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Herein, we report a Kumada cross-coupling reaction of benzylic sulfonamides. The scope of the transformation includes acyclic and cyclic sulfonamide precursors that cleanly produce highly substituted acyclic fragments. Preliminary data are consistent with a stereospecific mechanism that allows for a diastereoselective reaction.
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http://dx.doi.org/10.3390/molecules26195947 | DOI Listing |
Chem Soc Rev
November 2024
Department of Chemistry, Ludwig-Maximilians-University München, Butenandtstrasse 5-13, Haus F, 81377 Munich, Germany.
This review highlights the use of functionalized organo-Li, -Mg and -Zn reagents for the construction and selective functionalization of 5- and 6-membered fused bicyclic heteroaromatics. Special attention is given to the discussion of advanced syntheses for the preparation of highly functionalized heteroaromatic scaffolds, including quinolines, naphthyridines, indoles, benzofurans, benzothiophenes, benzoxazoles, benzothiazoles, benzopyrimidines, anthranils, thienothiophenes, purine coumarins, chromones, quinolones and phthalazines and their fused heterocyclic derivatives. The organometallic reagents used for the desired functionalizations of these scaffolds are generally prepared using the following methods: (i) through directed selective metalation reactions (DoM), (ii) by means of halogen/metal exchange reactions, (iii) through oxidative metal insertions (Li, Mg, Zn), and (iv) by transmetalation reactions (organo-Li and Mg transmetalations with ZnCl or ZnO(Piv)).
View Article and Find Full Text PDFHeliyon
July 2024
Faculty of Environmental Earth Science, Hokkaido University, Nishi 5, Kita 10, Kita-ku, Sapporo, 060-0810, Japan.
Kumada cross-coupling reaction is useful for producing biphenyls, where nickel and copper have been widely investigated as catalysts but mainly homogeneous ones. In this study, we investigated ultrasound-assisted-Kumada cross-coupling reaction over the heterogeneous catalysts in which Ni, Cu, or both was immobilized on aminopropylsilane-functionalized-SiO-TiO prepared in the presence of cetyltrimethylammonium bromide (CTAB). The presence of CTAB effectively prevented the particle growth and therefore SiO-TiO fine particles with high surface area (502 m g) were formed.
View Article and Find Full Text PDFOrg Lett
July 2024
Department of Organic Chemistry, University of Geneva, 30 Quai Ernest Ansermet, 1211 Geneva, Switzerland.
The development of protocols for the construction of congested quaternary centers is highly sought-after. Herein, we report a method for the cross-coupling of C(sp) tertiary Grignard reagents with C(sp) styrenyl bromides using readily available nickel precatalysts. We identified conditions that afford the products in practical yield for several combinations of electrophiles and nucleophiles, including sensitive α-magnesiated Grignard reagents.
View Article and Find Full Text PDFChem Soc Rev
May 2024
Shenzhen Grubbs Institute and Department of Chemistry, Guangdong Provincial Key Laboratory of Catalysis, Southern University of Science and Technology, Shenzhen, Guangdong 518055, China.
Given the critical importance of novel ligand development for transition-metal (TM) catalysis, as well as the resurgence of the field of organosilicon chemistry and silyl ligands, to summarize the topic of X-type silyl ligands for TM catalysis is highly attractive and timely. This review particularly emphasizes the unique σ-donating characteristics and -effects of silyl ligands, highlighting their crucial roles in enhancing the reactivity and selectivity of various catalytic reactions, including small molecule activation, Kumada cross-coupling, hydrofunctionalization, C-H functionalization, and dehydrogenative Si-O coupling reactions. Additionally, future developments in this field are also provided, which would inspire new insights and applications in catalytic synthetic chemistry.
View Article and Find Full Text PDFAcc Chem Res
March 2024
The Warren and Katharine Schlinger Laboratory for Chemistry and Chemical Engineering, Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125, United States.
ConspectusAfter decades of palladium dominating the realm of transition-metal-catalyzed cross-coupling, recent years have witnessed exciting advances in the development of new nickel-catalyzed cross-coupling reactions to form C(sp) centers. Nickel possesses distinct properties compared with palladium, such as facile single-electron transfer to C(sp) electrophiles and rapid C-C reductive elimination from Ni. These properties, among others, make nickel particularly well-suited for reductive cross-coupling (RCC) in which two electrophiles are coupled and an exogenous reductant is used to turn over the metal catalyst.
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