A practical guide for using lithium halocarbenoids in homologation reactions

Monticelli, Serena; Rui, Marta; Castoldi, Laura; Missere, G; Pace, Vittorio

doi:10.1007/s00706-018-2232-9

Cited by 9 publications

(3 citation statements)

References 52 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…An alternative procedure describes the synthesis of 2-chloro-1-phenylethanone from the phenyl Weinreb amide ( Scheme 85 ) [ 215 ]. The harsh reaction conditions and the use of unstable reagents (i.e., ICH 2 Cl) limit the protocol’s application considerably.…”

Section: Miscellaneous Routesmentioning

confidence: 99%

Synthetic Access to Aromatic α-Haloketones

et al. 2022

View full text Add to dashboard Cite

α-Haloketones play an essential role in the synthesis of complex N-, S-, O-heterocycles; of which some exhibit a remarkable biological activity. Research further illustrated that α-bromo-, α-chloro-, and α-iodoketones are key precursors for blockbuster pharmacological compounds. Over the past twenty years, substantial advances have been made in the synthesis of these industrially relevant building blocks. Efforts have focused on rendering the synthetic protocols greener, more effective and versatile. In this survey, we summarised and thoroughly evaluated the progress of the field, established in the past two decades, in terms of generality, efficacy and sustainability.

show abstract

Section: Miscellaneous Routesmentioning

confidence: 99%

Synthetic Access to Aromatic α-Haloketones

et al. 2022

View full text Add to dashboard Cite

show abstract

“…In 2018, Pace and co-workers reported the use of ICH 2 Cl/ MeLi·LiBr for the in situ formation of lithium chlorocarbenoid and the reactions with aldehydes and ketones (Scheme 30 ). 32…”

Section: Applications For the Synthesis Of 12-chlorohydrinsmentioning

confidence: 99%

The Synthetic Approaches to 1,2-Chlorohydrins

Hilt¹

2022

Synthesis

View full text Add to dashboard Cite

This short review highlights the hitherto realised synthetic approaches towards organic 1,2-chlorohydrins by functionalisation of alkenes (i.e., 1,2-chlorohydroxylation), which is the most prominent access route to this class of compounds. Also, some other synthetic approaches involving the reduction of α-chloroketones, the epoxide opening ring by chloride anions and the utilisation of Grignard reagents for the synthesis of these compounds and chlorination of allylic alcohols are highlighted. Finally, enzymatic reactions for the formation of chlorohydrins are briefly summarised followed by a short view on natural products containing this moiety.1 Introduction2 Applications for the Synthesis of 1,2-Chlorohydrins2.1 Chlorohydroxylation of Alkenes2.2 Reduction of Chloroketones2.3 Metalorganic Reagents2.4 Epoxide Ring Opening2.5 Chlorination of Allylic Alcohols2.6 Biochemical Methods2.7 Selected Applications in Natural Product Total Synthesis3 Conclusion

show abstract

“…Because of the adoption of halogen, hydrogen, metalloid or sulfoxide exchange strategies to generate the carbenoid, it could be convenient to use a small excess of these carbenoid precursors (compared to metalating agent) in order to preserve the electrophile from undesired attacks of these highly reactive nucleophiles/bases. 7b Although the con-trolled addition of the metalating agents via a syringe pump represents an adequate technique for preparing carbenoids, 11 the advent of microfluidic technologies contributed to further improve the critical methodological aspect of their generation, thus avoiding the requirement for Barbier-type conditions in some circumstances. 12 The chemistry of halocarbenoids attracted significant interest because of the innate potential of the approach to constitute a valid and effective alternative to classical diazomethane-based procedures.…”

mentioning

confidence: 99%

Carbenoid-Mediated Homologation Tactics for Assembling (Fluorinated) Epoxides and Aziridines

Ielo

Pillari

Miele

et al. 2020

Synlett

Self Cite

View full text Add to dashboard Cite

Homologation strategies provide highly versatile tools in organic synthesis for the introduction of a CH2 group into a given carbon skeleton. The operation can result in diverse structural motifs by tuning of the reaction conditions and the nature of the homologating agent. In this Account, concisely contextualizing our work with lithium carbenoids (LiCH2X, LiCHXY etc) for homologating carbon-centered electrophiles, we focus on the assembly of three-membered cycles featuring fluorinated substituents. Two illustrative case studies are considered: (1) the development and employment of fluorinated carbenoids en route to rare α-fluoroepoxides and aziridines, and (2) the installation of up to halomethylenic groups on trifluoroimidoylacetyl chlorides (TFAICs) for preparing CF3-containing halo- and halomethylaziridines. Collectively, we demonstrate that the initial homologation event generated by the installation of the carbenoid, upon modulation of the conditions, serves as a tool for creating fluorinated building blocks in a single operation.

show abstract

A practical guide for using lithium halocarbenoids in homologation reactions

Cited by 9 publications

References 52 publications

Synthetic Access to Aromatic α-Haloketones

Synthetic Access to Aromatic α-Haloketones

The Synthetic Approaches to 1,2-Chlorohydrins

Carbenoid-Mediated Homologation Tactics for Assembling (Fluorinated) Epoxides and Aziridines

Contact Info

Product

Resources

About