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. 2008 Nov 20;10(22):5313-6.
doi: 10.1021/ol802266s. Epub 2008 Oct 28.

Siloxacyclopentenes as dienophile-linked directing groups in intramolecular Diels-Alder reactions

Geoff T Halvorsen  1 , William R Roush
Affiliations

Siloxacyclopentenes as dienophile-linked directing groups in intramolecular Diels-Alder reactions

Geoff T Halvorsen et al. Org Lett. .

Abstract

The synthesis and intramolecular Diels-Alder reactions of trienes 5 and 6 with a siloxacyclopentene-constrained dienophile are described. These reactions provide the primary cycloadducts 7 and 8 with high diastereoselectivity. These cycloadducts possess trans-relationships between the ring fusion proton and the adjacent C(1) alkoxy group and can be further elaborated to alcohols 9 and 11 (via protiodesilylation) or to 10 and 12 (via Fleming-Tamao oxidation) depending on the substitutent R.

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Figures

Scheme 1
Scheme 1
Stereochemical Directing Group Strategies for IMDA Reactions
Scheme 2
Scheme 2
Strategy for Intramolecular Diels-Alder Cyclizations of Siloxacyclopentene-Constrained Trienes 5 and 6
Scheme 3
Scheme 3
Synthesis of Nonatrienes 5a-c
Scheme 4
Scheme 4
Synthesis of Decatrienes 6a-c
Scheme 5
Scheme 5
Attempted Hydrosilylation of 19d
See this image and copyright information in PMC

References

    1. Ciganek B. Org React. 1983;32:1.
    1. Craig D. Chem Soc Rev. 1986;16:187.
    1. Roush WR. In: Comprehensive Organic Synthesis. Trost BM, editor. Vol. 5. Pergamon Press; Oxford: 1991. pp. 513–550.
    1. Takao K, Munakata R, Tadano K. Chem Rev. 2005;105:4779. - PubMed
    1. Boeckman RK, Jr, Barta TE. J Org Chem. 1985;50:3421.

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