Chiral Aldehyde–Palladium Catalysis Enables Asymmetric Synthesis of α-Alkyl Tryptophans via Cascade Heck-Alkylation Reaction

Shen, Qi-Wen; Wen, Wei; Guo, Qi‐Xiang

doi:10.1021/acs.orglett.3c01119

Cited by 13 publications

(8 citation statements)

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“…In the same year, Guo and his research team reported the pioneering aldehyde-combining palladium co-catalyzed asymmetric cascade Heck-alkylation reaction between N-(2-Iodophenyl)allenamides 112 and NH 2 -unprotected amino acid esters 107 (as illustrated in Scheme 36). [95] The model reaction product 113 a was obtained in outstanding yields and enantioselectivities. Notably, chiral γ-lactam 113 b and chiral 1,2dihydroquinoline 113 d products were generated with good yields and excellent enantioselectivities.…”

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

confidence: 99%

“…[80] In 2018, Yu and colleagues introduced two novel transient directing groups that exhibit selectivity towards γ-methylene and δ-methyl C(sp 3 )À H bonds, even in the presence of other reactive CÀ H bonds. They successfully achieved palladiumcatalyzed γ-methylene-C(sp 3 )À H heteroarylation and δ-C(sp 3 )À H arylation reactions using simple aliphatic amines (94) and iodoarenes (95) or aryl bromide (95') as coupling partners. These reactions relied on the cooperative combination of the newly developed transient directing groups C-26/C-28 and the ligand pyridine L1.…”

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

confidence: 99%

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

confidence: 99%

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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“…Under the promotion of a combined catalytic system comprising chiral aldehyde A2k , chiral palladium complex, and ZnCl 2 , the cascade Heck-alkylation reaction of amino acid esters with N -(2-iodophenyl)allenamides 47 proceeded smoothly (Scheme ). The reaction was proposed to proceed via a palladium-catalyzed intramolecular addition of the C–I bond to allene, generating a π-allyl-palladium complex from 47 , followed by an enantioselective nucleophilic addition with the chiral aldehyde-activated amino acid esters to give the optically active α- quaternary tryptophans . Notably, chiral 1,2-dihydroquinoline 48g was also generated with the utilization of tert -butyl buta-2,3-dien-1-yl(2-iodophenyl)carbamate 47g as a reactant.…”

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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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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“…Diverse nucleophiles were applied to undergo the subsequent allylic substitution reaction, offering different opportunities for the difunctionalization of allenamides. 7 Representatively, dicarbofunctionalization processes were reported by Sato's, 8 Lin's, 9 Guo's, 10 Hoarau's, 11 Guo's, 12 and other groups, 13 using different carbon nucleophiles. For example, in 2018, Hoarau and co-workers reported a palladium-catalysed construction of isoquinolone-azole bisheterocyclic scaffolds through a C–H allylation reaction (Scheme 1b).…”

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confidence: 99%