Gold(I)-Catalyzed Oxidation of Acyl Acetylenes to Vicinal Tricarbonyls

Dubovtsev, Alexey Yu.; Dar’in, Dmitry; Kukushkin, Vadim Yu.

doi:10.1021/acs.orglett.9b01297

Cited by 30 publications

(23 citation statements)

References 58 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…They can be converted into several types of heterocycles using one-pot transformations (Scheme B) . 1,2,3-Tricarbonyl compounds can also be obtained using the same strategy . K. Severin reported that the C–C triple bond of alkynyl triazenes can be similarly double-oxidized under gold catalysis as long as the carbene 1,2-C–H insertion pathway is not available …”

Section: Reactions Without Metal Oxidation State Changementioning

confidence: 99%

“…54 1,2,3-Tricarbonyl compounds can also be obtained using the same strategy. 56 K. Severin reported that the C−C triple bond of alkynyl triazenes can be similarly double-oxidized under gold catalysis as long as the carbene 1,2-C−H insertion pathway is not available. 57 In 2011, L. Zhang extended this type of oxidative gold catalysis to terminal allene substrates.…”

Section: Reactions Without Metal Oxidation State Change 21 Activated ...mentioning

confidence: 99%

See 1 more Smart Citation

Homogeneous Gold-Catalyzed Oxidation Reactions

et al. 2021

View full text Add to dashboard Cite

Homogeneous gold catalysis has experienced extraordinary development since the dawn of this millennium. Oxidative gold catalysis is a vibrant and fertile subfield and has over the years delivered a diverse array of versatile synthetic methods of exceptional value to synthetic practices. This review aims to cover this topic in a comprehensive manner. The discussions are organized by the mechanistic aspects of the metal oxidation states and further by the types of oxidants or oxidizing functional groups. Synthetic applications of oxidative gold catalysis are also discussed. CONTENTS 4.5. Oxidation of Sulfides and Other Functional Groups 9029 5. Conclusion and Outlook 9030 Author Information 9030 Corresponding Author 9030 Authors 9030 Author Contributions 9030 Notes 9030 Biographies 9030 Acknowledgments 9031 References 9031

show abstract

Section: Reactions Without Metal Oxidation State Changementioning

confidence: 99%

Section: Reactions Without Metal Oxidation State Change 21 Activated ...mentioning

confidence: 99%

Homogeneous Gold-Catalyzed Oxidation Reactions

et al. 2021

View full text Add to dashboard Cite

show abstract

“…Moreover, alkynyl esters, amides and ketones are efficiently converted into their corresponding vicinal tricarbonyls under mild conditions without any acid additives (Scheme 7). [29] In some cases, the isolated products were mixture of keto and their hydrated form. When NÀ O oxidant is employed, the reduced oxidant can subsequently act as N-nucleophile resulting in oxoamination of alkyne.…”

Section: Oxidative 12-difunctionalizations Of Alkynesmentioning

confidence: 99%

Gold‐Catalyzed Oxidative Alkyne Functionalization by N−O/S−O/C−O Bond Oxidants

2020

View full text Add to dashboard Cite

Since the beginning of this century, homogeneous gold‐catalyzed alkyne transformations have been an active area of research in pursuit of developing efficient synthetic methodologies. This emerging area of research which at the beginning exploited the mild Lewis acid character of gold and its propensity to form π‐complex with alkyne, has been reinvigorated upon the discovery of gold‐catalyzed oxidative alkyne functionalization in 2007. The gold‐catalyzed alkyne oxidation enabled direct access to α‐oxo gold carbenes and gold alkynal complex with versatile reactivity which has been applied to achieve transformations including but not limited to oxyarylation, C−H, X−H (X=N, O) insertion, cyclization, cycloaddition, ring expansion, and various cascade reactions. This review provides a comprehensive summary of methods, applications and mechanistic insight of gold‐catalyzed oxidative alkyne functionalization by N−O/S−O/C−O bond oxidants covering the literature reports appeared since 2007.

show abstract

“…While the cyclopropanation of related α-oxo carbenes is known, − NT reactions utilizing α-imino carbenes are quite poorly explored: Hashmi and co-workers reported the only gold-catalyzed cyclopropanation of α-imino carbenes generated from anthranils and sulfilimines functioning as NTRs. Inspired by these works and on the basis of our previous experience in gold catalysis, − we hypothesized that benzofuroxans could also serve as a source of gold α-imino carbenes for intramolecular cyclopropanation (Scheme C). We also addressed N -allylynamides, as the reaction partners, in view of their high reactivity in the catalytic annulations and facile customization of their substitution pattern. − …”

Section: Introductionmentioning

confidence: 99%

Gold-Catalyzed Nitrene Transfer from Benzofuroxans to N-Allylynamides: Synthesis of 3-Azabicyclo[3.1.0]hexanes

et al. 2021

Self Cite

View full text Add to dashboard Cite

The gold-catalyzed reaction between benzofuroxans, functioning as nitrene transfer reagents, and N-allylynamides leads to 3-azabicyclo[3.1.0]hexan-2-imines. This highly selective annulation proceeds smoothly under mild conditions (5 mol % Ph3PAuNTf2, PhCl, 60 °C) and exhibits high functional group tolerance (21 examples, ≤96% yields). The obtained cyclopropanated products represent a useful synthetic platform with an easily modulated substitution pattern as illustrated by their postmodifications. Intramolecular cyclopropanation of gold α-imino carbene intermediates is suggested as a key step of the catalytic cycle.

show abstract

Gold(I)-Catalyzed Oxidation of Acyl Acetylenes to Vicinal Tricarbonyls

Cited by 30 publications

References 58 publications

Homogeneous Gold-Catalyzed Oxidation Reactions

Homogeneous Gold-Catalyzed Oxidation Reactions

Gold‐Catalyzed Oxidative Alkyne Functionalization by N−O/S−O/C−O Bond Oxidants

Gold-Catalyzed Nitrene Transfer from Benzofuroxans to N-Allylynamides: Synthesis of 3-Azabicyclo[3.1.0]hexanes

Contact Info

Product

Resources

About