Nickel-Catalyzed Reductive Csp<sup>3</sup>–Ge Coupling of Alkyl Bromides with Chlorogermanes

Guo, Peng; Pang, Xiaoyang; Wang, Ke; Su, Pei-Feng; Pan, Qiu-Quan; Han, Guan-Yu; Shen, Qian; Zhao, Zhenzhen; Zhang, Wenhua; Shu, Xing‐Zhong

doi:10.1021/acs.orglett.2c00207

Cited by 27 publications

(17 citation statements)

References 52 publications

(25 reference statements)

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“…The development of nickel-catalyzed reductive Csp 3 −Ge coupling of alkyl bromides with chlorogermanes results in the formation of alkylgermanes (Scheme 29). 51 The reaction proceeds under very mild conditions and tolerates various functionalities, including ether, alcohol, alkene, nitrile, amine, ester, phosphonates, amides, ketone, and aldehyde.…”

Section: Reductive Cross-coupling Of Chlorogermanesmentioning

confidence: 99%

Reductive Cross-Coupling of Unreactive Electrophiles

2022

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Metrics & MoreArticle Recommendations CONSPECTUS: Transition-metal-catalyzed reductive coupling of electrophiles has emerged as a powerful tool for the construction of molecules. While major achievements have been made in the field of cross-couplings between organic halides and pseudohalides, an increasing number of reports demonstrates reactions involving more readily available, low-cost, and stable, but unreactive electrophiles. This account summarizes the recent results in our laboratory focusing on this topic. These findings typically include deoxygenative C−C coupling of alcohols, reductive alkylation of alkenyl acetates, reductive C−Si coupling of chlorosilanes, and reductive C−Ge coupling of chlorogermanes.The reductive deoxygenative coupling of alcohols with electrophiles is synthetically appealing, but the potential of this chemistry remains to be disclosed. Our initial study focused on the reaction of allylic alcohols and aryl bromides by the combination of nickel and Lewis acid catalysis. This method offers a selectivity that is opposite to that of the classic Tsuji−Trost reactions. Further investigation on the reaction of benzylic alcohols led to the foundation of a dynamic kinetic cross-coupling strategy with applications in the nickelcatalyzed reductive arylation of benzylic alcohols and cobalt-catalyzed enantiospecific reductive alkenylation of allylic alcohols. The titanium catalysis was later established to produce carbon radicals directly from unactivated tertiary alcohols via C−OH cleavage.The development of their coupling reactions with carbon fragments delivers new methods for the construction of all-carbon quaternary centers. These reactions have shown high selectivity for the functionalization of tertiary alcohols, leaving primary and secondary alcohols intact. Alkenyl acetates are inexpensive, stable, and environmentally friendly and are considered the most attractive alkenyl reagents. The development of reductive alkylation of alkenyl acetates with benzyl ammoniums and alkyl bromides offers mild approaches for the conversion of ketones into aliphatic alkenes. Extensive studies in this field have enabled us to extend the cross-electrophile coupling from carbon to silicon and germanium chemistry. These reactions harness the ready availability of chlorosilanes and chlorogermanes but suffer from the challenge of their low reactivity toward transition metals. Under reductive nickel catalysis, a broad range of alkenyl and aryl electrophiles couple well with vinyl-and hydrochlorosilanes. The use of alkyl halides as coupling partners led to the formation of functionalized alkylsilanes. The C−Ge coupling seems less substrate-dependent, and various common chlorogermanes couple well with aryl, alkenyl, and alkyl electrophiles. In general, functionalities such as Grignard-sensitive groups (e.g., acid, amide, alcohol, ketone, and ester), acid-sensitive groups (e.g., ketal and THP protection), alkyl fluoride and chloride, aryl bromide, alkyl tosylate and mesylate, silyl ether, and amine are tolerated. ...

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Section: Reductive Cross-coupling Of Chlorogermanesmentioning

confidence: 99%

Reductive Cross-Coupling of Unreactive Electrophiles

2022

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“…Several transition metal-catalyzed methods for C-Ge bond formation have been reported. [25][26][27][28][29][30][31][32][33][34][35][36] Germatranes [37][38][39][40] and aryltriethylgermanes [41][42][43][44][45][46] have shown unique properties when applied as nucleophiles in Pd-or Au-catalyzed cross-coupling reactions. However, in visible-light photocatalytic systems, germanium compounds have not been widely used, till now.…”

Section: Bin Xiaomentioning

confidence: 99%

Organogermanium(iv) compounds in photo-induced radical reactions

Xiao

2022

Org. Chem. Front.

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“…Thus, the corresponding substrates that are sensitive to bases will be particularly tolerated, and the scope will be broadened . Compared to currently intense studies on assembling C–C bonds, other C–X bonds such as C–Si, C–Ge, and C–S formations are much less progressed due to the uncovered reactivity match and selective coupling of electrophilic fragments (Scheme a). This kind of novel method is featured with “base-free” conditions with excellent functional group tolerance, avoiding using odor thiols or thiophenols and readily accessible carbon electrophiles, providing a modular platform to access various thioethers with good efficiency.…”

Section: Introductionmentioning

confidence: 99%

Nonbasic Synthesis of Thioethers via Nickel-Catalyzed Reductive Thiolation Utilizing NBS-Like N-Thioimides as Electrophilic Sulfur Donors

Liu

Zhang

et al. 2023

J. Org. Chem.

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The nonbasic synthesis of unsymmetrical thioethers via nickel-catalyzed reductive thiolation between aryl(hetero) iodides and N-thioimides is illustrated. N-Bromosuccinimide (NBS)-like Nthioimides were found quite reactive toward thiolation with carbon electrophiles, and a series of structurally varied thioethers were successfully prepared under mild reaction conditions. The transformation was featured with the new application of the NBS-like reagents, good functional group tolerance, and late-stage modification of biologically active scaffolds, thus providing an expeditious and efficient platform to construct polyfunctional thioethers.

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Nickel-Catalyzed Reductive Csp³–Ge Coupling of Alkyl Bromides with Chlorogermanes

Cited by 27 publications

References 52 publications

Reductive Cross-Coupling of Unreactive Electrophiles

Reductive Cross-Coupling of Unreactive Electrophiles

Organogermanium(iv) compounds in photo-induced radical reactions

Nonbasic Synthesis of Thioethers via Nickel-Catalyzed Reductive Thiolation Utilizing NBS-Like N-Thioimides as Electrophilic Sulfur Donors

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Nickel-Catalyzed Reductive Csp3–Ge Coupling of Alkyl Bromides with Chlorogermanes

Cited by 27 publications

References 52 publications

Reductive Cross-Coupling of Unreactive Electrophiles

Reductive Cross-Coupling of Unreactive Electrophiles

Organogermanium(iv) compounds in photo-induced radical reactions

Nonbasic Synthesis of Thioethers via Nickel-Catalyzed Reductive Thiolation Utilizing NBS-Like N-Thioimides as Electrophilic Sulfur Donors

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Nickel-Catalyzed Reductive Csp³–Ge Coupling of Alkyl Bromides with Chlorogermanes