Synthesis of Chiral Allylic Thioesters: Enantio‐ and Regioselective Iridium‐Catalyzed Allylations of KSAc

Gao, Ning; Zhao, Xiaoming

doi:10.1002/ejoc.201201640

Cited by 13 publications

(5 citation statements)

References 59 publications

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“…An enantioselective Ir-catalyzed allylation reaction using a thioate nucleophile to access allylic thiols 535 was developed by Gao and Zhao in 2013. 373 The reaction proceeded smoothly with KSAc, though only with moderate regioselectivity, likely to be due to partial transformation of the branched products to the more stable linear isomers (Scheme 277).…”

Section: Thiolates and Thioatesmentioning

confidence: 99%

Iridium-Catalyzed Asymmetric Allylic Substitution Reactions

et al. 2018

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In this review, we summarize the origin and advancements of iridiumcatalyzed asymmetric allylic substitution reactions during the past two decades. Since the first report in 1997, Ir-catalyzed asymmetric allylic substitution reactions have attracted intense attention due to their exceptionally high regio-and enantioselectivities. Ircatalyzed asymmetric allylic substitution reactions have been significantly developed in recent years in many respects, including ligand development, mechanistic understanding, substrate scope, and application in the synthesis of complex functional molecules. In this review, an explicit outline of ligands, mechanism, scope of nucleophiles, and applications is presented.

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Section: Thiolates and Thioatesmentioning

confidence: 99%

Iridium-Catalyzed Asymmetric Allylic Substitution Reactions

et al. 2018

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“…[11] With this concept in mind, we envisaged that an asymmetric catalytic reaction of o-QMs with sulfur nucleophiles would provide access to chiral a-aryl-or a-alkyl-substituted benzyl mercaptans (Scheme 1). [14] This reaction will supply aunique catalytic method for the enantioselective synthesis of both a-aryl-and a-alkyl-substituted benzyl mercaptans,a s sulfa-Michael additions, [15] sulfa-1,2 additions, [16] sulfa-allylations, [17] and the kinetic resolution of thiols [18] generally do not afford a-aryl-substituted benzyl mercaptans.W er eport herein the first conjugate addition of tritylthiol to in situ generated o-QMs catalyzed by achiral organic base with good to excellent enantioselectivities (91:9-97:3 e.r. [13] Currently,s uch thiol compounds are mainly accessible through O-S exchange using chiral benzyl alcohols as the starting materials.…”

Section: Ortho-quinone Methides (O-qms) Are Important Intermedi-mentioning

confidence: 99%

Formal Asymmetric Catalytic Thiolation with a Bifunctional Catalyst at a Water–Oil Interface: Synthesis of Benzyl Thiols

Guo

Zhou

et al. 2015

Angewandte Chemie

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The enantioselective conjugated addition of tritylthiol to in situ generated ortho-quinone methides (o-QMs) is catalyzedb ya na cid-base bifunctional squaramide organocatalyst. The transformation proceeds with high yield (up to 99 %) and stereoselectivity (up to 97:3 e.r.)u sing water as solvent under mild conditions.T he catalyst system provides an ew strategy for the synthesis of optically active benzyl mercaptans.C ontrol experiments suggested that o-QMs are generated by the tertiary amine moiety of the squaramide organocatalyst and that the water-oil biphase is crucial for achieving high reactivity and stereoselectivity.

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“…On account of the transformation involving direct displacement of the allylic alcohol, the iridium-catalyzed allylation exhibits a high degree of atom-economy. Recently, the scope of sulfur nucleophiles has been further expanded to include potassium thioacetate, 87 which is easily cleaved after the reaction to give the free thiol. This nucleophile gave access to allylic thioesters with high regio-and enantioselectivities.…”

Section: Scheme 47mentioning

confidence: 99%

Carbon-Sulfur Bond Formation via Metal-Catalyzed Allylations of Sulfur Nucleophiles

Liu

Zhao

2013

Synthesis

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The development of practical approaches for the construction of carbon-sulfur bonds is of interest to scientists. In particular, carbon-sulfur bond formation by transition-metal-catalyzed allylations has been attracting great attention. Allylic sulfides are important substances owing to their broad applications in synthetic and pharmaceutical areas. The alkene and sulfur moieties in allylic sulfides can lead to numerous transformations. This review details the development of carbon-sulfur bond formation through palladium-catalyzed rearrangements, palladium-catalyzed allylations, iridium-catalyzed regio-and enantioselective allylations and miscellaneous metal-catalyzed allylic substitutions. Carbon-selenium bond formations via metal-catalyzed allylic substitutions are also reviewed. 1 Introduction 2 Carbon-Sulfur Bond Formation via Palladium-Catalyzed Reactions 2.1 Rearrangements of Allylic Substrates 2.2 Allylations 2.3 Asymmetric Allylations 3 Carbon-Sulfur Bond Formation via Iridium-Catalyzed Regio-and Enantioselective Allylations 4 Carbon-Sulfur Bond Formation via Miscellaneous Metal-Catalyzed Reactions 4.1 Nickel 4.2 Ruthenium 4.3 Gallium 4.4 Iron 5 Carbon-Selenium Bond Formation via Metal-Catalyzed Allylic Substitutions 6 Conclusions

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Synthesis of Chiral Allylic Thioesters: Enantio‐ and Regioselective Iridium‐Catalyzed Allylations of KSAc

Abstract: Chiral allylic thioesters were synthesized through a direct iridium‐catalyzed asymmetric allylation of KSAc in the presence of KOAc. This strategy provided branched allylic thioesters in good yields with the high levels of enantioselectivity.

Cited by 13 publications

References 59 publications

Iridium-Catalyzed Asymmetric Allylic Substitution Reactions

Iridium-Catalyzed Asymmetric Allylic Substitution Reactions

Formal Asymmetric Catalytic Thiolation with a Bifunctional Catalyst at a Water–Oil Interface: Synthesis of Benzyl Thiols

Carbon-Sulfur Bond Formation via Metal-Catalyzed Allylations of Sulfur Nucleophiles

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