Direct enantioselective α-amination of amides guided by DFT prediction of E/Z selectivity in a sulfonium intermediate

Feng, Minghao; Fernandes, Anthony J.; Meyrelles, Ricardo; Maulide, Nuno

doi:10.1016/j.chempr.2023.03.002

Cited by 16 publications

(5 citation statements)

References 47 publications

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“…The requirement of the first method for a highly electrophilic ketene and the disadvantages associated with the inevitable presence of two chlorine atoms in the lactone products led us to ponder whether a broader methodology could emerge if transiently generated keteniminium ions were employed instead. Readily formed by electrophilic activation of tertiary amides, [17,18] these electrophiles have been found to be ideal reagents for a range of chemo‐ and stereoselective bond‐forming domino processes [19–21] …”

Section: Methodsmentioning

confidence: 99%

Sulfonium Rearrangements Enable the Direct Preparation of Sulfenyl Imidinium Salts

Gonçalves,

Klose,

Placidi

et al. 2024

Angewandte Chemie

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Sulfenyl imidinium salts are a virtually unexplored class of intermediates in organic chemistry. Herein, we demonstrate how sulfonium rearrangements can be deployed to access these versatile synthetic intermediates, bearing three contiguous (and congested) stereogenic centers, with high levels of selectivity. The synthetic value of the scaffold was unraveled by selective transformations into a range of building blocks, including 1,4‐dicarbonyl derivatives and sulfonolactones.

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Section: Methodsmentioning

confidence: 99%

Sulfonium Rearrangements Enable the Direct Preparation of Sulfenyl Imidinium Salts

Gonçalves,

Klose,

Placidi

et al. 2024

Angewandte Chemie

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“…Maulide et al recently reported the application of chiral and racemic sulfinamides in α-amination of carbonyl compounds. 96 These studies notably describe a formal umpolung of the alpha position into a carbonyl. Typically, due to the known acidity of protons in the alpha position, enolates are formed, followed by a reaction with electrophilic species.…”

Section: Sulfur-based Surrogatesmentioning

confidence: 99%

Ammonia surrogates in the synthesis of primary amines

Urbiña-Alvarez,

Rincón-Carvajal,

Gamba-Sánchez

2023

Org. Biomol. Chem.

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“…[40] The direct enantioselective α-amination of unfunctionalized carbonyl compounds remains a synthetic challenge. In 2023, the Maulide group [41] reported the development of a metal-free method for the direct enantioselective amination of amides (Scheme 18). This innovative approach utilizes readily available sulfinamides as nitrogen sources and chiral auxiliaries, enabling the formation of a new CÀ N bond through a selective rearrangement known as the sulfonium [2,3]-rearrangement.…”

Section: Umpolung Of the C2 Position Of Amidesmentioning

confidence: 99%

Reactivity Umpolung of Amides in Organic Synthesis

Shi,

Liu

2023

Asian J Org Chem

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Amides are important carboxylic acid derivatives, having wide applications in chemistry, biochemistry, and materials sciences. Due to the conjugation (nN‐π*C=O), the carbonyl group of amides is the least electrophilic and the a C‐H bond of amides is the least acidic among the carbonyl derivatives, thereby making it challenging to develop highly efficient and selective transformations based on amides. Reactivity umpolung refers to the reversion of polarity of a functional group. The idea of inverting the innate polarity of organic functional groups, initially introduced by Wittig and later popularized by Seebach, marks a pivotal conceptual breakthrough in organic synthesis. In contrast to the progress for the umpolung of aldehyde, the umpolung of amides has proved challenging and only recently made notable progress. Following the elegant design, the C1 of the amide can become nucleophilic, and the C2 can be electrophilic. In this review, we attempt to summarize the reported examples that are broadly categorized as reactivity umpolung of amides. This review is organized by the umpolung of C1 and C2 of amide functional groups.

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Direct enantioselective α-amination of amides guided by DFT prediction of E/Z selectivity in a sulfonium intermediate

Cited by 16 publications

References 47 publications

Sulfonium Rearrangements Enable the Direct Preparation of Sulfenyl Imidinium Salts

Sulfonium Rearrangements Enable the Direct Preparation of Sulfenyl Imidinium Salts

Ammonia surrogates in the synthesis of primary amines

Reactivity Umpolung of Amides in Organic Synthesis

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