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Preparation of Stereodefined Secondary Alkyllithium Compounds

Authors

  • Stephanie Seel,

    1. Department Chemie, Ludwig-Maximilian-Universität München, Butenandtstrasse 5–13, Haus F, 81377 München (Germany), Fax: (+49) 89218077680
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  • Dr. Guillaume Dagousset,

    1. Department Chemie, Ludwig-Maximilian-Universität München, Butenandtstrasse 5–13, Haus F, 81377 München (Germany), Fax: (+49) 89218077680
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  • Dr. Tobias Thaler,

    1. Department Chemie, Ludwig-Maximilian-Universität München, Butenandtstrasse 5–13, Haus F, 81377 München (Germany), Fax: (+49) 89218077680
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  • Annette Frischmuth,

    1. Department Chemie, Ludwig-Maximilian-Universität München, Butenandtstrasse 5–13, Haus F, 81377 München (Germany), Fax: (+49) 89218077680
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  • Prof. Dr. Konstantin Karaghiosoff,

    1. Department Chemie, Ludwig-Maximilian-Universität München, Butenandtstrasse 5–13, Haus F, 81377 München (Germany), Fax: (+49) 89218077680
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  • Prof. Dr. Hendrik Zipse,

    Corresponding author
    1. Department Chemie, Ludwig-Maximilian-Universität München, Butenandtstrasse 5–13, Haus F, 81377 München (Germany), Fax: (+49) 89218077680
    • Department Chemie, Ludwig-Maximilian-Universität München, Butenandtstrasse 5–13, Haus F, 81377 München (Germany), Fax: (+49) 89218077680
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  • Prof. Dr. Paul Knochel

    Corresponding author
    1. Department Chemie, Ludwig-Maximilian-Universität München, Butenandtstrasse 5–13, Haus F, 81377 München (Germany), Fax: (+49) 89218077680
    • Department Chemie, Ludwig-Maximilian-Universität München, Butenandtstrasse 5–13, Haus F, 81377 München (Germany), Fax: (+49) 89218077680
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Abstract

We have developed a practical stereoretentive iodine/lithium-exchange process that allows the stereodefined preparation of cis- and trans-cycloalkyllithium compounds from their corresponding stereodefined iodides. Quenching with electrophiles offers stereospecific access to both cis- (up to 96 % cis) and trans-cycloalkyl derivatives (up to 99 % trans). A detailed study of the thermodynamic stabilities, stereochemical behavior, and reactivities of axially and equatorially substituted cyclohexyllithium reagents is reported. Ab initio calculations demonstrate that the formation of oligomeric cyclohexyllithium structures is pivotal for explaining the observed stereochemical preference.

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