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. 2012 Nov 2;14(21):5614-7.
doi: 10.1021/ol302744t. Epub 2012 Oct 24.

Cyclopropane compatibility with oxidative carbocation formation: total synthesis of clavosolide A

GuangRong Peh  1 , Paul E Floreancig
Affiliations

Cyclopropane compatibility with oxidative carbocation formation: total synthesis of clavosolide A

GuangRong Peh et al. Org Lett. .

Abstract

Cyclopropane-substituted allylic ethers react with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone to form oxocarbenium ions with no competitive ring cleavage. This reaction can be used for the preparation of cyclopropane-substituted tetrahydropyrans. The protocol was used as a key step in the total synthesis of the sponge-derived macrolide clavosolide A.

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Figures

Scheme 1
Scheme 1
Energetics of cyclopropyl carbinyl cation ring opening.
Scheme 2
Scheme 2
Oxidative synthesis of cyclopropane-containing tetrahydropyrans.
Scheme 3
Scheme 3
Oxidative cyclization of cyclopropane-containing substrates.
Scheme 4
Scheme 4
Retrosynthetic analysis of clavosolide A.
Scheme 5
Scheme 5
Synthesis of the cyclopropane-containing subunit.
Scheme 6
Scheme 6
Synthesis of the cyclization substrates.
Scheme 7
Scheme 7
Comparison of oxidative cyclization substrates.
Scheme 8
Scheme 8
Completion of the synthesis.
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