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. 2017 Aug 30;58(35):3406-3409.
doi: 10.1016/j.tetlet.2017.07.045. Epub 2017 Jul 11.

Iodine-mediated rearrangements of diallylsilanes

Gregory W O'Neil  1 , Elizabeth J Cummins  1
Affiliations

Iodine-mediated rearrangements of diallylsilanes

Gregory W O'Neil et al. Tetrahedron Lett. .

Abstract

Diallylsilanes can be made to rearrange upon treatment with I2. Of the silanes tested, diallyldiphenylsilane showed the greatest propensity to undergo this intramolecular carbocation allylation process. After etherification of the initially formed iodosilane, the products from this transformation represent useful synthetic intermediates, suitable for alkylation and cross-metathesis/annulation reactions.

Keywords: Amine annulation; Cross-metathesis; Diallylsilane; Rearrangement; Silacyclobutane.

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Figures

Figure 1
Figure 1
1H NMR analysis of iodine-catalyzed etherification of 2 showing small amounts of putative compound 4.
Figure 2
Figure 2
NMR analysis of iodination/rearrangement for different substituted diallylsilanes. Numbers given are integration values for the signals indicated. Increased amounts of allyl iodide formation correspond to lower amounts of rearranged products 9.
Scheme 1
Scheme 1
Reactivity and initial synthesis of 1.
Scheme 2
Scheme 2
Synthesis of 1 via diallylsilane 2.
Scheme 3
Scheme 3
Previously reported electrophilic rearrangements of diallylsilanes.
Scheme 4
Scheme 4
Iodine-mediated rearrangement of diallylsilane 2.
Scheme 5
Scheme 5
Synthesis of 10 from diallyldiphenylsilane.
Scheme 6
Scheme 6
Further synthetic manipulations of product 10.
See this image and copyright information in PMC

References

    1. Medina CR, Carter KP, Miller MM, Clark TB, O’Neil GW. J Org Chem. 2013;78:9093–9101. - PubMed
    2. O’Neil GW, Miller MM, Carter KP. Org Lett. 2010;12:5350–5353. - PubMed
    1. Matsumoto K, Oshima K, Utimoto K. J Org Chem. 1994;59:7152–7155.
    1. Myers AG, Kephart SE, Chen H. J Am Chem Soc. 1992;114:7922–7923.
    2. Denmark SE, Griedel BD, Coe DM, Schnute ME. J Am Chem Soc. 1994;116:7026–7043.
    1. Li Z, Yang C, Zheng H, Qiu H, Lai G. J Organomet Chem. 2008;693:3771–3779.
    1. Li ZF, Cao GQ, Lai JH, Liu Y, Ni JR, Wu HY, Qiu J. J Organomet Chem. 2006;691:4740–4746.

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