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. 2014 Aug 13;136(32):11292-5.
doi: 10.1021/ja506579t. Epub 2014 Aug 5.

Rh(III)-catalyzed cyclopropanation initiated by C-H activation: ligand development enables a diastereoselective [2 + 1] annulation of N-enoxyphthalimides and alkenes

Tiffany Piou  1 , Tomislav Rovis
Affiliations

Rh(III)-catalyzed cyclopropanation initiated by C-H activation: ligand development enables a diastereoselective [2 + 1] annulation of N-enoxyphthalimides and alkenes

Tiffany Piou et al. J Am Chem Soc. .

Abstract

N-Enoxyphthalimides undergo a Rh(III)-catalyzed C-H activation initiated cyclopropanation of electron deficient alkenes. The reaction is proposed to proceed via a directed activation of the olefinic C-H bond followed by two migratory insertions, first across the electron-deficient alkene and then by cyclization back onto the enol moiety. A newly designed isopropylcyclopentadienyl ligand drastically improves yield and diastereoselectivity.

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Figures

Scheme 1
Scheme 1. Reaction Discovery
Scheme 2
Scheme 2. Reaction with (E)-1,2-Disubstituted Alkenes
Scheme 3
Scheme 3. Mechanistic Experiments
Scheme 4
Scheme 4. Proposed Mechanism
See this image and copyright information in PMC

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