Development of Asymmetric Deacylative Allylation

Grenning, Alexander J.; Allen, Christie K. Van; Maji, Tapan; Lang, Simon B.; Tunge, Jon A.

doi:10.1021/jo400793a

Cited by 39 publications

(22 citation statements)

References 44 publications

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“…Asymmetric deacylative allylation of cyclic ketone enolates with allylic alcohols has been described by Tunge et al Racemic studies with tetralones, substituted at the α‐position by an acetyl group, demonstrated to be better substrates than propanoyl or formyl derivatives for the DaA with different allylic alcohols working with NaH in THF at room temp. (Scheme ).…”

Section: Deacylative Alkylationmentioning

confidence: 97%

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Deacylative Reactions: Synthetic Applications

et al. 2018

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Herein we introduce the recent developments of a new strategy based on deacylative alkylation (DaA) reactions for the generation of quaternary stereocenters based on the in situ preparation and functionalization of enolates under very mild reaction conditions. Palladium‐catalyzed deacylative allylation and benzylation reactions of carbon nucleophiles are performed with the corresponding alcohols. This methodology has been applied to the synthesis of the calcium ion channel blocker verapamil, the antiviral (+)‐hamigeran B, several oxindole precursors of esermethole, horsfiline, physostigmine, phenserine, meso‐folicanthine, meso‐chinonanthine and the dimer cyclotriptamine alkaloids. Base‐promoted deacylative reactions enable the functionalization of 2‐oxindole enolates at the 3‐position with alkyl halides and electrophilic alkenes. In the presence of oxygen or air, 3‐hydroxy‐2‐oxindoles are prepared by deacylative oxidation. Detrifluoroacylative reactions are promoted by a base generating fluoroenolates, which can participate in aldol, Mannich and Michael reactions for the preparation of important fluorinated intermediates. Finally, palladium‐catalyzed deacylative cross‐coupling of acetyl diazoacetates and phosphonates with aryl iodides let to the formation of aryl diazoacetates and phosphonates, respectively. The same process, with 2‐iodoazoarenes and 2‐iodoaryltriazenes, gives 2H‐indazoles, which are important pharmacophores.

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Section: Deacylative Alkylationmentioning

confidence: 97%

“…For the asymmetric version of this DaA, different chiral PHOX ligands were assayed . Ligands L1 and L2 gave the best enantioselectivities affording highly enantioenriched α,α‐diallylated tetralones (Scheme ).…”

Section: Deacylative Alkylationmentioning

confidence: 99%

Deacylative Reactions: Synthetic Applications

et al. 2018

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“…Two years later, Tunge et al reported an enantioselective protocol for the allylic alkylation of 1,3-diketones derived from tetralone (Scheme 82). [122] They made use of the PHOX-ligands L6a and L6b, which resulted in acceptable enantiomeric excesses in the allylation products.…”

Section: Allylic Alkylations Of Enolates Formed In 14-additionsmentioning

confidence: 99%

The Allylic Alkylation of Ketone Enolates

Junk

Kazmaier

2020

ChemistryOpen

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The palladium‐catalyzed allylic alkylation of non‐stabilized ketone enolates was thought for a long time to be not as efficient as the analogous reactions of stabilized enolates, e. g. of malonates and β‐ketoesters. The field has experienced a rapid development during the last two decades, with a range of new, highly efficient protocols evolved. In this review, the early developments as well as current methods and applications of palladium‐catalyzed ketone enolate allylations will be discussed.

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“…27 In 2013, the same group developed the first enantioselective variant of this approach involving the condensation of -diketones 57 with allylic alcohols 58 (Scheme 21). 28 The process is initiated by the addition of the sodium alcoholate to the -diketone 57 liberating a reactive enolate 61 and an allylic acetate 62 (Scheme 21). This allylic acetate is able to undergo activation by the palladium complex generating the required -allyl complex necessary for the eno-late trapping.…”

Section: Short Review Syn Thesismentioning

confidence: 99%

Acyl Transfer Strategies as Transient Activations for Enantioselective Synthesis

Rodríguez¹,

Quintard

2019

Synthesis

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In order to circumvent reactivity or selectivity issues associated with the addition of enolates to electrophiles, chemists have devised innovative methods involving transient activating groups. One of these powerful methods consists of the use of activated ketones, such as α-nitroketones, β-dicarbonyl compounds or β-ketosulfones, with electrophiles possessing a latent hydroxy or amine function. In the presence of a suitable catalyst, an enantioselective addition to the electrophile is facilitated triggering a subsequent Claisen-type fragmentation resulting in an acyl transfer. This subsequent step unveils the desired mono-activated function while directly transferring the ketone, forming in situ on the other side an ester or an amide.1 Introduction2 Intramolecular Acyl Transfer with Acyclic Substrates2.1 Bifunctional Catalysis2.2 Aminocatalysis3 Intermolecular Acyl Transfer with Acyclic Substrates4 Medium-Sized-Ring Formation with Cyclic Substrates5 Conclusion

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Development of Asymmetric Deacylative Allylation

Cited by 39 publications

References 44 publications

Deacylative Reactions: Synthetic Applications

Deacylative Reactions: Synthetic Applications

The Allylic Alkylation of Ketone Enolates

Acyl Transfer Strategies as Transient Activations for Enantioselective Synthesis

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