Recent Advances in Catalytic Asymmetric Decarboxylative Addition Reactions

Wang, Zu‐Li

doi:10.1002/adsc.201300375

Cited by 151 publications

(50 citation statements)

References 34 publications

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“…Higher selectivities (>90 % ee ) have, so far, only been achieved either in the presence of stoichiometric amounts of base or by employing transition metals, for example, palladium complexes or enzymes . Unlike the former examples, as well as decarboxylative addition reactions,, the DW reaction described herein is particularly challenging as it presupposes the stereoselective transfer of the smallest electrophile, a proton, in the presence of significant amounts of acid in a complex multistep reaction (Scheme ).…”

Section: Methodsmentioning

confidence: 99%

The Enantioselective Dakin–West Reaction

et al. 2016

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Here we report the development of the first enantioselective Dakin-West reaction, yielding a-acetamido methylketones with up to 58 %eewith good yields.T wo of the obtained products were recrystallized once to achieve up to 84 %ee. The employed methylimidazole-containing oligopeptides catalyze both the acetylation of the azlactone intermediate and the terminal enantioselective decarboxylative protonation. We propose ad ispersion-controlled reaction path that determines the asymmetric reprotonation of the intermediate enolate after the decarboxylation.Even though the Dakin-West (DW) reaction dates back to 1928, [1] it is still one of the most effective synthetic procedures to prepare a-acylamido ketones from primary a-amino acids.[2] Generally,t he treatment of an amino acid with an acid anhydride and base,t ypically pyridine,a te levated temperature provides the desired product upon liberation of CO 2 (Scheme 1). Numerous modifications of the original reaction conditions were developed, [2] including catalytic variants, [3] broadening its scope and applicability.U nsurprisingly,the DW reaction found application in the preparation of a-acylamido ketones as valuable precursors for various biologically active compounds, [4] and even in Woodwards fundamental total synthesis of strychnine.[5] Remarkably,n o asymmetric variant has been developed to date,thus restricting the use of this important reaction in modern synthetic chemistry.According to the currently accepted mechanism, [6] the reaction of an amino acid with the anhydride leads to the Nacetyl derivative 1 and subsequently to the mixed anhydride 2 (Scheme 2). Cyclization of 2 provides the oxazol-5(4H)-one (azlactone) 3.S uch azlactones are acidic owing to the formation of resonance stabilized enolate 4 upon deprotonation. Subsequent acetylation may occur at the enolate oxygen atom (affording 5)ordirectly at the carbon atom to give 6. [7] However, 6 is exclusively produced under the typical DW reaction conditions because of concomitant O!Cacyltransfer (Steglich rearrangement).[8] Opening of 6 with acetic acid, formed in previous steps,t ot he mixed anhydride 7 and transacylation gives the b-keto acid 8, [6f] which is prone to decarboxylation upon deprotonation. This final reaction step affords the desired a-acetamido methylketone 10,l ikely via enolate 9.Other pathways,for example,the acylationof2 to directly give 7, [9] were discussed as well but have been shown to be rather improbable.I ti se vident from this mechanistic picture that the intermediacyo f4 and 9 (Scheme 2) leads to the observed complete racemization, making an asymmetric reaction ad ifficult endeavor. We surmized, however, that an enantioselective decarboxylative protonation [10] of 8 (via 9) would afford enantioenriched products.Herein we show that this is indeed possible with at ailor-made catalytic system.We chose synthetic oligopeptides as catalysts [11] as these should be well-suited for binding the amino acid derived intermediates,a sd emonstrated for such platforms in acyl tra...

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Section: Methodsmentioning

confidence: 99%

The Enantioselective Dakin–West Reaction

et al. 2016

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“…Decarboxylative reactions constitute a traditional and very powerful tool in the contemporary synthetic chemistry. [1][2][3] This approach to organic transformations relies on the introduction of the carboxylic acid group into the starting material in order to enhance its nucleophilic or electrophilic property with the possibility to remove it from the target molecule at devised stage of a given synthetic route by the means of decarboxylation reaction. Notably, in a classical approach the corresponding ester is used as the precursor of carboxylic acid moiety.…”

Section: Introductionmentioning

confidence: 99%

Carboxylic‐Acid‐Activated Olefins in Decarboxylative Reactions

Bojanowski

Albrecht

2019

Asian J Org Chem

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This Minireview summarizes the application of carboxylic-acid-activated olefins in organic synthesis. The ability of carboxylic acid moiety to increase the electrophilic character of alkenes combined with the possibility to remove it under mild reaction conditions via decarboxylation process allows for the development of new reactivity patterns. These strategies involve mainly cascade reactions consisting of either Michael addition followed by decarboxylation or cycloaddition followed by decarboxylation. New synthetic possibilities provided by these approaches are summarized and discussed within this review article.[a] J.

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“…Formation of new C−C bonds by decarboxylative coupling process has become a powerful asset to the synthetic toolkit in academic and industrial researches. This synthetic approach provided simple method of coupling with various advantageous features such as the nontoxic by‐product (CO 2 ), regiospecific functionalization, straightforward bond formation, and in‐situ generation of nucleophilic partner . Consequently, the decarboxylative coupling has become a beneficial approach compared to other cross‐coupling reactions .…”

Section: Introductionmentioning

confidence: 99%

Green Decarboxylative Aminoalkylation of Coumarin‐3‐Carboxylic Acids

et al. 2019

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A new metal‐free decarboxylative coupling reaction between coumarin‐3‐carboxylic acid derivatives, formaldehyde, and amines is developed. The use of water as the solvent without using any catalyst or additive, excellent functional group tolerance, and good yields are the beneficial features of this synthetic pathway. The cholinesterase inhibitory activity of some selected target compounds is also evaluated.

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Recent Advances in Catalytic Asymmetric Decarboxylative Addition Reactions

Cited by 151 publications

References 34 publications

The Enantioselective Dakin–West Reaction

The Enantioselective Dakin–West Reaction

Carboxylic‐Acid‐Activated Olefins in Decarboxylative Reactions

Green Decarboxylative Aminoalkylation of Coumarin‐3‐Carboxylic Acids

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