Anionic Access to Silylated and Germylated Binuclear Heterocycles

Boddaert, Thomas; Colleoni, François; Mistico, Laetitia; Querolle, Olivier; Meerpoel, Lieven; Angibaud, Patrick; Durandetti, Muriel; Maddaluno, Jacques

doi:10.1002/chem.201402597

Cited by 29 publications

(8 citation statements)

References 35 publications

(21 reference statements)

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“…One can wonder if such a structure can rearrange via ring expansion, driven by a favorable strain release, to form a new tetravalent species with a six-membered ring (Scheme 3). This behavior, related to a sila-Matteson rearrangement [21][22][23], has already been observed for isolable pentacoordinate [24] and hexacoordinate chloromethylsilicates [25]. O-Migration, N-migration and C-migration have been reported and are usually triggered by thermal conditions when the hypercoordinate species are isolable.…”

Section: Lewis Acid-assisted Ring Expansionmentioning

confidence: 71%

Synthesis and Reactivity of Martin’s Spirosilane-Derived Chloromethylsilicate

et al. 2022

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Pentacoordinate silicon derivatives with a chloromethyl ligand are versatile compounds that are usually obtained from the corresponding tetravalent trialkoxy- or trihalogeno(chloromethyl)silane. We describe herein the synthesis of a chloromethylsilicate bearing two Martin’s ligands readily obtained by addition of in situ generated chloromethyllithium to a spirosilane. The reactivity of this new species was evaluated and it has been established that the chloride is displaced by strong nucleophiles such as alkyllithiums and (hetero)aryllithiums. In Lewis acidic conditions, the pentacoordinate silicon species rearranges through a formal insertion of a methylene into one Si–C bond, to form a new tetravalent spirosilane with a six-membered ring. The same kind of rearrangement can be triggered also by addition of a Lewis base. The mechanism of the rearrangement in both conditions has been studied by means of DFT calculations.

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Section: Lewis Acid-assisted Ring Expansionmentioning

confidence: 71%

Synthesis and Reactivity of Martin’s Spirosilane-Derived Chloromethylsilicate

et al. 2022

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“…Since the seminal studies by Köbrich, lithium halomethylcarbenoids have emerged as synthetically versatile reagents for accomplishing homologation reactions on a plethora of electrophiles not limited to carbon species (e.g., boron,35,50,54,74 zirconium,36 germanium/silicon,75 sulfur‐containing substrates76). Without any doubt, the important contributions by Hammerschmidt and co‐workers55,57,77 on the configurational stability of halo‐[D 1 ]‐methyllithium will open the field to the establishment of chiral carbenoid‐mediated homologation techniques to access enantiomerically pure functionalized halomethyl derivatives.…”

Section: Discussionmentioning

confidence: 99%

Lithium Halomethylcarbenoids: Preparation and Use in the Homologation of Carbon Electrophiles

Pace

Hölzer

Kimpe

2016

The Chemical Record

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α-Halomethyllithium carbenoids are useful homologating reagents which - reacting under proper reaction conditions as carbanions - enable the installation via nucleophilic addition of a reactive halomethyl fragment onto a preformed carbon-heteroatom bond. The pronounced thermolability represented - since seminal studies by Köbrich - the Achilles' heel of these reagents: the use of Barbier-type methodologies (i.e., the electrophile should be present in the reaction mixture prior to the formation of the carbenoid) was pivotal in order to suppress decomposition through α-elimination processes. Nowadays, the use of low temperatures (-78 °C) guarantees reliable procedures and, significantly, the employment of microreactor technologies allows external trapping to be performed even at higher temperatures as reported by Luisi. We will discuss the α-halomethyllithium-mediated homologations of a series of carbon electrophiles such as carbonyl compounds, imines, esters, Weinreb amides, and isocyanates.

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“…Interestingly, the substrate bearing a pyridyl ring underwent CH 2 –Si bond migration completely to deliver 1,2,3,4-tetrahydropyrido[3,4- e ][1,3]azasilines 101a – c in high yields. 37…”

Section: Six-membered Silaazacyclesmentioning

confidence: 99%

Synthetic Approaches for the Construction of Five- and Six-Membered Silaazacycles

Song

Wang

2022

Synthesis

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Silaazacycles, containing both nitrogen and silicon atoms, are emerging as the appealing ring structures in the development of silicon-containing functional molecules. Development of general and efficient methods towards these motifs has therefore attracted considerable attentions of synthetic chemists. This short review intends to highlight the representative advances in the synthesis of five- and six-membered silaazacycles.

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Anionic Access to Silylated and Germylated Binuclear Heterocycles

Cited by 29 publications

References 35 publications

Synthesis and Reactivity of Martin’s Spirosilane-Derived Chloromethylsilicate

Synthesis and Reactivity of Martin’s Spirosilane-Derived Chloromethylsilicate

Lithium Halomethylcarbenoids: Preparation and Use in the Homologation of Carbon Electrophiles

Synthetic Approaches for the Construction of Five- and Six-Membered Silaazacycles

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