that ester C-O cleavage by Cr and subsequent silylation leads to the formation of arylated silachromate, which regioselectively adds to carbonyls of amides through reductive elimination and deoxygenative hydrogen transfer. This reaction provides a strategy for the synthesis of pharmaceutically interesting diarylmethylated amines.
Article
Chemistry, Physical
Chao Li, Liang Ling, Zheng Luo, Sha Wang, Xiaoyu Zhang, Xiaoming Zeng
Summary: In this study, a deoxygenative cross-coupling reaction between unactivated aryl esters and unsaturated amides was achieved using chromium catalysis. The reaction involves cleavage of C-O bonds by Cr and subsequent silylation, leading to the formation of arylated silachromate that undergoes reductive elimination and deoxygenative hydrogen transfer to cross-couple with carbonyls of amides. This method offers a strategy for the synthesis of pharmaceutically relevant diarylmethylated amines.
Article
Chemistry, Multidisciplinary
Janette McKnight, Andre Shavnya, Neal W. Sach, David C. Blakemore, Ian B. Moses, Michael C. Willis
Summary: An efficient one-pot desulfinative cross-coupling reaction catalyzed by Pd is reported for the synthesis of medicinally relevant di(hetero)arylmethanes.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Review
Chemistry, Organic
Baosheng Wei, Paul Knochel
Summary: Cross-couplings involving organozinc reagents can proceed well in the absence of transition-metal catalysts with reactive electrophiles. Highly diastereoselective and enantioselective cross-couplings can be readily performed with room-temperature configurationally stable alkylzinc species, producing diastereoselectively and enantiomerically enriched products. Highly regioselective magnesiations of functionalized arenes and heteroarenes undergo Negishi or Cu-catalyzed cross-couplings.
SYNTHESIS-STUTTGART
(2022)
Article
Chemistry, Multidisciplinary
Alisa S. Sunagatullina, Ferdinand H. Lutter, Paul Knochel
Summary: In this study, various dialkylmagnesiums were synthesized by reacting primary or secondary alkyl iodides with sBu(2)Mg, and these reagents underwent diverse reactions with different compounds to yield stereodefined products. Mechanistic studies revealed that these reactions proceed via a radical pathway.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Alexander Kremsmair, Andreas Hess, Benjamin Heinz, Paul Knochel
Summary: Mixed TMP-bases are excellent reagents for the metalation of functionalized aromatics and heterocycles. By combining with Lewis acids, the metalation scope can be increased, and regioselectivity switches can be achieved. Highly reactive lithium bases are also compatible with various Lewis acids, and performing metalations in continuous flow using commercial setups allows for practical and convenient reaction conditions.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
A. Hess, H. C. Guelen, N. Alandini, A. Mourati, Y. C. Guersoy, P. Knochel
Summary: This study presents a novel method for the selective ortho, ortho'-functionalization of readily available aryl oxazolines using sBu(2)Mg in toluene followed by trapping reactions with electrophiles. The conversions of these nitriles to valuable heterocycles are reported, and a tentative mechanism is proposed for the reactions.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Dimitrije Djukanovic, Maximilian A. Ganiek, Kohei Nishi, Konstantin Karaghiosoff, Kazushi Mashima, Paul Knochel
Summary: A new convenient method for the preparation of dicarbamoylzincs is reported in this study. The target compounds were obtained by reacting ZnCl2 and formamides or TMP2Zn with formamides. This method is compatible with sensitive functional groups such as esters, ketones, or nitro groups. The reaction of these dicarbamoylzincs with various functionalized allylic, benzylic, aryl, alkenyl compounds, acid chlorides, aldehydes, or enones resulted in the synthesis of polyfunctional amides in high yields. The C-13 NMR characterization of these new compounds is presented.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Andreas Hess, Nurtalya Alandini, Yusuf C. Guersoy, Paul Knochel
Summary: A new and storable magnesium amide was prepared and found to be suitable for the non-cryogenic magnesiation of fluoro-substituted arenes and heteroarenes. Further reactions produced a range of polyfunctional fluoro-substituted unsaturated building blocks.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Johannes H. Harenberg, Rajasekar Reddy Annapureddy, Konstantin Karaghiosoff, Paul Knochel
Summary: This study reports a lateral sodiation reaction for alkyl(hetero)arenes using a hexane-soluble sodium compound generated on demand, in the presence of TMEDA. The reaction can be conducted under batch and continuous flow conditions. The resulting benzylic sodium species can react with various electrophiles. This method has great potential for synthetic applications.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Saroj Kumar Rout, Agonist Kastrati, Harish Jangra, Kuno Schwaerzer, Alisa S. Sunagatullina, Maximilien Garny, Fabio Lima, Cara E. Brocklehurst, Konstantin Karaghiosoff, Hendrik Zipse, Paul Knochel
Summary: DFT calculations can predict the reactivity of uncommon N-heterocyclic scaffolds and facilitate their functionalization. Experimental results show that specific catalysts and reagents can achieve the regioselective derivatization of these compounds.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Alexander Kremsmair, Alisa S. Sunagatullina, Leonie J. Bole, Pasquale Mastropierro, Simon Grassl, Henrik R. Wilke, Edouard Godineau, Eva Hevia, Paul Knochel
Summary: A new method for selectively zincating challenging N-heterocyclic substrates has been reported using mixed Li/Zn bases. The method allows for mild regioselective reactions and provides insights into the composition and reactivity of the reaction mixtures.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Applied
Alisa S. Sunagatullina, Ferdinand H. Lutter, Konstantin Karaghiosoff, Paul Knochel
Summary: We have developed a new iron-catalyzed reaction for converting alkyl iodides into alkylzinc iodides. The reaction exhibits diastereoselective ring closures when a remote double bond is present at position 5. Furthermore, the resulting zinc reagents can be further reacted with various electrophiles under copper or palladium catalysis to provide diverse polyfunctional products.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Multidisciplinary
Alexander Kremsmair, Henrik R. R. Wilke, Johannes H. H. Harenberg, Benjamin R. G. Bissinger, Matthias M. M. Simon, Nurtalya Alandini, Paul Knochel
Summary: This study reports a practical in situ quench procedure for the generation of chiral secondary alkyl lithiums from secondary alkyl iodides. The reaction can be carried out in the presence of various electrophiles, resulting in the preparation of a wide range of optically enriched organic compounds.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Alisa S. Sunagatullina, Andreas Hess, Alexander Kremsmair, Yifan Li, Yi-Hung Chen, Paul Knochel
Summary: We present a novel electrophilic amination method for primary, secondary, and tertiary alkyl, benzylic, and allylic zinc and magnesium organometallics using O-2,4,6-trimethylbenzoyl hydroxylamines (O-TBHAs) with yields ranging from 52-99%. These O-TBHAs exhibit excellent long-term stability and can be conveniently synthesized from various highly functionalized secondary amines through a three-step procedure. The amination reactions demonstrate remarkable chemoselectivity without the need for transition-metal catalysts, and are typically completed within 1-3 hours at 25 degrees Celsius. Furthermore, this electrophilic amination process enables the synthesis of enantioenriched tertiary amines (up to 88% ee) using optically enriched secondary alkylmagnesium reagents of the type s-AlkylMgCH(2)SiMe(3).
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Clemence Hamze, Julie Brossier, Konstantin Karaghiosoff, Edouard Godineau, Paul Knochel
Summary: A regioselective tri- and tetra-functionalization of the pyridazine scaffold was achieved using two readily available building blocks, resulting in the synthesis of a range of pyridazine derivatives.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Agonist Kastrati, Alexander Kremsmair, Alisa S. Sunagatullina, Vasilii Korotenko, Yusuf C. Guersoy, Saroj K. Rout, Fabio Lima, Cara E. Brocklehurst, Konstantin Karaghiosoff, Hendrik Zipse, Paul Knochel
Summary: Straightforward calculations have led to the development of a set of organometallic reactions for the regioselective functionalization of the underexplored fused N-heterocycle imidazo[1,2-a]pyrazine. These reactions provide a way to access polyfunctionalized imidazopyrazine heterocycles.
Article
Chemistry, Multidisciplinary
Andreas Hess, Nurtalya Alandini, Hasret C. Guelen, Jan P. Prohaska, Paul Knochel
Summary: We report the preparation of a new hydrocarbon-soluble magnesium amide TMP2Mg (TMP = 2,2,6,6-tetramethylpiperidyl). This base showed excellent properties for the regioselective magnesiation of various arenes and heteroarenes bearing ethyl esters and carbamates under very mild reaction conditions. Subsequent trapping with aryl iodides (Negishi cross-coupling) gave access to a range of highly functionalized valuable building blocks.
CHEMICAL COMMUNICATIONS
(2022)