2109-87-7Relevant academic research and scientific papers
Iron-Catalyzed Nucleophilic Addition Reaction of Organic Carbanion Equivalents via Hydrazones
Li, Chen-Chen,Dai, Xi-Jie,Wang, Haining,Zhu, Dianhu,Gao, Jian,Li, Chao-Jun
, p. 3801 - 3805 (2018/07/25)
Earth-abundant and well-defined iron complexes are found to be cheap and effective catalysts for a series of "umpolung" nucleophilic additions of hydrazones. The new catalytic system not only maintains the broad substrate scope of an earlier expensive ruthenium system but also attains chemoselectivity of different kinds of carbonyl groups. Furthermore, the iron catalyst enables this reaction at ambient temperature.
Aldehydes as alkyl carbanion equivalents for additions to carbonyl compounds
Wang, Haining,Dai, Xi-Jie,Li, Chao-Jun
, p. 374 - 378 (2017/04/03)
Nucleophilic addition reactions of organometallic reagents to carbonyl compounds for carbon-carbon bond construction have played a pivotal role in modern chemistry. However, this reaction's reliance on petroleum-derived chemical feedstocks and a stoichiometric quantity of metal have prompted the development of many carbanion equivalents and catalytic metal alternatives. Here, we show that naturally occurring carbonyls can be used as latent alkyl carbanion equivalents for additions to carbonyl compounds, via reductive polarity reversal. Such 'umpolung' reactivity is facilitated by a ruthenium catalyst and diphosphine ligand under mild conditions, delivering synthetically valuable secondary and tertiary alcohols in up to 98% yield. The unique chemoselectivity exhibited by carbonyl-derived carbanion equivalents is demonstrated by their tolerance to protic reaction media and good functional group compatibility. Enantioenriched tertiary alcohols can also be accessed with the aid of chiral ligands, albeit with moderate stereocontrol. Such carbonyl-derived carbanion equivalents are anticipated to find broad utility in chemical bond formation.
Alcoxymethyltributyletains precurseurs d'alcoxymethyllithiums: application a la synthese de monoethers d'α-glycols et a l'homologation de cetones en aldehydes
Duchene, Alain,Mouko-Mpegna, David,Quintard, Jean-Paul
, p. 787 - 793 (2007/10/02)
Ethoxymethyltributyltin (obtained from diethoxymethyltributyltin, acetyl chloride and tributyltin hydride) and methoxymethyltributyltin (obtained from chloromethyl-methyl ether and tributylstannylmagnesium chloride) have been transmetallated with butyllithium to give the corresponding alkoxymethyl lithium reagents.This reaction, although usually performed in ether, is possible in a variety of other solvents thus simplifying some of the problems encountered during isolation of the products.The alkoxymethyllithiums obtained react with aldehydes and ketones to give cleanly the corresponding monoprotected α-glycols.Stereochemical trends were observed for hydratropaldehyde and 4-tertiarybutylcyclohexanone, while regiochemical trends were evaluated in the case of cyclohexen-2-one.Syntheis of aldehydes has been achieved in good yields from tertiary monoprotected α-glycols using conventional methods.
