β‐Keto Amides: A Jack‐of‐All‐Trades Building Block in Organic Chemistry

Abstract

β‐Keto amides are a versatile class of compounds that find wide applications in organic chemistry owing to the juxtaposition of multiple reaction sites within their molecular structures. Due to the importance of β‐keto amides in modern organic chemistry, numerous novel preparation methods, synthetic applications and unprecedented reactivities have been recorded over the past decade. Taking advantage of transition‐metal‐catalysis and organocatalysis, β‐keto amides have emerged into a jack‐of‐all‐trades building block for many stereoselective or tandemized multicomponent reactions. But so far, no reviews have been documented on these recent achievements with β‐keto amides. Our Review aims to provide a thorough summary regarding: (a) the synthesis of β‐keto amides, (b) the reactivities of β‐keto amides, (c) the synthetic applications of β‐keto amides in various important heterocyclic compounds, and (d) the coordination of β‐keto amides with main group elements and transition metals and the relevant applications.

Synthesis of N-[1-(2-Acetyl-4,5-dimethoxyphenyl)propan-2-yl]benzamide and Its Copper(II) Complex

“…The crystal structure of bis(1-N-benzylamino-1,3-butane-dionate)copper(II) was determined by B. Corain et al [17]. Recently, a review for synthesis and reactivities of β-ketoamides and their applications for heterocycle constructions and coordination chemistry was presented by Wanfang Li et al [18].…”

The applications of β‐keto amides for heterocycle synthesis

“…With the development of transition‐metal‐catalyzed cross‐coupling reactions, many new protocols for the construction of β ‐keto amides had been established, such as Pd‐catalyzed carbonylations [34], Ni‐catalyzed cross‐Claisen condensation between amides and Rh‐catalyzed hydroacylation of alkenes and alkynes [35], which allowed for the efficient synthesis of many functionalized β ‐keto amides. We have also summarized these synthetic advances in our recent review [36] and will not describe more details here.…”

“…During the past decades, the development of transition‐metal‐catalysis and organocatalysis spurred the role of β ‐keto amides as a jack‐of‐all‐trades building block for much quick construction of complex molecules. In our recent review on β ‐keto amides [36], we briefly touched upon the applications of β ‐keto amides in the synthesis of heterocycles and some carbocycles. Herein, we decide to recount the use of β ‐keto amides for the synthesis of the typical heterocyclic compounds, especially focusing on the recent synthesis with the assistance of transition‐metal‐catalyzed and organocatalyzed multicomponent reactions (MCRs).…”

Pd/C-Catalyzed Carbonylative Amidation for the Synthesis of 2-Carboxamidocyclohexane-1,3-diones

“…β-Ketoamides, being some of the most privileged scaffolds, have been used extensively to synthesize a range of agrochemicals, organic dyes, and other biologically active molecules . Furthermore, they form the core structure of various drug molecules such as piroxicam and teriflunomide and are exemplified as a crucial functionality in a series of tetracycline-class drugs such as tetracycline, minocycline, oxycycline, doxycycline, sarecycline, eravacycline, and omadacycline (Scheme a) .…”