Enantioselective Total Synthesis of (+)-Sieboldine A

El-Gaber, Mohammed K. Abd; Yasuda, Shigeo; Iida, Eisuke; Mukai, Chisato

doi:10.1021/acs.orglett.6b03416

Cited by 19 publications

(9 citation statements)

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“…An ultimate challenge in synthesis is the development of methods to prepare enantioenriched compounds. α-Acyloxy and α-hydroxy cyclopentenones, and their corresponding redox derivatives, appear in numerous natural products, but enantioselective access to these functional group arrays is limited. α-Oxygenated ketones are typically prepared via the installation of a hydroxyl group adjacent to an existing carbonyl .…”

Section: Introductionmentioning

confidence: 99%

Computationally Guided Catalyst Design in the Type I Dynamic Kinetic Asymmetric Pauson–Khand Reaction of Allenyl Acetates

et al. 2017

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The Rh(I)-catalyzed allenic Pauson-Khand reaction (APKR) is an efficient, redox-neutral method of synthesizing α-acyloxy cyclopentenones. An enantioselective APKR could provide access to chiral, nonracemic α-acyloxy and α-hydroxy cyclopentenones and their corresponding redox derivatives, such as thapsigargin, a cytotoxic natural product with potent antitumor activity. Rapid scrambling of axial chirality of allenyl acetates in the presence of Rh(I) catalysts enables the conversion of racemic allene to enantiopure cyclopentenone product in a dynamic kinetic asymmetric transformation (DyKAT). A combined experimental and computational approach was taken to develop an effective catalytic system to achieve the asymmetric transformation. The optimization of the denticity, and steric and electronic properties of the ancillary ligand (initially (S)-MonoPhos, 58:42 er), afforded a hemilabile bidentate (S)-MonoPhos-alkene-Rh(I) catalyst that provided α-acyloxy cyclopentenone product in up to 14:86 er. Enantioselectivity of the Rh(I)-(S)-MonoPhos-alkene catalyst was rationalized using ligand-substrate steric interactions and distortion energies in the computed transition states. This asymmetric APKR of allenyl acetates is a rare example of a Type I DyKAT reaction of an allene, the first example of DyKAT in a cyclocarbonylation reaction, and the first catalyst-controlled enantioselective APKR.

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Section: Introductionmentioning

confidence: 99%

Computationally Guided Catalyst Design in the Type I Dynamic Kinetic Asymmetric Pauson–Khand Reaction of Allenyl Acetates

et al. 2017

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“…Finally, in 2017, Mukai group reported their synthesis of (+)‐ 2 (Scheme c) . The Mukai synthesis relied again on an intramolecular Pauson‐Khand reaction to generate the indenone core ( 80 ).…”

Section: Fawcettimine Alkaloids With Level 1 Oxidation State At C16mentioning

confidence: 99%

Fawcettimine‐Type Lycopodium Alkaloids as a Driving Force for Discoveries in Organic Synthesis

Lei

2017

The Chemical Record

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Ever since the pioneering synthetic work reported by both Inubushi and Heathcock back in 1980s, the fawcettimine-type Lycopodium alkaloids have continuously served as a driving force for discoveries in organic synthesis. In this personal account, we summarized our recent synthetic efforts towards the total synthesis of fawcettimine-type Lycopodium alkaloids, along with a brief summary of relevant syntheses reported by others. Our discussions focus mainly on the key reactions applied during the synthesis of fawcettimine-type Lycopodium alkaloids.

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“…Due to its appealing structural complexities and potential biological properties, 1 has received prolonged research interest in its synthesis. To date, three successful strategies have been reported to achieve the total synthesis of 1 , including a late-stage biomimetic oxidation protocol developed by our group. , Despite the precedence, the intricate molecular structure still inspires innovations on novel synthetic approaches.…”

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confidence: 99%

Total Synthesis of Sieboldine A

et al. 2020

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Previously, we have finished the total synthesis of lycojaponicumin A (2) via development of an efficient synthetic strategy using semipinacol rearrangement as a key step. In order to further demonstrate the generality of this synthetic route, herein, we report the total synthesis of another fawcettimine-type alkaloid sieboldine A (1) from the same intermediate, which possesses an A/B/D tricyclic ring system and vicinal quaternary centers of 1. The synthesis features late-stage site-selective redox reactions, Schmidt glycosylation cyclization, and highly selective transformations.

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Enantioselective Total Synthesis of (+)-Sieboldine A

Cited by 19 publications

References 50 publications

Computationally Guided Catalyst Design in the Type I Dynamic Kinetic Asymmetric Pauson–Khand Reaction of Allenyl Acetates

Computationally Guided Catalyst Design in the Type I Dynamic Kinetic Asymmetric Pauson–Khand Reaction of Allenyl Acetates

Fawcettimine‐Type Lycopodium Alkaloids as a Driving Force for Discoveries in Organic Synthesis

Total Synthesis of Sieboldine A

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