Enantioselective Synthesis of 3a‐Amino‐Pyrroloindolines by Copper‐Catalyzed Direct Asymmetric Dearomative Amination of Tryptamines

Liu, Chuan; Yi, Jiawei; Zheng, Zhong‐Bo; Tang, Yong; Dai, Li‐Xin; You, Shu‐Li

doi:10.1002/anie.201508570

Cited by 105 publications

(40 citation statements)

References 71 publications

(4 reference statements)

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“…36,37 Using the mesolytic cleavage conditions described above with ortho- iodoaniline as the nucleophile resulted in formation of expected N -aryl pyrroloindoline 22 in 64% yield. Adopting a strategy originally developed by Baran in his synthesis of psychotriasine, the iodoaniline was subjected to a Larock annulation with alkyne 30 to furnish the core of the natural product.…”

Section: Resultsmentioning

confidence: 99%

Enantioselective Synthesis of Pyrroloindolines via Noncovalent Stabilization of Indole Radical Cations and Applications to the Synthesis of Alkaloid Natural Products

et al. 2018

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While interest in the synthetic chemistry of radical cations continues to grow, controlling enantioselectivity in the reactions of these intermediates remains a challenge. Based on recent insights into the oxidation of tryptophan in enzymatic systems, we report a photocatalytic method for the generation of indole radical cations as hydrogen-bonded adducts with chiral phosphate anions. These non-covalent open-shell complexes can be intercepted by the stable nitroxyl radical TEMPO• to form alkoxyamine-substituted pyrroloindolines with high levels of enantioselectivity. Further elaboration of these optically-enriched adducts can be achieved via a catalytic single-electron oxidation/mesolytic cleavage sequence to furnish transient carbocation intermediates that may be intercepted by a wide range of nucleophiles. Taken together, this two-step sequence provides a simple catalytic method to access a wide range of substituted pyrroloindolines in enantioenriched form via a standard experimental protocol from a common synthetic intermediate. The design, development, mechanistic study, and scope of this process are presented, as are applications of this method to the synthesis of several dimeric pyrroloindoline natural products.

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Section: Resultsmentioning

confidence: 99%

Enantioselective Synthesis of Pyrroloindolines via Noncovalent Stabilization of Indole Radical Cations and Applications to the Synthesis of Alkaloid Natural Products

et al. 2018

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“…97 A chiral Cu-based catalyst supported by an amino-indanolderived BOX ligand was used in this reaction, and the steric bulkiness at the metaposition of the two phenyl groups of the ligand was found to be crucial for achieving a high level of enantioselectivity. A newly synthesized chiral BOX ligand L27 bearing i Pr groups at the meta-positions was the best.…”

Section: Cada Reactions Via Formation Of Carbon-heteroatom Bondsmentioning

confidence: 99%

“…Aromatic compoundsScheme 30. Rh-or Cu-Catalyzed Aminative Dearomatization of IndolesOriginally reported by the Lai, Zhu, and Xie group 96 and the Tang and You group 97. Scheme 31.…”

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confidence: 99%

Catalytic Asymmetric Dearomatization by Transition-Metal Catalysis: A Method for Transformations of Aromatic Compounds

Zheng

You

2016

Chem

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481

105

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Catalytic asymmetric dearomatization (CADA) reactions refer to those reactions converting aromatic compounds into enantio-enriched three-dimensional cyclic molecules in a catalytic fashion. In the past, this area has seen significant progress since a series of valuable strategies for asymmetric catalysis were successfully applied. In this review, we provide insightful discussions on recent representative examples of asymmetric dearomatization reactions catalyzed by transition-metal complexes. Close attention is paid to the mechanism, scope, limitations, and the future direction of CADA reactions.

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“…B. die Verwendung der Ylidchemie in der organischen Synthese und die asymmetrische Katalyse, und von Olefinpolymerisationskatalysatoren. In der Angewandten Chemie hat er die enantioselektive Synthese von 3a‐Aminopyrroloindolinen vorgestellt …”

Section: Gewählt …unclassified

Neue Mitglieder der Chinesischen Akademie der Wissenschaften

2016

Angewandte Chemie

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Enantioselective Synthesis of 3a‐Amino‐Pyrroloindolines by Copper‐Catalyzed Direct Asymmetric Dearomative Amination of Tryptamines

Cited by 105 publications

References 71 publications

Enantioselective Synthesis of Pyrroloindolines via Noncovalent Stabilization of Indole Radical Cations and Applications to the Synthesis of Alkaloid Natural Products

Enantioselective Synthesis of Pyrroloindolines via Noncovalent Stabilization of Indole Radical Cations and Applications to the Synthesis of Alkaloid Natural Products

Catalytic Asymmetric Dearomatization by Transition-Metal Catalysis: A Method for Transformations of Aromatic Compounds

Neue Mitglieder der Chinesischen Akademie der Wissenschaften

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