Stereoselective synthesis and reactions of secondary alkyllithium reagents functionalized at the 3-position

Kohei Moriya, Dorian Didier, Meike Simon, Jeffrey M. Hammann, Guillaume Berionni, Konstantin Karaghiosoff, Hendrik Zipse, Herbert Mayr, Paul Knochel, K. Moriya, D. Didier, M. Simon, J. M. Hammann, Guillaume Berionni, Prof K. Karaghiosoff, Prof H. Zipse, Prof H. Mayr, Prof P. Knochel

Research output: Contribution to journalArticle

Abstract

Secondary alkyllithium reagents bearing an OTBS group (TBS = tert-butyldimethylsilyl) at the 3-position can be prepared stereoconvergently through an I/Li exchange from a diastereomeric mixture of the corresponding secondary alkyl iodides. These lithium reagents react with a range of electrophiles, including carbon electrophiles, with retention of configuration to yield various 1,3-difunctionalized derivatives with good diastereoselectivities. Kinetic studies show that the 3- siloxy group strongly accelerates the epimerization at the lithium-substituted carbon atom. This method offers a new way to construct chiral open-chain molecules with excellent stereoselectivity.

Original languageEnglish
Pages (from-to)2754-2757
Number of pages4
JournalAngewandte Chemie - International Edition
Volume54
Issue number9
DOIs
Publication statusPublished - 23 Feb 2015
Externally publishedYes

Keywords

  • Carbanions
  • Diastereoselectivity
  • Kinetics
  • Lithiation
  • Nucleophilic substitution

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  • Datasets

    CCDC 1015348: Experimental Crystal Structure Determination

    Berionni, G. (Contributor), Didier, D. (Contributor), Hammann, J. M. (Contributor), Karaghiosoff, P. K. (Contributor), Knochel, P. P. (Contributor), Mayr, H. (Contributor), Moriya, K. (Contributor) & Simon, M. (Contributor), Cambridge Crystallographic Data Centre, 1 Jan 2015

    Dataset

    CCDC 1015349: Experimental Crystal Structure Determination

    Berionni, G. (Contributor), Didier, D. (Contributor), Hammann, J. M. (Contributor), Karaghiosoff, P. K. (Contributor), Knochel, P. P. (Contributor), Mayr, H. (Contributor), Moriya, K. (Contributor) & Simon, M. (Contributor), Cambridge Crystallographic Data Centre, 1 Jan 2015

    Dataset

    Cite this

    Moriya, K., Didier, D., Simon, M., Hammann, J. M., Berionni, G., Karaghiosoff, K., Zipse, H., Mayr, H., Knochel, P., Moriya, K., Didier, D., Simon, M., Hammann, J. M., Berionni, G., Karaghiosoff, P. K., Zipse, P. H., Mayr, P. H., & Knochel, P. P. (2015). Stereoselective synthesis and reactions of secondary alkyllithium reagents functionalized at the 3-position. Angewandte Chemie - International Edition, 54(9), 2754-2757. https://doi.org/10.1002/anie.201409165