Access to a Guanacastepene and Cortistatin-Related Skeleton via Ethynyl Lactone Ireland-Claisen Rearrangement and Transannular (4 + 3)-Cycloaddition of an Azatrimethylenemethane Diyl

Oleksandr Zhurakovskyi; Sam R. Ellis; Amber L. Thompson; Jeremy Robertson

doi:10.1021/acs.orglett.7b00834

Access to a Guanacastepene and Cortistatin-Related Skeleton via Ethynyl Lactone Ireland-Claisen Rearrangement and Transannular (4 + 3)-Cycloaddition of an Azatrimethylenemethane Diyl

Oleksandr Zhurakovskyi, Sam R. Ellis, Amber L. Thompson, Jeremy Robertson^*

^*Corresponding author for this work

School of Chemistry

Research output: Contribution to journal › Article (Academic Journal) › peer-review

13 Citations (Scopus)

Abstract

Heating a 2,5-furanocyclic (2-azidoethyl)allene initiates a cascade reaction comprising azide-allene cycloaddition, loss of nitrogen, and azatrimethylenemethane (ATMM) diyl-furan transannular (4 + 3)-cycloaddition. The major product of this reaction contains the pentacyclic core common to guanacastepenes D and H and radianspenes J-L; in addition, the central oxa-bridged cycloheptene ring, flanked by two carbocyclic rings, is structurally related to the ABC-ring system found in the cortistatins. This is the first reported synthetic application of a "free" (nonconjugated) ATMM. The cyclization precursors were prepared via the first reported examples of the Ireland-Claisen rearrangement of an ethynyl lactone.

Original language	English
Pages (from-to)	2174-2177
Number of pages	4
Journal	Organic Letters
Volume	19
Issue number	8
DOIs	https://doi.org/10.1021/acs.orglett.7b00834
Publication status	Published - 21 Apr 2017

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title = "Access to a Guanacastepene and Cortistatin-Related Skeleton via Ethynyl Lactone Ireland-Claisen Rearrangement and Transannular (4 + 3)-Cycloaddition of an Azatrimethylenemethane Diyl",

abstract = "Heating a 2,5-furanocyclic (2-azidoethyl)allene initiates a cascade reaction comprising azide-allene cycloaddition, loss of nitrogen, and azatrimethylenemethane (ATMM) diyl-furan transannular (4 + 3)-cycloaddition. The major product of this reaction contains the pentacyclic core common to guanacastepenes D and H and radianspenes J-L; in addition, the central oxa-bridged cycloheptene ring, flanked by two carbocyclic rings, is structurally related to the ABC-ring system found in the cortistatins. This is the first reported synthetic application of a {"}free{"} (nonconjugated) ATMM. The cyclization precursors were prepared via the first reported examples of the Ireland-Claisen rearrangement of an ethynyl lactone.",

author = "Oleksandr Zhurakovskyi and Ellis, {Sam R.} and Thompson, {Amber L.} and Jeremy Robertson",

year = "2017",

month = apr,

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doi = "10.1021/acs.orglett.7b00834",

language = "English",

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journal = "Organic Letters",

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Access to a Guanacastepene and Cortistatin-Related Skeleton via Ethynyl Lactone Ireland-Claisen Rearrangement and Transannular (4 + 3)-Cycloaddition of an Azatrimethylenemethane Diyl. / Zhurakovskyi, Oleksandr; Ellis, Sam R.; Thompson, Amber L. et al.
In: Organic Letters, Vol. 19, No. 8, 21.04.2017, p. 2174-2177.

Research output: Contribution to journal › Article (Academic Journal) › peer-review

TY - JOUR

T1 - Access to a Guanacastepene and Cortistatin-Related Skeleton via Ethynyl Lactone Ireland-Claisen Rearrangement and Transannular (4 + 3)-Cycloaddition of an Azatrimethylenemethane Diyl

AU - Zhurakovskyi, Oleksandr

AU - Ellis, Sam R.

AU - Thompson, Amber L.

AU - Robertson, Jeremy

PY - 2017/4/21

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N2 - Heating a 2,5-furanocyclic (2-azidoethyl)allene initiates a cascade reaction comprising azide-allene cycloaddition, loss of nitrogen, and azatrimethylenemethane (ATMM) diyl-furan transannular (4 + 3)-cycloaddition. The major product of this reaction contains the pentacyclic core common to guanacastepenes D and H and radianspenes J-L; in addition, the central oxa-bridged cycloheptene ring, flanked by two carbocyclic rings, is structurally related to the ABC-ring system found in the cortistatins. This is the first reported synthetic application of a "free" (nonconjugated) ATMM. The cyclization precursors were prepared via the first reported examples of the Ireland-Claisen rearrangement of an ethynyl lactone.

AB - Heating a 2,5-furanocyclic (2-azidoethyl)allene initiates a cascade reaction comprising azide-allene cycloaddition, loss of nitrogen, and azatrimethylenemethane (ATMM) diyl-furan transannular (4 + 3)-cycloaddition. The major product of this reaction contains the pentacyclic core common to guanacastepenes D and H and radianspenes J-L; in addition, the central oxa-bridged cycloheptene ring, flanked by two carbocyclic rings, is structurally related to the ABC-ring system found in the cortistatins. This is the first reported synthetic application of a "free" (nonconjugated) ATMM. The cyclization precursors were prepared via the first reported examples of the Ireland-Claisen rearrangement of an ethynyl lactone.

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DO - 10.1021/acs.orglett.7b00834

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SN - 1523-7060

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JO - Organic Letters

JF - Organic Letters

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ER -

Access to a Guanacastepene and Cortistatin-Related Skeleton via Ethynyl Lactone Ireland-Claisen Rearrangement and Transannular (4 + 3)-Cycloaddition of an Azatrimethylenemethane Diyl

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