Synthesis of Sterically Hindered β‑Diketones via Condensation of Acid Chlorides with Enolates

Bulky β-diketones have rarely exceeded dipivaloylmethane (DPM) in steric demand, largely due to synthetic limitations of the Claisen condensation. This work demonstrates hindered acid chlorides to be selective electrophiles in noncoordinating solvents for condensations with enolates. An improved syn...

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Bibliographic Details
Published in:Journal of organic chemistry 2019-06, Vol.84 (11), p.7434-7442
Main Authors: Crossman, Aaron S, Larson, Alec T, Shi, Jake X, Krajewski, Sebastian M, Akturk, Eser S, Marshak, Michael P
Format: Article
Language:English
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Summary:Bulky β-diketones have rarely exceeded dipivaloylmethane (DPM) in steric demand, largely due to synthetic limitations of the Claisen condensation. This work demonstrates hindered acid chlorides to be selective electrophiles in noncoordinating solvents for condensations with enolates. An improved synthesis of DPM is described (90% yield), and crowded β-diketones featuring bulky o-biphenyl or m-terphenyl fragments were prepared in good to excellent yields. These compounds are anticipated to have a steric profile far greater than that of DPM. General reaction conditions and mechanistic considerations are included.
ISSN:0022-3263
1520-6904
DOI:10.1021/acs.joc.9b00433