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Lithium halomethylcarbenoids : preparation and use in the homologation of carbon electrophiles

(2016) CHEMICAL RECORD. 16(4). p.2061-2076
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Abstract
alpha-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 Kobrich - 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 -elimination processes. Nowadays, the use of low temperatures (-78 degrees 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 -halomethyllithium-mediated homologations of a series of carbon electrophiles such as carbonyl compounds, imines, esters, Weinreb amides, and isocyanates.
Keywords
carbenoids, carbonyl compounds, lithium, homologation reactions, synthetic methods, HIV PROTEASE INHIBITORS, ALPHA'-CHLOROMETHYLKETONE DERIVATIVES, REAGENT-CONTROLLED HOMOLOGATION, LOW-TEMPERATURE C-13-NMR, ASSEMBLY-LINE SYNTHESIS, CHLORO BORONIC ESTERS, WEINREB AMIDES, EFFICIENT SYNTHESIS, ORGANIC-SYNTHESIS, CONFIGURATIONAL STABILITY

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Citation

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MLA
Pace, Vittorio, Wolfgang Holzer, and Norbert De Kimpe. “Lithium Halomethylcarbenoids : Preparation and Use in the Homologation of Carbon Electrophiles.” CHEMICAL RECORD 16.4 (2016): 2061–2076. Print.
APA
Pace, V., Holzer, W., & De Kimpe, N. (2016). Lithium halomethylcarbenoids : preparation and use in the homologation of carbon electrophiles. CHEMICAL RECORD, 16(4), 2061–2076.
Chicago author-date
Pace, Vittorio, Wolfgang Holzer, and Norbert De Kimpe. 2016. “Lithium Halomethylcarbenoids : Preparation and Use in the Homologation of Carbon Electrophiles.” Chemical Record 16 (4): 2061–2076.
Chicago author-date (all authors)
Pace, Vittorio, Wolfgang Holzer, and Norbert De Kimpe. 2016. “Lithium Halomethylcarbenoids : Preparation and Use in the Homologation of Carbon Electrophiles.” Chemical Record 16 (4): 2061–2076.
Vancouver
1.
Pace V, Holzer W, De Kimpe N. Lithium halomethylcarbenoids : preparation and use in the homologation of carbon electrophiles. CHEMICAL RECORD. 2016;16(4):2061–76.
IEEE
[1]
V. Pace, W. Holzer, and N. De Kimpe, “Lithium halomethylcarbenoids : preparation and use in the homologation of carbon electrophiles,” CHEMICAL RECORD, vol. 16, no. 4, pp. 2061–2076, 2016.
@article{8510152,
  abstract     = {alpha-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 Kobrich - 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 -elimination processes. Nowadays, the use of low temperatures (-78 degrees 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 -halomethyllithium-mediated homologations of a series of carbon electrophiles such as carbonyl compounds, imines, esters, Weinreb amides, and isocyanates.},
  author       = {Pace, Vittorio and Holzer, Wolfgang and De Kimpe, Norbert},
  issn         = {1527-8999},
  journal      = {CHEMICAL RECORD},
  keywords     = {carbenoids,carbonyl compounds,lithium,homologation reactions,synthetic methods,HIV PROTEASE INHIBITORS,ALPHA'-CHLOROMETHYLKETONE DERIVATIVES,REAGENT-CONTROLLED HOMOLOGATION,LOW-TEMPERATURE C-13-NMR,ASSEMBLY-LINE SYNTHESIS,CHLORO BORONIC ESTERS,WEINREB AMIDES,EFFICIENT SYNTHESIS,ORGANIC-SYNTHESIS,CONFIGURATIONAL STABILITY},
  language     = {eng},
  number       = {4},
  pages        = {2061--2076},
  title        = {Lithium halomethylcarbenoids : preparation and use in the homologation of carbon electrophiles},
  url          = {http://dx.doi.org/10.1002/tcr.201600011},
  volume       = {16},
  year         = {2016},
}

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