Synthesis of Thiomorpholin‐3‐ones by a Gold‐Catalysed Oxidative Cyclisation‐Rearrangement Cascade from Ynamides

Baker, Thomas A.; Davies, Paul W.

doi:10.1002/ejoc.201900603

Cited by 15 publications

(5 citation statements)

References 60 publications

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“…The fact that a P,N-bidentate ligand is not compulsory for this trapping could be attributed to the less reactive nature of the imide gold carbene intermediate in comparison with the ketone gold carbene generated in L. Zhang's work. In 2019, Davies 71 developed the synthesis of α-aryl-α-allylthiomorpholine-3-ones 40 from ynamides 39 bearing a tethered thioether via intramolecular carbene trapping. 54 Notably, when benzyl sulfide was employed, a 1,2-benzyl migration occurs, affording 41 in 50% yield.…”

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

confidence: 99%

Homogeneous Gold-Catalyzed Oxidation Reactions

et al. 2021

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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

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

confidence: 99%

Homogeneous Gold-Catalyzed Oxidation Reactions

et al. 2021

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“…In this process, the [2,3]-sigmatropic rearrangement of the allyl sulfonium ylide allows for the formation of new C−C bonds. In 2014 and later in 2019, the group of Davies took advantage of this chemistry to synthesize tertiary thioethers 86 132 (Scheme 34, part A) and thiomorpholinones 87 134 (Scheme 34, part B) in an interor intramolecular fashion from ynamides 129 and 130. The key gold carbenoid intermediate required to proceed with the trapping with thioether was generated in the presence of pyridine N-oxide derivatives 131a−b.…”

Section: Ynamidesmentioning

confidence: 99%

Gold-Catalyzed Reactions of Specially Activated Alkynes, Allenes, and Alkenes

et al. 2020

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This review describes the gold-catalyzed reactions of specially activated alkynes, allenes, and alkenes. Such species are characterized by the presence of either electron-donating or electron-withdrawing groups as substituents of the carbon π-system. They are intrinsically polarized, and when compared to their nonspecially activated counterparts can therefore be involved in gold-catalyzed transformations featuring increased regio-, stereo-, and chemoselectivities. The chemistry of specially activated carbon π-systems under homogeneous gold catalysis is extremely rich and varied. The reactivity observed with nonspecially activated unsaturated systems can often be transposed to specially activated ones without loss of efficiency. However, specially activated carbon π-systems also exhibit specific reactivities that cannot be attained with regular substrates. In this family of carbon π-systems, ynamides and their analogs, along with alkynyl carbonyl derivatives, are the classes of substrates that have retained the most attention. This review provides an overview of the chemistry developed with all classes of specially activated carbon π-systems by discussing their general and specific reactivities, presenting and commenting on their gold-catalyzed transformations as well as their applications.

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“…The cascade sequences of gold-catalyzed alkyne oxidation/cyclization/ [2,3]-sigmatropic rearrangement were also observed in the case of S-allyl ynamides 164 with pyridine N-oxide as external oxidant (Scheme 96). [121] Here, the generation and subsequent rearrangement of cyclic sulfonium ylide 165 demonstrate a convenient route for the synthesis of functionalized thiomorpholin-3-one scaffold. Interestingly, the S-benzyl ynamids also produces similar thiomorpholin-3-ones following the Stevens [1,2]-rearrangement at the final step.…”

Section: Intramolecular Trapping Of α-Oxo Gold Carbene and Simultaneousmentioning

confidence: 99%

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

2020

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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.

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Synthesis of Thiomorpholin‐3‐ones by a Gold‐Catalysed Oxidative Cyclisation‐Rearrangement Cascade from Ynamides

Cited by 15 publications

References 60 publications

Homogeneous Gold-Catalyzed Oxidation Reactions

Homogeneous Gold-Catalyzed Oxidation Reactions

Gold-Catalyzed Reactions of Specially Activated Alkynes, Allenes, and Alkenes

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

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