Modular Chiral-Aldehyde/Palladium Catalysis Enables Atom-Economical α-Allylation of N-Unprotected Amino Acid Esters with 1,3-Dienes and Allenes

Liu, Jianhua; Zhou, Qing; Lin, Yao; Wu, Zhu-Lian; Cai, Tian; Wen, Wei; Huang, Yanmin; Guo, Qi‐Xiang

doi:10.1021/acscatal.3c00790

Cited by 20 publications

(6 citation statements)

References 73 publications

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“…1,3-Dienes and allenes can form π-metal-allyl species by the migratory insertion of a metal hydride, − which then undergoes attack by nucleophiles, providing an atom-economic approach to the synthesis of allylic compounds. − Recently, we accomplished a highly enantioselective α-allylation of amino acid esters with 1,3-dienes by exploiting the cooperative catalysis of chiral aldehyde/palladium/ZnCl 2 (Scheme a) . AcOH was added and reacted with a Pd(0) to generate Pd–H species.…”

Section: Cooperative Catalysis Of Chiral Aldehydes and Transition Met...mentioning

confidence: 99%

“…Prompted by the aforementioned work, we have also accomplished the enantioselective α-allylation of amino acid esters with allenes (Scheme b) . The screening of conditions showed that the combination of chiral aldehyde ( R )- A2k and chiral ligand ( R )- L2 could enable optimal results in terms of yield and enantioselectivity.…”

Section: Cooperative Catalysis Of Chiral Aldehydes and Transition Met...mentioning

confidence: 99%

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Chiral Aldehyde Catalysis-Enabled Asymmetric α-Functionalization of Activated Primary Amines

Wen,

Guo

2024

Acc. Chem. Res.

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Metrics & MoreArticle Recommendations CONSPECTUS:The development of catalytic activation modes provides a reliable and effective platform for designing new enantioselective reactions and preparing chiral molecules with diverse structures. Chiral aldehyde catalysis is an attractive concept in asymmetric catalysis, which utilizes a chiral aldehyde catalyst to promote the asymmetric hydroamination of allylic amines, the asymmetric α-functionalization of primary amines, or the asymmetric transamination of α-keto esters. Typically, the chiral aldehyde-catalyzed asymmetric α-functionalization of primary amines provides an efficient and straightforward method for the synthesis of α-functionalized chiral amines, which does not require any additional protection or deprotection manipulations of the amine group. However, achieving catalytic stereoselective transformations with high efficiency and enantioselectivity by this strategy has remained an intractable challenge. This Account summarizes our endeavors in the development and application of chiral aldehyde catalysis. Using a chiral aldehyde as a catalyst, we reported the catalytic asymmetric α-C alkylation of 2-aminomalonate with 3-indolylmethanol in 2014, which represents the first chiral aldehyde-catalyzed asymmetric α-functionalization of an activated primary amine. Subsequently, several axially chiral aldehyde catalysts were continuously prepared by using chiral BINOL as the starting material, and their applications in asymmetric synthesis were explored. On the one hand, they were used as organocatalysts to realize the various transformations of α-amino acid esters, such as asymmetric 1,4-addition toward conjugated enones/α,β-unsaturated diesters and cyclic 1-azadienes as well as asymmetric α-arylation/allylation and benzylation with corresponding halohydrocarbons. Notably, taking advantage of the difference in the distribution of catalytic sites between two chiral aldehyde catalysts, we disclosed chiral aldehyde-catalyzed diastereodivergent 1,6-conjugated addition and Mannich reactions. On the other hand, the potential for the cooperative catalysis of a chiral aldehyde with a transition metal has also been demonstrated. Enabled by the combination of a chiral aldehyde, a palladium complex, and a Lewis acid, the enantioselective α-allylation of amino acid esters with allyl alcohol esters was established. Moreover, the ternary catalytic system has been successfully used for the α-functionalization of amino acid esters with 1,3-dienes, allenes, allenylic alcohol esters, 1,3-disubstituted allyl alcohol esters, and arylmethanol esters as well as the asymmetric cascade Heck-alkylation reaction. The combination of a chiral aldehyde and nickel complex allows for the asymmetric α-propargylation of amino acid esters with propargylic alcohol esters and provides excellent enantioselectivities. These transformations provide a large library of optically active amines and amino acids. With those chiral amino acid esters as key building blocks, the synthesis or formal synthesis of ...

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Section: Cooperative Catalysis Of Chiral Aldehydes and Transition Met...mentioning

confidence: 99%

Section: Cooperative Catalysis Of Chiral Aldehydes and Transition Met...mentioning

confidence: 99%

Chiral Aldehyde Catalysis-Enabled Asymmetric α-Functionalization of Activated Primary Amines

Wen,

Guo

2024

Acc. Chem. Res.

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“…In 2023, Guo and his research team successfully achieved asymmetric α-allylation of N-free amino acid esters 107 with 1,3-diene 108 and allenes 110 through a co-catalytic system containing chiral aldehydes and the transition metal palladium (Scheme 35). [92] On one hand, when L5 was employed as the ligand and 1,3dienes 108 were utilized as the substrates, an exploration of the substrate scope for the asymmetric allylation of N-unprotected amino acid esters 107 with 1,3-dienes 108 was conducted (as shown in Scheme 35a). A diverse range of substituted 1,3dienes 109 a proved effective as allylation reagents.…”

Section: The Usage Of the Aldehyde/transition Metal Combining Catalyt...mentioning

confidence: 99%

The Development of Aldehyde Catalytic System

Chen,

Yang,

Huang

et al. 2023

Chemistry An Asian Journal

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Aldehyde catalysts have proven to be highly effective in facilitating and accelerating a wide range of challenging transformations in organic chemistry. This article is structured into three main sections, focusing on the utilization of aldehydes as organocatalysts, the aldehydes/transition metals catalytic systems, and photochemical initiators. Finally, we provide a concise summary of the advancements in this fascinating research field, offering our perspectives and insights.

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“…2 On the basis of their catalytic systems, these strategies can be categorized as PTC-catalyzed allylic alkylation, 3 metal-catalyzed allylic alkylation, 4 dual metal-cocatalyzed allylic alkylation, 5 organocatalyst-catalyzed allylic alkylation, 6 and organocatalyst and metal-cocatalyzed allylic alkylation. 7 However, these reactions are limited to the preparation of chiral disubstituted allylic amino acid scaffolds with the E -configuration. To the best of our knowledge, methods using palladium catalysts for the construction of functionalized chiral allylic amino acids with the ( Z )-configuration are still scarce and underdeveloped.…”

Section: Introductionmentioning

confidence: 99%

Palladium-catalyzed regio- and stereoselective allylic alkylation of 5-vinyloxazolidine-2,4-diones with azlactones: synthesis of chiral (Z)-trisubstituted allylic amino acid derivatives

Li,

Wang,

Zhen

et al. 2023

Org. Chem. Front.

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Modular Chiral-Aldehyde/Palladium Catalysis Enables Atom-Economical α-Allylation of N-Unprotected Amino Acid Esters with 1,3-Dienes and Allenes

Cited by 20 publications

References 73 publications

Chiral Aldehyde Catalysis-Enabled Asymmetric α-Functionalization of Activated Primary Amines

Chiral Aldehyde Catalysis-Enabled Asymmetric α-Functionalization of Activated Primary Amines

The Development of Aldehyde Catalytic System

Palladium-catalyzed regio- and stereoselective allylic alkylation of 5-vinyloxazolidine-2,4-diones with azlactones: synthesis of chiral (Z)-trisubstituted allylic amino acid derivatives

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