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. 2017 Oct 11:13:2122-2127.
doi: 10.3762/bjoc.13.209. eCollection 2017.

Synthesis of substituted Z-styrenes by Hiyama-type coupling of oxasilacycloalkenes: application to the synthesis of a 1-benzoxocane

James R Vyvyan  1 , Courtney A Engles  1 , Scott L Bray  1 , Erik D Wold  1 , Christopher L Porter  1 , Mikhail O Konev  1
Affiliations

Synthesis of substituted Z-styrenes by Hiyama-type coupling of oxasilacycloalkenes: application to the synthesis of a 1-benzoxocane

James R Vyvyan et al. Beilstein J Org Chem. .

Abstract

Several Hiyama cross-coupling reactions of oxasilacycloalkenes and aryl iodides are described that produce trisubstituted Z-styrenes in moderate to excellent yields. Both electron-rich and electron-poor aryl iodides are tolerated in the cross-coupling reaction. The oxasilacycloalkene coupling partners were prepared by ruthenium-catalyzed intramolecular anti-hydrosilylation of alkynols. One of the cross-coupling products was converted to a 1-benzoxocane, albeit in low yield, using an intramolecular Buchwald-Hartwig etherification. The cyclic ether produced contains the carbon skeleton of heliannuol A.

Keywords: cross-coupling; heterocycles; hydrosilylation; palladium; silicon.

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Figures

Figure 1
Figure 1
Retrosynthetic analysis of heliannuol A.
Scheme 1
Scheme 1
Hydrosilylation of alkynols.
Scheme 2
Scheme 2
Hydrogenation of benzoxocane 24.
See this image and copyright information in PMC

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