Synthesis of the ABC Tricyclic System of Daphnicyclidin A

Li, Jian Long; Shi, Hongwei; Wang, Qi; Chai, Yong Hai; Yang, Jun

doi:10.1021/acs.orglett.7b00230

Cited by 27 publications

(11 citation statements)

References 36 publications

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“…1 Their highly congested, polycyclic architectures have long provided organic chemists with challenging targets for development of innovative synthetic strategies and methodologies, resulting in a number of elegant total syntheses (Figure 1). 2,3 For example, in the 1980s and 1990s, Heathcock and co-workers completed several remarkable syntheses of daphniphylline-type, secodaphniphyllinetype, bukittinggine-type, and daphnilactone A-type alkaloids. 4 More recently, many prominent total syntheses of daphmani-din A-type, calyciphylline A-type, and calyciphylline B-type alkaloids have been reported by the groups of Carreira, 5 Li, 6 Smith, 7 Fukuyama, 8 Hanessian, 9 Dixon, 10 Zhai, 11 Qiu, 12 Xu,13a Gao, 14 and Sarpong.…”

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confidence: 99%

Total Synthesis of (−)-Daphnezomines A and B

et al. 2020

J. Am. Chem. Soc.

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Daphnezomines A and B are structurally unusual Daphniphyllum alkaloids that contain a unique aza-adamantane core skeleton. Herein, a modular approach to these alkaloids is presented that exploits a diverse array of reaction strategies. Commencing from a chiral pool terpene–(S)-carvone, the azabicyclo[3.3.1]nonane backbone, which occurs widely in Daphniphyllum alkaloids, was easily accessed through a Sharpless allylic amination and a palladium-catalyzed oxidative cyclization. A protecting group enabled a stereoselective B-alkyl Suzuki–Miyaura coupling sequence and an Fe-mediated hydrogen atom transfer (HAT)-based radical cyclization were then applied to construct C6 and C8 stereocenters. A final epimer locking strategy enabled the assembly of the highly congested aza-adamantane core, thereby achieving the first total synthesis of (−)-daphnezomines A and B in 14 steps.

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confidence: 99%

Total Synthesis of (−)-Daphnezomines A and B

et al. 2020

J. Am. Chem. Soc.

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“…This structural complexity and biological activity of 1 and its congeners have inspired the development of synthetic approaches to daphnicyclidin A without, however, a conclusion in the form of the total synthesis. Previous synthetic approaches to the ABC tricyclic substructure of daphnicyclidin A include a 17‐step process resulting in the preparation of 9 in 4.8 % yield, [7] and a 7‐step process affording 10 in 11.4 % yield [8] . An approach to the BCD system [9] with an overall 19‐step synthesis gave 11 in 5.6 % yield, [9] and a route to the ACE substructure [10] 12 proceeded in 2.5 % yield over 19 steps (Figure 2).…”

Section: Methodsmentioning

confidence: 99%

“…Previous synthetic approaches to the ABC tricyclic substructure of daphnicyclidin A include a 17-step process resulting in the preparation of 9 in 4.8 % yield, [7] and a 7-step process affording 10 in 11.4 % yield. [8] An approach to the BCD system [9] with an overall 19-step synthesis gave 11 in 5.6 % yield, [9] and a route to the ACE substructure [10] 12 proceeded in 2.5 % yield over 19 steps (Figure 2). Several other substructures of daphnicyclidin A have also been prepared.…”

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confidence: 99%

Intramolecular (4+3) Cycloadditions of Oxidopyridinium Ions: Towards Daphnicyclidin A

Ripa

Kelley

et al. 2022

Chemistry A European J

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N-alkylation of 5-hydroxynicotinic acid esters with electrophiles containing diene functionality produces salts that undergo intramolecular (4 + 3) cycloaddition reactions upon heating in the presence of base. Initial studies used a three-carbon tether to join the pyridinium ion and diene, revealing some aspects of the inherent selectivity of the reaction with such substrates. Much more challenging was the synthesis of related species possessing only a two-carbon tether. Nevertheless, the cycloaddition of such compounds was successful, leading directly to the ABC ring system of the alkaloid daphnicyclidin A.

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“…In the synthesis of the bridged tricyclic ABC ring system of daphnicyclidin A (4), Yang utilized a series of two intramolecular HWE olefinations. 26 Following the synthesis of the densely functionalized pyrrolidine 77 (Scheme 13, syn-…”

Section: Horner-wadsworth-emmons (Hwe) Reactionmentioning

confidence: 99%

Synthetic Approaches to Non-Tropane, Bridged, Azapolycyclic Ring Systems Containing Seven-Membered Carbocycles

Shoemaker

Griffith²

2020

Synthesis

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This Short Review highlights various synthetic approaches to bridged azabicyclic ring systems containing seven-membered carbocyclic rings. Such ring systems are common to a number of biologically active natural products. The seven-membered ring in such systems is generally formed in one of four ways: 1) cyclization of an acyclic precursor; 2) ring expansion or rearrangement of a different ring size; 3) cycloaddition; and 4) use of a synthetic building block with the seven-membered ring already present. Representative examples of each approach from both total synthesis and methodological studies are discussed, with an emphasis on work publishedin the last twenty years.1 Introduction2 Cyclization Reactions3 Ring Expansions and Rearrangements4 Cycloadditions5 Strategies Involving Seven-Membered Ring Building Blocks6 Conclusion

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Synthesis of the ABC Tricyclic System of Daphnicyclidin A

Cited by 27 publications

References 36 publications

Total Synthesis of (−)-Daphnezomines A and B

Total Synthesis of (−)-Daphnezomines A and B

Intramolecular (4+3) Cycloadditions of Oxidopyridinium Ions: Towards Daphnicyclidin A

Synthetic Approaches to Non-Tropane, Bridged, Azapolycyclic Ring Systems Containing Seven-Membered Carbocycles

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