Organocatalytic asymmetric aldol reaction using protonated chiral 1,2-diamines

Shim, Jooyong; Kim, Min Joon; Lee, Ji Yeon; Kim, Kyoung Hoon; Ha, Deok Chan

doi:10.1016/j.tetlet.2020.152295

Cited by 13 publications

(13 citation statements)

References 49 publications

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“…In addition, the interfacial reaction mechanism of the DPEN-based catalyst and the factors that increase the catalytic reactivity were confirmed through quantum calculations under the reaction conditions without the acid additive used in the previous study. The study on the reaction mechanism according to the type of configurational diastereomers [37] and the reactivity of each solvent was verified through quantum calculation. In addition, the effect of the fluorine substituent on the organic catalyst 1b confirmed in the previous study was confirmed in more depth [33,34].…”

Section: Introductionmentioning

confidence: 99%

Organocatalysis for the Asymmetric Michael Addition of Aldehydes and α,β-Unsaturated Nitroalkenes

et al. 2022

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Michael addition is an important reaction because it can be used to synthesize a wide range of natural products or complex compounds that exhibit biological activities. In this study, a mirror image of an aldehyde and α,β-unsaturated nitroalkene were reacted in the presence of (R,R)-1,2-diphenylethylenediamine (DPEN). Herein, thiourea was introduced as an organic catalyst, and a selective Michael addition reaction was carried out. The primary amine moiety of DPEN reacts with aldehydes to form enamines, which is activated by the hydrogen bond formation between the nitro groups of α,β-unsaturated nitroalkenes and thiourea. Our aim was to obtain an asymmetric Michael product by adding 1,4-enamine to an alkene to form a new carbon–carbon bond. As a result, the primary amine of the chiral diamine was converted to an enamine. The reaction proceeded with a relatively high degree of enantioselectivity, which was achieved using double activation via hydrogen bonding of the nitro group and thiourea. Michael products with a high degree of enantioselectivity (97–99% synee) and diastereoselectivity (syn/anti = 9/1) were obtained in yields ranging from 94–99% depending on the aldehydes.

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Section: Introductionmentioning

confidence: 99%

Organocatalysis for the Asymmetric Michael Addition of Aldehydes and α,β-Unsaturated Nitroalkenes

et al. 2022

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“…Several enantioselective Michael reactions using organic catalysts are known. Among them, the proline-catalyzed reactions studied by Seebach and Blarer in 1981 have received significant attention, and many related studies have been conducted since [2][3][4][5][6][7][8][9][10]. Seebach and Blarer reported the Michael reaction of an α, β-unsaturated nitroalkene using a chiral proline derivative [11,12].…”

Section: Introductionmentioning

confidence: 99%

“…Although it was previously assumed that reactions using proline derivatives are limited, many previous studies have reported Michael reactions that use proline derivatives as a basic structure. Moreover, N-monoalkylated thiourea catalysts based on the basic chiral skeleton of (R, R)-1,2-diphenylethylenediamine (DPEN) can be applied to various reactions, such as the Diels-Alder reaction, Aldol reaction, and Michael reaction, with relatively good yields [9,10,39].…”

Section: Introductionmentioning

confidence: 99%

Organocatalysis for the Asymmetric Michael Addition of Cycloketones and α, β-Unsaturated Nitroalkenes

et al. 2021

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Michael addition is one of the most important carbon–carbon bond formation reactions. In this study, an (R, R)-1,2-diphenylethylenediamine (DPEN)-based thiourea organocatalyst was applied to the asymmetric Michael addition of nitroalkenes and cycloketones to produce a chiral product. The primary amine moiety in DPEN reacts with the ketone to form an enamine and is activated through the hydrogen bond formation between the nitro group in the α, β-unsaturated nitroalkene and thiourea. Here, the aim was to obtain an asymmetric Michael product through the 1,4-addition of the enamine to an alkene to form a new carbon–carbon bond. As a result, the primary amine of the chiral diamine was converted into an enamine. The reaction proceeded with a relatively high level of enantioselectivity achieved using double activation through the hydrogen bonding of the nitro group and thiourea. Michael products with high levels of enantioselectivity (76–99% syn ee) and diastereoselectivity (syn/anti = 9/1) were obtained with yields in the range of 88–99% depending on the ketone.

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Section: Introductionmentioning

confidence: 99%

“…Although it was previously assumed that reactions using proline derivatives are limited, many previous studies have reported Michael reactions that use proline derivatives as a basic structure. Moreover, Nmonoalkylated thiourea catalysts based on the basic chiral skeleton of (R, R)-1,2-diphenylethylenediamine (DPEN) can be applied to various reactions, such as the Diels-Alder reaction, Aldol reaction, and Michael reaction, with relatively good yields [9,10,39]. www.videleaf.com In this study, the asymmetric Michael reaction was applied to a cycloketone using (R, R)-1,2-diphenylethylenediamine (DPEN) as a catalyst.…”

Section: Introductionmentioning

confidence: 99%

Organocatalysis for the Asymmetric Michael Addition of Cycloketones and α, β-Unsaturated Nitroalkenes

Shim¹,

Ahn²,

Lee³

et al. 2021

Prime Archives in Chemistry

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Michael addition is one of the most important carbon-carbon bond formation reactions. In this study, an (R, R)-1,2diphenylethylenediamine (DPEN)-based thiourea organocatalyst was applied to the asymmetric Michael addition of nitroalkenes and cycloketones to produce a chiral product. The primary amine moiety in DPEN reacts with the ketone to form an enamine and is activated through the hydrogen bond formation between the nitro group in the α, βunsaturated nitroalkene and thiourea. Here, the aim was to

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Organocatalytic asymmetric aldol reaction using protonated chiral 1,2-diamines

Cited by 13 publications

References 49 publications

Organocatalysis for the Asymmetric Michael Addition of Aldehydes and α,β-Unsaturated Nitroalkenes

Organocatalysis for the Asymmetric Michael Addition of Aldehydes and α,β-Unsaturated Nitroalkenes

Organocatalysis for the Asymmetric Michael Addition of Cycloketones and α, β-Unsaturated Nitroalkenes

Organocatalysis for the Asymmetric Michael Addition of Cycloketones and α, β-Unsaturated Nitroalkenes

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