α‐Oxo‐Ketenimines from Isocyanides and α‐Haloketones: Synthesis and Divergent Reactivity

Mamboury, Mathias; Wang, Qian; Zhu, Jieping

doi:10.1002/chem.201703458

Cited by 21 publications

(9 citation statements)

References 72 publications

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“…Radical scavenging and 18 O labelling experiments pointed to the involvement of the key oxidation step of 110 to 111 (Scheme 20). In 2017, the Zhu group [81] reported a Pd‐catalyzed cross‐coupling between α ‐bromo ketone 113 and 109 to afford α ‐oxo‐ketenimine 114 , which was directly hydrolyzed to β ‐keto amide 115 in 81 % yield (Scheme 21a). The Passerini three‐component‐reaction of glyoxals 116 , isonitriles 117 and HOAc afforded α ‐acetoxy β ‐keto amides 118 in 60–89 % yields (Scheme 21b).…”

Section: Synthesis Of β‐Keto Amidesmentioning

confidence: 99%

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

Zheng

et al. 2021

Eur J Org Chem

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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.

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Section: Synthesis Of β‐Keto Amidesmentioning

confidence: 99%

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

Zheng

et al. 2021

Eur J Org Chem

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“…A Pd-catalyzed imidoylative MCR cascade to β-ketoamidines 90 or 5-aminopyrazoles 91 was reported by the group of Zhu [ 59 ]. Oxidative addition of the alkyl halide 87 , and subsequent isocyanide insertion is followed by β-hydride elimination of intermediate 92 , affording the ketenimine 93 as a common intermediate ( Scheme 28 ).…”

Section: Pd 0 -Catalyzed Isocyanide Insertionsmentioning

confidence: 99%

Recent Advances in Palladium-Catalyzed Isocyanide Insertions

et al. 2020

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Isocyanides have long been known as versatile chemical reagents in organic synthesis. Their ambivalent nature also allows them to function as a CO-substitute in palladium-catalyzed cross couplings. Over the past decades, isocyanides have emerged as practical and versatile C1 building blocks, whose inherent N-substitution allows for the rapid incorporation of nitrogeneous fragments in a wide variety of products. Recent developments in palladium catalyzed isocyanide insertion reactions have significantly expanded the scope and applicability of these imidoylative cross-couplings. This review highlights the advances made in this field over the past eight years.

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“…-Keto amide 63 was formed from the Pd(OAc) 2 -catalyzed reaction of -bromo ketone 61 and tert-butyl isocyanide (Scheme 21). 73 The reaction proceeds via an imidoylpalladium process to generate intermediate 62 followed by addition of water to yield amide 63. This strategy for the synthesis of intermediate 62 was used for the generation of the various important synthetic compounds, such as 5-aminopyrazoles, an -cyano ketone, tetrazoles, and an enaminone.…”

Section: Scheme 19 Pd-catalyzed Reaction Of Isocyanides and Allyl Ethmentioning

confidence: 99%

Transition Metal and Inner Transition Metal Catalyzed Amide Derivatives Formation through Isocyanide Chemistry

et al. 2020

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The synthesis of amides is a substantial research area in organic chemistry because of their ubiquitous presence in natural products and bioactive molecules. The use of easily accessible isocyanides as amidoyl (carbamoyl) synthons in cross-coupling reactions using transition metal and inner transition metöal catalysts is a current trend in this area. Isocyanides, owing to their coordination ability as a ligand and inherent electronic properties for reactions with various partners, have expanded the potential application of these transformations for the preparation of novel synthetic molecules and pharmaceutical candidates. This review gives an overview of the achievements in isocyanide-based transition metal and inner transition metal catalyzed amide formation and discusses highlights of the proposed distinct mechanisms.1 Introduction2 Synthesis of Arenecarboxamides3 Synthesis of Alkanamides4 Synthesis of Cyclic Amides5 Formation of Alkynamides6 Formation of Acrylamide-like Molecules7 Formation of Ureas and Carbamates8 Conclusion

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α‐Oxo‐Ketenimines from Isocyanides and α‐Haloketones: Synthesis and Divergent Reactivity

Cited by 21 publications

References 72 publications

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

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

Recent Advances in Palladium-Catalyzed Isocyanide Insertions

Transition Metal and Inner Transition Metal Catalyzed Amide Derivatives Formation through Isocyanide Chemistry

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