Enantioselective para-Claisen Rearrangement for the Synthesis of Illicium-Derived Prenylated Phenylpropanoids

Joshua A. Homer; Irene De Silvestro; Eilidh J. Matheson; Jake T. Stuart; Andrew L. Lawrence

doi:10.1021/acs.orglett.1c00620

Enantioselective para-Claisen Rearrangement for the Synthesis of Illicium-Derived Prenylated Phenylpropanoids

Joshua A. Homer, Irene De Silvestro, Eilidh J. Matheson, Jake T. Stuart, Andrew L. Lawrence^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

Abstract

The development of the first enantioselective para-Claisen rearrangement has been achieved. Using a chiral aluminum Lewis acid, illicinole is rearranged to give (-)-illicinone A (er 87:13), which can then be converted into more complex Illicium-derived prenylated phenylpropanoids. The absolute configurations of the natural products (+)-cycloillicinone and (-)-illicarborene A have been determined, and our results cast doubt on the enantiopurity of the natural samples.

Original language	English
Pages (from-to)	3248–3252
Journal	Organic letters
Volume	23
Issue number	9
Early online date	15 Apr 2021
DOIs	https://doi.org/10.1021/acs.orglett.1c00620
Publication status	Published - 7 May 2021

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10.1021/acs.orglett.1c00620

20210520_Lawrence_acs.orglett.1c00620Final published version, 1.2 MBLicence: Creative Commons: Attribution-NonCommercial-NoDerivatives (CC BY-NC-ND)

https://pubs.acs.org/doi/10.1021/acs.orglett.1c00620

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title = "Enantioselective para-Claisen Rearrangement for the Synthesis of Illicium-Derived Prenylated Phenylpropanoids",

abstract = "The development of the first enantioselective para-Claisen rearrangement has been achieved. Using a chiral aluminum Lewis acid, illicinole is rearranged to give (-)-illicinone A (er 87:13), which can then be converted into more complex Illicium-derived prenylated phenylpropanoids. The absolute configurations of the natural products (+)-cycloillicinone and (-)-illicarborene A have been determined, and our results cast doubt on the enantiopurity of the natural samples. ",

author = "Homer, \{Joshua A.\} and \{De Silvestro\}, Irene and Matheson, \{Eilidh J.\} and Stuart, \{Jake T.\} and Lawrence, \{Andrew L.\}",

note = "Funding Information: This work was supported by funding from the European Research Council (ERC) under the European Union{\textquoteright}s Horizon 2020 research and innovation programme (Grant Agreement No. 759552). I.D.S thanks the University of Edinburgh for the provision of a studentship. Fraser Milne (University of Edinburgh) is thanked for conducting preliminary experiments. Publisher Copyright: {\textcopyright} Copyright: Copyright 2021 Elsevier B.V., All rights reserved.",

year = "2021",

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doi = "10.1021/acs.orglett.1c00620",

language = "English",

volume = "23",

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AU - Homer, Joshua A.

AU - De Silvestro, Irene

AU - Matheson, Eilidh J.

AU - Stuart, Jake T.

AU - Lawrence, Andrew L.

N1 - Funding Information: This work was supported by funding from the European Research Council (ERC) under the European Union’s Horizon 2020 research and innovation programme (Grant Agreement No. 759552). I.D.S thanks the University of Edinburgh for the provision of a studentship. Fraser Milne (University of Edinburgh) is thanked for conducting preliminary experiments. Publisher Copyright: © Copyright: Copyright 2021 Elsevier B.V., All rights reserved.

PY - 2021/5/7

Y1 - 2021/5/7

N2 - The development of the first enantioselective para-Claisen rearrangement has been achieved. Using a chiral aluminum Lewis acid, illicinole is rearranged to give (-)-illicinone A (er 87:13), which can then be converted into more complex Illicium-derived prenylated phenylpropanoids. The absolute configurations of the natural products (+)-cycloillicinone and (-)-illicarborene A have been determined, and our results cast doubt on the enantiopurity of the natural samples.

AB - The development of the first enantioselective para-Claisen rearrangement has been achieved. Using a chiral aluminum Lewis acid, illicinole is rearranged to give (-)-illicinone A (er 87:13), which can then be converted into more complex Illicium-derived prenylated phenylpropanoids. The absolute configurations of the natural products (+)-cycloillicinone and (-)-illicarborene A have been determined, and our results cast doubt on the enantiopurity of the natural samples.

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DO - 10.1021/acs.orglett.1c00620

M3 - Article

AN - SCOPUS:85105034550

SN - 1523-7060

VL - 23

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JO - Organic letters

JF - Organic letters

IS - 9

ER -

Enantioselective para-Claisen Rearrangement for the Synthesis of Illicium-Derived Prenylated Phenylpropanoids

Abstract

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