The development of orthogonal C -C coupling regimes to the omnipresent Pd-catalysis class would enable an additional dimension of modularity in the construction of densely functionalized biaryl motifs. In this context, the identification of potent functional groups for selective transformations is in high demand. Although organogermanium compounds are generally believed to be of low reactivity in homogenous catalysis, this report discloses the highly efficient and orthogonal reactivity of aryl germanes with arenes under gold catalysis. The method is characterized by mildness, the employment of an air- and moisture-stable gold catalyst, and robustness. Our mechanistic studies show that aryl germanes are highly reactive with Au and Au. Our computational data suggest that the origin of this reactivity primarily lies in the relatively low bond dissociation energy and as such low distortion energy to reach the key bond activating transition state.
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http://dx.doi.org/10.1021/acscatal.9b02841 | DOI Listing |
Chemistry
December 2024
Department of Drug Design and Pharmacology, Faculty of Health and Medical Sciences, University of Copenhagen, Jagtvej 162, 2100, Copenhagen, Denmark.
Organometallics can be used as precursors for electrophilic At-statinations. In this report, we compared the potential of aryl trimethylsilanes, -germanes, or -stannanes to be used as precursors to At-label highly reactive tetrazines. Tetrazines can be used for pretargeted radioligand therapies or be applied as synthons to radiolabel rapidly and orthogonally a broad set of precursors such as peptides, mAbs or nanomedicines.
View Article and Find Full Text PDFOrg Lett
October 2023
Institute of Organic Chemistry, RWTH Aachen University, Landoltweg 1, 52074 Aachen, Germany.
We report a site-selective -nitration of aryl germanes in the presence of boronic esters, silanes, halogens, and additional functionalities. The protocol is characterized by operational simplicity, proceeds at room temperature, and is enabled by [Ru(bpy)](PF)/blue light photocatalysis. Owing to the exquisite robustness of the [Ge] functionality, nitrations of alternative functional handles in the presence of the germane are also feasible, as showcased herein.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
October 2023
State Key Laboratory of Coordination Chemistry, Jiangsu Key Laboratory of Advanced Organic Materials, Chemistry and Biomedicine Innovation Center (ChemBIC), School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, 210023, China.
Angew Chem Int Ed Engl
October 2023
Institute of Organic Chemistry, RWTH Aachen University, Landoltweg 1, 52074, Aachen, Germany.
Reported herein is a fully orthogonal olefination, which involves the site- and E-selective coupling of aryl germanes with alkenes, tolerating otherwise widely employed coupling handles such as aromatic (pseudo)halogens (C-I, C-Br, C-Cl, C-F, C-OTf, C-OSO F), silanes and boronic acid derivatives as well as alternative functionalities. This unprecedented [Ge]-based oxidative Heck coupling proceeds at room temperature with high speed (10 min to 2 hours) and operational simplicity owing to its base-free and air-tolerant features.
View Article and Find Full Text PDFJ Am Chem Soc
February 2023
Westfälische Wilhelms-Universität Münster, Organisch-Chemisches Institut, Corrensstraße 36, 48149 Münster, Germany.
A catalytic approach of synthesizing the -selective saturated carbo- and heterocyclic germanium compounds (3D framework) is reported the hydrogenation of readily accessible aromatic germanes (2D framework). Among the numerous catalysts tested, Nishimura's catalyst (RhO/PtO·HO) exhibited the best hydrogenation reactivity with an isolated yield of up to 96%. A broad range of substrates including the synthesis of unprecedented saturated heterocyclic germanes was explored.
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