Gold-Catalyzed Oxidation of Thioalkynes To Form Phenylthio Ketene Derivatives via a Noncarbene Route

Sharma, Pankaj; Singh, Rahulkumar Rajmani; Giri, Sovan Sundar; Chen, Liang Yu; Cheng, Mu Jeng; Liu, Rai Shung

doi:10.1021/acs.orglett.9b01768

Cited by 25 publications

(16 citation statements)

References 59 publications

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“…In 2019, R.-S. Liu reported a 1,2-arylthio migration in the oxidation of thioalkyne substrates (Scheme ). Arylthioketenes AS are generated and subsequently trapped by alcohols to afford the corresponding α-arylthio esters 42 . Various arylthio groups are allowed, and the electronic properties of the aryl group were shown to not significantly influence the reaction outcome.…”

Section: Reactions Without Metal Oxidation State Changementioning

confidence: 99%

“…In 2019, R.-S. Liu reported a 1,2-arylthio migration in the oxidation of thioalkyne substrates (Scheme 23). 72 73 One quinoline molecule is incorporated into the final product, which exhibits two conformers that are stabilized by different hydrogen-bonding interactions. The proposed mechanism entails trapping of the gold carbene by the tethered sulfide to form four-membered sulfonium AT, its subsequent ring opening by residual water to arrive at gold enolate AS, and finally the reaction of the gold O-enolate with another molecule of the oxidant.…”

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

confidence: 99%

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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 Changementioning

confidence: 99%

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

confidence: 99%

Homogeneous Gold-Catalyzed Oxidation Reactions

et al. 2021

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“…The possibility to perform oxidative transformations of alkynyl sulfides in the presence of 8-methylquinoline N-oxide 352 has been studied by Liu and Cheng. 157 It was shown that alkynyl sulfides 351 could be oxidatively rearranged into functionalized ketones 353 when treated with (Ph 3 P)AuCl/ AgNTf 2 in the presence of an excess nucleophile (Scheme 84, part A). On the basis of DFT calculations, it was proposed that the oxidation of 351 does not proceed via the formation of an α-oxo gold carbene, as usually described for related oxidative transformations, but directly via a gold-bound ketene intermediate 354.…”

Section: Alkynyl Sulfides and Selenidesmentioning

confidence: 99%

“…The possibility to perform oxidative transformations of alkynyl sulfides in the presence of 8-methylquinoline N -oxide 352 has been studied by Liu and Cheng . It was shown that alkynyl sulfides 351 could be oxidatively rearranged into functionalized ketones 353 when treated with (Ph 3 P)AuCl/AgNTf 2 in the presence of an excess nucleophile (Scheme , part A).…”

Section: Carbon π-Systems With Electron-donating Groupsmentioning

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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“…Simultaneously, Liu and coworkers developed [100] gold-catalyzed oxidation of thioalkynes 119 to phenyl/ arylthioketene derivatives using external 8-methylquinoline N-oxides presumably via a noncarbene route (Scheme 72). A wide range of terminal and internal thioalkynes bearing alkyl, ketone, ester, and oxime ether substituents are used.…”

Section: 2-alkyl Aryl Thiol Alkenyl Alkynyl Benzoyloxy or Acylmentioning

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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Gold-Catalyzed Oxidation of Thioalkynes To Form Phenylthio Ketene Derivatives via a Noncarbene Route

Cited by 25 publications

References 59 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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