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

被引：16

作者：

Crossman, Aaron S. ^{[1
]}

Larson, Alec T. ^{[1
]}

Shi, Jake X. ^{[1
]}

Krajewski, Sebastian M. ^{[1
]}

Akturk, Eser S. ^{[1
]}

Marshak, Michael P. ^{[1
]}

机构：

[1] Univ Colorado, Dept Chem, Boulder, CO 80303 USA

来源：

JOURNAL OF ORGANIC CHEMISTRY | 2019年 / 84卷 / 11期

关键词：

CARBON BOND FORMATION; GRIGNARD-REAGENTS; AEROBIC EPOXIDATION; COUPLING REACTIONS; MOLECULAR-OXYGEN; SOFT ENOLIZATION; SODIUM AMIDE; O-ACYLATION; COMPLEXES; LIGAND;

D O I：

10.1021/acs.joc.9b00433

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Bulky beta-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 beta-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.

引用

页码：7434 / 7442

页数：9

共 69 条

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