Carbon–Germanium Bond Formation via Low-Valent Cobalt-Catalyzed Cross-Electrophile Coupling

Chen, Haifeng; Zhu, Chen; Yue, Huifeng; Rueping, Magnus

doi:10.1021/acscatal.3c01244

“…Furthermore, for heteroarenes, where the latter methods are less suitable, a direct, basemediated germylation of arenes utilizing lithium tetramethylpiperidine (LiTMP) and Et 3 GeCl (in onepot) at room temperature was possible (Figure 12B, Method C). [14a] Besides Pd-based germylation of arenes, electrochemical [37] or Ni-catalyzed [38] cross-electrophile coupling of commercially available chlorogermanes (ClGeR 3 ) with (hetero)aryl (as well as alkenyl and alkyl halides) has been showcased (Figure 12C, Methods D/E). The method also allowed for the facile synthesis of arenes containing multiple cross coupling handles, as the germylation successfully took place in the presence of CÀ Bpin, CÀ SnBu 3 , and CÀ SiMe 3 groups.…”

Section: Synthesis Of Aryl Germanes From Arh and Arxmentioning

confidence: 99%

“… A) Historically developed methods for accessing organogermanes B) Direct C−H germylation or via thianthrenium salt intermediate [14,36] C . Ni‐catalyzed and electrochemical syntheses of ArGeR 3 [37,38] …”

Section: Synthesis Of Organogermanesmentioning

confidence: 99%

Recent Developments with Organogermanes: their Preparation and Application in Synthesis and Catalysis

Rogova,

Ahrweiler,

Schoetz

et al. 2023

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Within the sphere of traditional Pd0/PdII cross coupling reactions, organogermanes have been historically outperformed both in terms of scope and reactivity by more conventional transmetalating reagents. Subsequently, this class of compounds has been largely underutilized as a coupling partner in bond‐forming strategies. Most recent studies, however, have shown that alternative modes of activation of these notoriously robust building blocks transform organogermanes into the most reactive site of the molecule – capable of outcompeting other functional groups (such as boronic acids, esters and silanes) for both C–C and C–heteroatom bond formation. As a result, over the past few years, the literature has increasingly featured methodologies that explore the potential of organogermanes as chemoselective and orthogonal coupling partners. Herein we highlight some of these recent advances in the field of organogermane chemistry both with respect to their synthesis and applications in synthetic and catalytic transformations.

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“…Alkyl halides are readily available, and their direct cross-coupling, i.e., XEC, offers a promising route to achieving this goal. [36] These transformations circumvent the need to prepare any carbon nucleophiles and the typical stability and functional group tolerance issues that are often associated with these reagents. However, achieving high selectivity in C(sp 3 )À C(sp 3 ) XEC remains a significant hurdle.…”

Section: Electrochemical Cross-electrophile Coupling Of Alkyl Electro...mentioning

confidence: 99%

Electroreductive Cross‐Electrophile Coupling (eXEC) Reactions

Liu

¹

,

Li

²

,

Wang

³

et al. 2023

Angewandte Chemie

1

0

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Electrochemistry utilizes electrons as a potent, controllable, and traceless alternative to chemical oxidants or reductants, and typically offers a more sustainable option for achieving selective organic synthesis. Recently, the merger of electrochemistry with readily available electrophiles has been recognized as a viable and increasingly popular methodology for efficiently constructing challenging C−C and C‐heteroatom bonds in a sustainable manner for complex organic molecules. In this mini‐review, we have systematically summarized the most recent advances in electroreductive cross‐electrophile coupling (eXEC) reactions during the last decade. Our focus has been on readily available electrophiles, including aryl and alkyl organic (pseudo)halides, as well as small molecules such as CO2, SO2, and D2O.

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“…A) Historically developed methods for accessing organogermanes B) Direct CÀ H germylation or via thianthrenium salt intermediate [14,36] C. Ni-catalyzed and electrochemical syntheses of ArGeR 3 . [37,38] and stereocontrol of the resulting vinylgermane products as compared with earlier approaches. [43] Moreover, metal-free approaches using borane catalysis with B(C 6 F 5 ) 3 also gives ready access to highly functionalized, cyclic and acyclic alkylgermanes, under metal-free hydrogermylation conditions.…”

Section: Synthesis Of Alkenyl Alkyl and Alkynyl Germanesmentioning

confidence: 99%

Recent Developments with Organogermanes: their Preparation and Application in Synthesis and Catalysis

Rogova,

Ahrweiler,

Schoetz

et al. 2023

Angewandte Chemie

1

0

View full text Add to dashboard Cite

Within the sphere of traditional Pd0/PdII cross coupling reactions, organogermanes have been historically outperformed both in terms of scope and reactivity by more conventional transmetalating reagents. Subsequently, this class of compounds has been largely underutilized as a coupling partner in bond‐forming strategies. Most recent studies, however, have shown that alternative modes of activation of these notoriously robust building blocks transform organogermanes into the most reactive site of the molecule – capable of outcompeting other functional groups (such as boronic acids, esters and silanes) for both C–C and C–heteroatom bond formation. As a result, over the past few years, the literature has increasingly featured methodologies that explore the potential of organogermanes as chemoselective and orthogonal coupling partners. Herein we highlight some of these recent advances in the field of organogermane chemistry both with respect to their synthesis and applications in synthetic and catalytic transformations.

show abstract

Carbon–Germanium Bond Formation via Low-Valent Cobalt-Catalyzed Cross-Electrophile Coupling

Cited by 24 publications

References 68 publications

Recent Developments with Organogermanes: their Preparation and Application in Synthesis and Catalysis

Recent Developments with Organogermanes: their Preparation and Application in Synthesis and Catalysis

Electroreductive Cross‐Electrophile Coupling (eXEC) Reactions

Recent Developments with Organogermanes: their Preparation and Application in Synthesis and Catalysis

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