Total Synthesis of (−)‐Daphenylline

Yamada, R.; Adachi, Yoshinori; Yokoshima, Satoshi; Fukuyama, Tohru

doi:10.1002/anie.201601958

Cited by 96 publications

(77 citation statements)

References 44 publications

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“…Daphenylline ( 12 ), one of the notable Daphniphyllum alkaloids isolated from the fruit of D. longeracemosum by Hao and co‐workers in 2009, is the first member of the Daphniphyllum alkaloids containing a benzene ring in the core structure. Recently, the groups of Li,, Fukuyama, and Zhai have accomplished the total synthesis of this synthetically challenging cage‐like structure (Figure ). Herein, we wish to disclose a concise stereoselective total synthesis of (−)‐daphenylline starting from ( S )‐carvone.…”

Section: Figurementioning

confidence: 99%

Total Synthesis of (−)‐Daphenylline

Wang

Xun

et al. 2019

Angew Chem Int Ed

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A concise and highly stereoselective total synthesis of the Daphniphyllum alkaloids (−)‐daphenylline has been accomplished. The synthesis was started from (S)‐carvone and proceeded via a stereoselective Mg(ClO4)2‐catalyzed intramolecular amide addition cyclization, an intramolecular Diels–Alder reaction to construct the ABCD tetracyclic core architecture, and a Robinson annulation coupled with an oxidative aromatization sequence. Finally, the DF ring system was installed through an intramolecular Friedel–Crafts cyclization. The total synthesis of (−)‐daphenylline is achieved in 19 steps in the longest reaction sequence and in 7.6 % overall yield.

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Section: Figurementioning

confidence: 99%

Total Synthesis of (−)‐Daphenylline

Wang

Xun

et al. 2019

Angew Chem Int Ed

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“…The congested polycyclic ring systems of these alkaloids, along with their promising bioactivities, make them highly attractive synthetic targets ,,. Since the pioneering syntheses of several daphniphyllum alkaloids by the Heathcock group, impressive total syntheses of various daphniphyllum alkaloids have been reported by the Carreira, Smith, Li, Hanessian, Fukuyama, Zhai, Dixon, and Qiu groups …”

Section: Figurementioning

confidence: 99%

A Concise Total Synthesis of (−)‐Himalensine A

Chen

Guo

et al. 2019

Angewandte Chemie

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The daphniphyllum alkaloids are a structurally fascinating and remarkably diverse family of natural products. General strategies for the chemical synthesis of their challenging architectures are highly desirable for efficiently accessing these intriguing alkaloids and addressing their pharmaceutical potential. Herein, a concise strategy designed to provide general and diversifiable access to various daphniphyllum alkaloids is described and utilized in the asymmetric synthesis of (−)‐himalensine A, which was accomplished in 14 steps. Key features of this strategy include a Cu‐catalyzed nitrile hydration, a Heck reaction to construct the challenging 2‐azabicyclo[3.3.1]nonane motif, a Meinwald rearrangement reaction, six, pot‐economic reactions, and the minimal use of protecting groups, which significantly improved the overall synthetic efficiency.

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“…1 Following the pioneering synthetic studies by Heathcock and co-workers on a subset of these alkaloids, 2 the sheer complexity and varied biological activities of these natural products have continued to entice synthetic chemists to build other congeners. 1e Specifically, calyciphylline A-type and daphmanidin A-type alkaloids have received the most attention from synthetic chemists in the past decade ( Figure 1a), with the groups of Carreira, 3 Li, 4 Smith, 5 Fukuyama, 6 Zhai, 7 and Dixon 8 having elegantly solved the formidable synthetic challenges associated with preparing these dauntingly complex molecules.…”

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confidence: 99%

The Calyciphylline B-type Alkaloids: Total Syntheses of (–)-Daphlongamine H and (–)-Isodaphlongamine H

Hugelshofer

Palani²,

Sarpong³

2019

Preprint

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The first total synthesis of the complex hexacylic Daphniphyllum alkaloid (–)-daphlongamine H in enantioenriched form has been accomplished. Key to the success of the strategy are a complexity-building Mannich reaction, efficient cyclizations, and a highly diastereoselective hydrogenation to assemble multigram quantities of the tricyclic core bearing four contiguous stereocenters. Following construction of the hydro-indene substructure by means of a Pauson–Khand reaction, endgame redox manipulations delivered the natural product. Importantly, the synthetic studies have also given access to (–)-isodaphlongamine H and led to a revision of the reported structure of deoxyisocalyciphylline B, which resulted in the proposal of a modified biosynthetic pathway to the calyciphylline B-type alkaloids.

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Total Synthesis of (−)‐Daphenylline

Cited by 96 publications

References 44 publications

Total Synthesis of (−)‐Daphenylline

Total Synthesis of (−)‐Daphenylline

A Concise Total Synthesis of (−)‐Himalensine A

The Calyciphylline B-type Alkaloids: Total Syntheses of (–)-Daphlongamine H and (–)-Isodaphlongamine H

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