Aziridine-based concise synthesis of (±)-alstonerine

Craig, Donald C.; Goldberg, Frederick W.; Pett, Richard W.; Tholen, Niels T. H.; White, Andrew J. P.

doi:10.1039/c3cc45543b

Cited by 18 publications

(17 citation statements)

References 31 publications

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“…Similarly, when 2-hydroxymethyl-N-tosylaziridine 419 was reacted with (cinnamylsulfonyl)benzene 420 under the similar reaction condition, the corresponding ring-opened product sulfonamide 421 was formed which was cyclized with paraformaldehyde under acidic conditions to produce the corresponding N-tosylaminal 422 in good yield (Scheme 104). The same group later exploited this methodology for the total synthesis of (AE)-lepadiformine [182] and (AE)-alstonerine [183].…”

Section: Synthesis Of Six-membered Rings From Activated Aziridines Anmentioning

confidence: 98%

Ring Expansions of Activated Aziridines and Azetidines

Ghorai

Bhattacharyya

Das

et al. 2015

Topics in Heterocyclic Chemistry

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Facile construction of small and normal-sized, or more precisely, four to seven-membered aza-heterocyclic ring systems is always a challenging yet rewarding task for the synthetic organic chemists. Fortunately, activated aziridines and azetidines provide a direct and convenient access to this coveted molecular architectures through several elegant ring-expansion approaches. This chapter presents some of the illustrative and contemporary examples to demonstrate the synthetic diversity and efficiency of the ring-expansion strategies of activated aziridines and azetidines towards a vast array of small to normal-sized aza-heterocyclic moieties.

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Section: Synthesis Of Six-membered Rings From Activated Aziridines Anmentioning

confidence: 98%

Ring Expansions of Activated Aziridines and Azetidines

Ghorai

Bhattacharyya

Das

et al. 2015

Topics in Heterocyclic Chemistry

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“…The latter oxaheterocycles enabled the construction of (±)-alstonerine (145) upon further synthetic modification (Scheme 33). 40 Scheme 33 Synthesis of (±)-alstonerine…”

Section: Scheme 32 Synthesis Of (-)-Alstonerinementioning

confidence: 99%

Deployment of Aziridines for the Synthesis of Alkaloids and Their Derivatives

Macha

D’hooghe

2019

Synthesis

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Various (activated and non-activated) aziridines with diverse substitution patterns have been deployed successfully as starting materials for the synthesis of a wide variety of alkaloids via suitable functionalization and aziridine ring transformation. Alternatively, the preparation and interception of reactive aziridine intermediates has also been shown to constitute a valid approach toward alkaloid synthesis. This review summarizes aziridine-mediated syntheses of alkaloids, in which the aziridine is mobilized as either a substrate or an advanced synthetic intermediate.1 Introduction2 Alkaloids Synthesis from Aziridine Starting Materials2.1 (2R)- and (2S)-Hydroxymethyl-N-(1-phenylethyl)aziridines2.2 N-Benzylaziridine-2-carboxylates2.3 2-Substituted N-Tosyl- or N-Tritylaziridines2.4 2,3-Disubstituted N-Cbz- or N-Tosylaziridines2.5 N-DMB-aziridines3 Alkaloids Synthesis from Aziridines as Key Advanced Synthetic Intermediates3.1 Alkylative Aziridine Ring Opening3.2 Arylative Aziridine Ring Opening3.3 Ring Expansion3.4 Oxidative Aziridine Ring Opening3.5 Heteroatomic Nucleophilic Aziridine Ring Opening3.6 Reductive Aziridine Ring Opening4 Conclusion

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“…Total synthesis of this class of natural products has attracted the attention of synthetic chemists for many years . The representative approaches developed by Tamelen, Kutney, Cook, Martin, Kuethe, Kwon, Craig, and Gaich are depicted in Scheme . As can be seen, all of these successful routes involve stepwise construction of the C and D rings to attain the [3.3.1] bicyclic ring system.…”

Section: Introductionmentioning

confidence: 99%

Towards the Sarpagine‐Ajmaline‐Macroline Family of Indole Alkaloids: Enantioselective Synthesis of an N‐Demethyl Alstolactone Diastereomer

Dagoneau

Wang

2020

Chemistry A European J

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the strategy involving the use of functionalized tetrahydro‐6H‐cycloocta[b]indol‐6‐one is reported as a key intermediate for synthesis of members of the sarpagine‐ajmaline‐macroline family of monoterpene indole alkaloids. The desired tricycle was synthesized through the following key steps: 1) Evans’ syn‐selective aldolization; 2) Liebeskind–Srogl cross‐coupling using the phenylthiol ester of 3‐chloropropanoic acid as a surrogate of acrylic thioester for the synthesis of 2,3‐disubstituted indoles; and 3) ring‐closing metathesis (RCM) for the formation of the eight‐membered ring. An N‐allylation followed by intramolecular 1,4‐addition was planned for synthesis of the vobasine class of natural products. However, attempted cyclizations under a diverse set of conditions involving anionic, radical, and organopalladium/organonickel species failed to produce the bridged ring system. On the other hand, esterification of the pendant primary alcohol function with acetoacetic acid, followed by intramolecular Michael addition, afforded the desired tetracycle with excellent diastereoselectivity. Subsequent functional group manipulation and transannular cyclization of the amino alcohol afforded the N(1)‐demethyl‐3,5‐diepi‐alstolactone. We believe that the same synthetic route would afford the alstolactone should the amino alcohol with appropriate stereochemistry be used as the starting material.

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Aziridine-based concise synthesis of (±)-alstonerine

Cited by 18 publications

References 31 publications

Ring Expansions of Activated Aziridines and Azetidines

Ring Expansions of Activated Aziridines and Azetidines

Deployment of Aziridines for the Synthesis of Alkaloids and Their Derivatives

Towards the Sarpagine‐Ajmaline‐Macroline Family of Indole Alkaloids: Enantioselective Synthesis of an N‐Demethyl Alstolactone Diastereomer

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