Synlett 2014; 25(16): 2285-2288
DOI: 10.1055/s-0034-1378512
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© Georg Thieme Verlag Stuttgart · New York

Diester-Substituted Aminocyclopropanes: Synthesis and Use in [3+2]-Annulation Reactions

Eloisa Serrano
Laboratory of Catalysis and Organic Synthesis, Ecole Polytechnique Fédérale de Lausanne, EPFL SB ISIC LCSO, BCH 4306, 1015 Lausanne, Switzerland   Fax: +41(21)6939700   Email: jerome.waser@epfl.ch
,
Florian de Nanteuil
Laboratory of Catalysis and Organic Synthesis, Ecole Polytechnique Fédérale de Lausanne, EPFL SB ISIC LCSO, BCH 4306, 1015 Lausanne, Switzerland   Fax: +41(21)6939700   Email: jerome.waser@epfl.ch
,
Jerome Waser*
Laboratory of Catalysis and Organic Synthesis, Ecole Polytechnique Fédérale de Lausanne, EPFL SB ISIC LCSO, BCH 4306, 1015 Lausanne, Switzerland   Fax: +41(21)6939700   Email: jerome.waser@epfl.ch
› Author Affiliations
Further Information

Publication History

Received: 14 May 2014

Accepted after revision: 19 June 2014

Publication Date:
28 July 2014 (eFirst)

Abstract

In this Letter, we describe the synthesis of new donor-acceptor substituted cyclopropanes bearing various imido groups and their use in [3+2]-annulation reactions. A sequence of palladium-catalyzed vinylation and rhodium-catalyzed cyclopropanation gave access to the required cyclopropanes in only two steps and high overall yields. The obtained compounds were used successfully in the tin-catalyzed [3+2] annulation with enol ethers to give cyclopentylamine derivatives in 22–95% yield.

Supporting Information

 
  • References and Notes

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  • 10 All substrates were obtained with a diastereoselectivity higher than 20:1 as determined by the 1H NMR of the crude reaction mixture. The trans relationship between the nitrogen and oxygen groups had been determined previously on phthalimido-substituted products via X-ray diffraction studies3e and was assumed to be identical for the products obtained in this work based on the similitude of the NMR data. The high diastereoselectivity observed may be due to minimization of the dipoles of the C–N and the C–O bonds during ring closing, but further studies will be required to support this hypothesis.
  • 11 General Procedure for Vinylation: Method A: Following a modified procedure,8b Na2PdCl4 (2 mol%) was added to a stirred solution of the corresponding imide (1.00 equiv) in vinyl acetate (27 equiv) and the mixture was heated under reflux for 48–96 h. The solvent was evaporated and the residue was purified by column chromatography to obtain solid compounds. Method B: PdCl2 (10 mol%) and lithium chloride (1.0 equiv weighted in a glovebox) were added to a stirred solution of the corresponding imide (1.00 equiv) in vinyl acetate (27 equiv) and the mixture was heated under reflux for 20–48 h. The mixture was cooled to r.t. and the solvent was evaporated. The residue was purified by column chromatography to obtain solid compounds. General Procedure for Cyclopropanation: Following a modified procedure,5b the corresponding N-vinyl imide (1.00 equiv) was dissolved in anhyd CH2Cl2 (10 mL) and the solution was cooled to 0 °C with an ice/water bath. Then, bis[rhodium(α,α,α′,α′-tetramethyl-1,3-benzenedipropionic acid)] (5, 0.1 mol%) was added in one portion. A solution in CH2Cl2 (2.0 mL) of the corresponding malonate (1.20 equiv) was added dropwise over 5 min. After the addition, the mixture was allowed to warm to r.t. and stirred overnight. The solvent was then removed under reduced pressure and the crude was directly purified by column chromatography. General Procedure for [3+2] Annulation: Following a reported procedure,3e in an oven-dried flask sealed with a septum, the corresponding aminocyclopropane (1.00 equiv) and triisopropyl[(1-phenylvinyl)oxy]silane (7; 1.50 equiv) were dissolved in anhyd CH2Cl2 (2.0 mL). The solution was then cooled to –78 °C and 23 μL of a 0.43 M solution of tin tetrachloride (5.0 mol%; ref. 12) in anhyd CH2Cl2 was added. The reaction was stirred for 1–3 h at –78 °C and then quenched at –78 °C with Et3N (0.30 mL). The reaction was warmed to r.t. and stirred for 15 min. CH2Cl2 was removed under reduced pressure and the crude was directly purified by column chromatography.
  • 12 Higher catalyst loading was required for some substrates; see the Supporting Information for more details.