Total Synthesis of (−)‐Vindorosine

Chen, Wen; Yang, Xiaodong; Tan, Wen-Yun; Zhang, Xiangyang; Liao, Xiali; Zhang, Hongbin

doi:10.1002/ange.201707249

Cited by 18 publications

(7 citation statements)

References 64 publications

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“…The NMR spectra as well as physical data of our synthetic sample were consistent with those reported in the literature [3a] . With kopsaporine in hand, we next synthesized kopsinol by treatment of kopsaporine with sodium methoxide in methanol [23c] . The desired product was isolated in 77 % yield, and data of this compound are agreed well with that of natural kopsinol [3b] …”

Section: Resultssupporting

confidence: 85%

Total Syntheses of Kopsaporine, Kopsinol and Kopsiloscine A

Zhang

Tian

et al. 2023

Angewandte Chemie

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Kopsia alkaloids represent a complex class of natural products bearing a polycyclic ring system with two or three consecutive quaternary carbon centers. In this article, we report the first total synthesis of Kopsaporine related alkaloids. Features of our structure‐unit‐based strategy are an intramolecular Pummerer rearrangement induced nucleophilic cyclization/aza‐Prins cyclization to construct the highly functional hexahydrocarbazole skeleton, an olefin migration vinylogous alkylation to establish the C20 all‐carbon quaternary center, an iridium complex mediated radical addition to fuse the aspidofractine framework, an unprecedented IBX oxidation to introduce the α‐hydroxyketone moiety, and a bioinspired retro‐Aldol/Aldol reaction to convert kopsaporine to kopsiloscine A.

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Section: Resultssupporting

confidence: 85%

Total Syntheses of Kopsaporine, Kopsinol and Kopsiloscine A

Zhang

Tian

et al. 2023

Angewandte Chemie

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“…Since the first total synthesis of vindorosine reported by the Büchi group in 1971, 5 various efficient total syntheses have been reported including Kuehne's first asymmetric total synthesis in 1987. 6 Recently, the groups of Boger 7 and Zhang 8 reported their asymmetric total syntheses via tandem intermolecular Diels-Alder/1,3-dipolar cycloaddition of 1,3,4-oxadiazoles or intramolecular Heathcock/aza-Prins cyclization, respectively. However, to the best of our knowledge, the asymmetric syntheses reported to date have relied on chiral pool strategies or diastereoselective reactions with the use of chiral auxiliaries.…”

Section: Introductionmentioning

confidence: 99%

Construction of the Pyrrolo[2,3-d]carbazole Core of Spiroindoline Alkaloids by Gold-Catalyzed Cascade Cyclization of Ynamide

et al. 2019

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We achieved direct construction of the common pyrrolo [2,3-d]carbazole core of aspidosperma and malagasy alkaloids by a gold-catalyzed cascade cyclization of ynamide. This reaction involves intramolecular cyclization from indole to ynamide followed by trapping of the resulting iminium intermediate. Through the use of chiral gold complexes, an enantiomerically enriched pyrrolo[2,3-d]carbazole was obtained in up to 74% ee. This methodology was successfully applied to the asymmetric formal synthesis of vindorosine.

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“…Retrosynthetic analysis. As part of our ongoing program in seeking flexible and divergent synthetic strategies toward bioactive natural products and its analogues [57][58][59][60][61] , we recently disclosed a Lewis acid-mediated intramolecular Prins reaction of dioxinones to construct medium-sized carbocycles bearing oxabridged bicyclic structural units 62 . We envisioned that the Mannich-type-cyclization version of our previous protocol might lead to the highly functional 9-azabicyclo[3.3.1]nonane ring system (16, Fig.…”

Section: Resultsmentioning

confidence: 99%

Structure units oriented approach towards collective synthesis of sarpagine-ajmaline-koumine type alkaloids

Chen

et al. 2022

Nat Commun

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Sarpagine-Ajmaline-Koumine type monoterpenoid indole alkaloids represent a fascinating class of natural products with polycyclic and cage-like structures, interesting biological activities, and related biosynthetic origins. Herein we report a unified approach towards the asymmetric synthesis of these three types of alkaloids, leading to a collective synthesis of 14 natural alkaloids. Among them, akuammidine, 19-Z-akuammidine, vincamedine, vincarine, quebrachidine, vincamajine, alstiphylianine J, and dihydrokoumine are accomplished for the first time. Features of our synthesis are a new Mannich-type cyclization to construct the key indole-fused azabicyclo[3.3.1]nonane common intermediate, a SmI2 mediated coupling to fuse the aza-bridged E-ring, stereoselective olefinations to install either the 19-E or 19-Z terminal alkenes presented in the natural alkaloids, and an efficient iodo-induced cyclization to establish the two vicinal all-carbon quaternary centers in the Koumine-type alkaloids.

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Total Synthesis of (−)‐Vindorosine

Cited by 18 publications

References 64 publications

Total Syntheses of Kopsaporine, Kopsinol and Kopsiloscine A

Total Syntheses of Kopsaporine, Kopsinol and Kopsiloscine A

Construction of the Pyrrolo[2,3-d]carbazole Core of Spiroindoline Alkaloids by Gold-Catalyzed Cascade Cyclization of Ynamide

Structure units oriented approach towards collective synthesis of sarpagine-ajmaline-koumine type alkaloids

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