Stabile Stammlösungen von Silicium‐Grignard‐Reagenzien: Anwendung in eisen‐ und cobaltkatalysierten radikalischen C(sp<sup>3</sup>)‐Si‐Kreuzkupplungsreaktionen

Xue, Weichao; Shishido, Ryosuke; Oestreich, Martin

doi:10.1002/ange.201807640

Cited by 23 publications

(4 citation statements)

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“…In 2018, Oestreich and co-workers 30 122 123 reported robust methodology for preparing silylmagnesium. This method made tremendous advancement in silylmagnesium synthesis by avoiding the synthesis of silyl pronucleophiles such as Si–Si, and Si–B compounds.…”

Section: Silyl Anions Of Group II Metalsmentioning

confidence: 99%

“…R 3 SiLi was added into the refluxing ethereal solution of MgBr 2 ·THF leading to the formation of 0.5 M R 3 SiMgX (Scheme 39 ). 30…”

Section: Silyl Anions Of Group II Metalsmentioning

confidence: 99%

“…29 This reaction failed to produce silyl anions if all of the aryl groups on silicon were substituted with an alkyl group, this is because the aryl group acts as an electron acceptor and facilitates the reductive metalation of the disilane (Scheme 2c ). 29 30 31…”

Section: Introductionmentioning

confidence: 99%

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Preparations of Silyl Anions

Rasappan,

Pulikkottil,

Balakrishnan

et al. 2023

Synthesis

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This review is collective writing on synthetic procedures for the synthesis of different silyl nucleophiles which are valuable reagents for chemists, particularly in the field of organic synthesis and organometallic chemistry. We have described the preparations of silyl nucleophiles of lithium, sodium, potassium, rubidium, and caesium from group I metals. We have also focused on silyl anions of beryllium, magnesium, calcium, strontium, and barium from group II metals. We included synthetic procedures for silyl anions of zirconium, hafnium, cadmium, and zinc. The synthesis of group XIII silyl anions of boron and aluminium is also highlighted in this short review.

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Section: Silyl Anions Of Group II Metalsmentioning

confidence: 99%

“…R 3 SiLi was added into the refluxing ethereal solution of MgBr 2 ·THF leading to the formation of 0.5 M R 3 SiMgX (Scheme 39 ). 30…”

Section: Silyl Anions Of Group II Metalsmentioning

confidence: 99%

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Preparations of Silyl Anions

Rasappan,

Pulikkottil,

Balakrishnan

et al. 2023

Synthesis

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“…It was not until 2018 that Oestreich and coworkers made a breakthrough in this area. This transformation could proceed well with the use of a magnesium‐based silicon reagent via iron catalysis (Scheme ) . In this reaction, although the yields of the tertiary alkyl bromides were unsatisfied, the primary and secondary alkyl bromides could undergo this reaction smoothly and afforded the corresponding products in high yields.…”

Section: Iron‐catalyzed C−si Bond Formationmentioning

confidence: 99%

Iron‐Catalyzed Cross‐Coupling Reactions for the Construction of Carbon‐Heteroatom Bonds

et al. 2020

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Carbon-heteroatom bonds are ubiquitous among pesticides, pharmaceutical agents, and natural products. In recent years, significant progress has been made in transition-metal-catalyzed carbon-heteroatom bond formation. Especially, iron-catalyzed reactions have become a focused area in organic chemistry owing to their advantages of low cost, economical and environmental benignity. This review intends to summarize the recent advances in the construction of carbon-heteroatom bonds via cross-coupling reactions using iron as a catalyst, including the formation of CÀ N, CÀ O, CÀ S, CÀ B, and CÀ Si bonds. A series of nucleophilic heteroatoms reagents, reaction classifications, and iron catalytic systems are discussed. In addition, some mechanistic studies have also been described. formation of CÀ N, CÀ O, CÀ S, CÀ B, and CÀ Si bonds are mainly focused. 2. Iron-Catalyzed CÀ N Bond Formation The construction of CÀ N bond by transition metal-catalyzed is one of the most significant transformations in organic synthesis, which is widely employed in chemical, pharmaceutical, and materials industries. [8] The classical method to access CÀ N bond is through the transition metal-catalyzed cross-coupling reaction between aryl or alkenyl halides and amines, also known as Buchwald-Hartwig amination reaction. In recent years, the formation of CÀ N bond via CÀ H activation has been welldocumented. [9] After decades of development, the great progress has been achieved in the transition metals (Cu, Pd, Ni, Fe, Co) catalyzed the construction of the CÀ N bond. [10] However, compared with other transition metals, iron-catalyzed CÀ N bond formation has less been studied, which might be caused by the negative effect of trace metals. [21-22] 2.1. Iron-Catalyzed CspÀ N Bond Formation Alkynamines are essential compounds, widely used in organic reactions such as pericyclic reaction, tandem RCM, Pauson-Khand reaction, Kinugasa reaction, Saucy-Marbet rearrangement, and Ficini-Claisen rearrangement. [11] In 2009, Zhang and coworkers [11e] developed the first example of iron-catalyzed amination of alkynyl bromides (Scheme 1). Nucleophiles such as amide, sulfonamide, and indole could react with alkynyl bromides to obtain alkynamines in high yields under FeCl 3 * 6H 2 O and DMEDA catalytic system. This reaction exhibits good functional group tolerance, and the functional groups

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Enantioselektiver Aufbau von α‐chiralen Silanen durch nickelkatalysierte C(sp³)‐C(sp³)‐Kreuzkupplung

Mao

Oestreich

2019

Angewandte Chemie

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Es wird über eine enantioselektive C(sp 3 )-C(sp 3 )-Kreuzkupplung von racemischen a-silylierten Alkyliodiden und Alkylzinkreagenzien berichtet. Die Reaktion wird von NiCl 2 /(S,S)-Bn-Pyboxkatalysiert und erbringt a-chirale Silane mit hoher Enantiokontrolle.Das Katalysatorsystem ist nicht in der Lage,d ie Kreuzkupplung des entsprechenden Kohlenstoffanalogons zu vermitteln, was den stabilisierenden Effekt der Silylgruppe auf die Alkylradikalzwischenstufe untermauert (a-Siliciumeffekt). Beide Kupplungspartner kçnnen, müssen aber nicht, funktionalisiert sein und damit werden selbst achirale Silane ohne funktionelle Gruppe in unmittelbarer Nähe zum asymmetrischsubstituierten Kohlenstoffatom zugänglich. Dies unterscheidet das neue Verfahren von den etablierten Methoden zur Synthese von a-chiralen Silanen.

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Stabile Stammlösungen von Silicium‐Grignard‐Reagenzien: Anwendung in eisen‐ und cobaltkatalysierten radikalischen C(sp³)‐Si‐Kreuzkupplungsreaktionen

Cited by 23 publications

References 51 publications

Preparations of Silyl Anions

Preparations of Silyl Anions

Iron‐Catalyzed Cross‐Coupling Reactions for the Construction of Carbon‐Heteroatom Bonds

Enantioselektiver Aufbau von α‐chiralen Silanen durch nickelkatalysierte C(sp³)‐C(sp³)‐Kreuzkupplung

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Stabile Stammlösungen von Silicium‐Grignard‐Reagenzien: Anwendung in eisen‐ und cobaltkatalysierten radikalischen C(sp3)‐Si‐Kreuzkupplungsreaktionen

Cited by 23 publications

References 51 publications

Preparations of Silyl Anions

Preparations of Silyl Anions

Iron‐Catalyzed Cross‐Coupling Reactions for the Construction of Carbon‐Heteroatom Bonds

Enantioselektiver Aufbau von α‐chiralen Silanen durch nickelkatalysierte C(sp3)‐C(sp3)‐Kreuzkupplung

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Product

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Stabile Stammlösungen von Silicium‐Grignard‐Reagenzien: Anwendung in eisen‐ und cobaltkatalysierten radikalischen C(sp³)‐Si‐Kreuzkupplungsreaktionen

Enantioselektiver Aufbau von α‐chiralen Silanen durch nickelkatalysierte C(sp³)‐C(sp³)‐Kreuzkupplung