Cooperation between an alcoholic proton and boryl species in the catalytic gem-hydrodiborylation of carboxylic esters to access 1,1-diborylalkanes

Cooperation between an alcoholic proton and boryl species in the selective gem-hydrodiborylation of carboxylic esters is described. The simple iron salt FeBr2 was used as an effective catalyst. Experimental evidence suggests that the ester is initially hydrogenated with the alcoholic proton as the h...

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Bibliographic Details
Published in:Organic chemistry frontiers an international journal of organic chemistry 2019-04, Vol.6 (7), p.900-907
Main Authors: He, Zeyu, Zhu, Qing, Hu, Xiyu, Wang, Lu, Xia, Chungu, Liu, Chao
Format: Article
Language:English
Subjects:
Acetic acid
Alcohols
Aliphatic compounds
Catalysis
Chemical synthesis
Cooperation
Esters
Ethanol
Ethyl acetate
Functional groups
Hydrides
Iron
Organic chemistry
Protonation
Protons
Species
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Summary:Cooperation between an alcoholic proton and boryl species in the selective gem-hydrodiborylation of carboxylic esters is described. The simple iron salt FeBr2 was used as an effective catalyst. Experimental evidence suggests that the ester is initially hydrogenated with the alcoholic proton as the hydride source to provide an intermediate aldehyde, followed by a gem-diborylation with B2pin2 (bis(pinacolato)diboron) to selectively achieve gem-hydrodiborylation. The structure of the alkoxide used is important for chemoselective transformation of the ester functional group. When tert-butoxide is used, protonation of the iron boryl species to form an iron hydride species is rate-limiting, making hydrodiborylation of the ester selectively occur. When ethoxide or methoxide is used, the protonation of the iron boryl species to form an iron hydride species is relatively facile, making hydrogenation of the ester to an alcohol selectively occur with the alcoholic proton acting as the hydride source. With NaOtBu as the base and EtOH as the proton source, various aliphatic esters like ethyl acetate were selectively converted to 1,1-diborylalkanes in the presence of B2pin2. Diverse transformations of the obtained 1,1-diborylalkanes exhibit the advantages of this methodology for hetero multi-functionalization of ester functional groups for the synthesis of various value-added molecules.
ISSN:2052-4110
2052-4110
DOI:10.1039/c9qo00007k