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Synthesis 2009(1): 113-126  
DOI: 10.1055/s-0028-1083276
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

Inverse-Electron-Demand Diels-Alder Reactions of N-(Heteroarylsulfonyl)-1-aza-1,3-dienes Catalyzed by Chiral Lewis Acids

Jorge Esquivias, Inés Alonso, Ramón Gómez Arrayás*, Juan Carlos Carretero*
Departamento de Química Orgánica, Universidad Autónoma de Madrid (UAM), Cantoblanco, 28049 Madrid, Spain
Fax: +34(91)4973966; e-Mail: ramon.gomez@uam.es; e-Mail: juancarlos.carretero@uam.es;
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Publication History

Received 4 November 2008
Publication Date:
12 December 2008 (online)

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Abstract

The feasibility of using chiral Lewis acids as catalysts to promote the inverse-electron-demand Diels-Alder reactions of 1-azadienes with vinyl ethers has been demonstrated. Two catalyst systems were identified for this reaction, both relying on the presence of a coordinating 2-pyridylsulfonyl or 8-quinolylsulfonyl group at the imine nitrogen of the 1-azadiene. The combination of a 8-quinolylsulfonyl moiety and nickel(II)/DBFOX-Ph proved to be highly efficient, allowing the synthesis of substituted piperidine derivatives in good yields, excellent endo selectivity, and enantio­selectivities typically in the range of 77 to 92% ee.

Key words

Diels-Alder reactions - N-sulfonyl-1-azadienes - vinyl ethers - chiral Lewis acids - imines - asymmetric catalysis

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23

For the synthesis of 2-pyridylsulfonyl imines 1-4 and 7-10, see ref. 21a. For the synthesis of 8-quinolylsulfonyl imines 20, 28-35, 44, 45, and 48, see ref. 22.

24

In agreement with literature data, only decomposition products were obtained in the reactions of N-tosyl-, N-(2-thienylsulfonyl)-, and N-(2-pyridylsulfonyl)imines of benzaldehyde with 5 in the presence of 10 mol% of Cu(OTf)2 after 48 hours at room temperature.

25

Amounts of dienophile lower than 20 equivalents led to incomplete conversions.

26

Similar enantioselectivities were obtained in other solvents, such as toluene (61% ee), 1,2-dichloroethane (62% ee), tetrahydrofuran (58% ee), or 1,4-dioxane (60% ee).

28

Dichloromethane proved to be the optimal solvent (DCE led to poorer endo selectivity while no reaction was observed in toluene, Et2O, or THF).

32

Unit cell parameters: a = 9.4345 (2), b = 11.1796 (3), c = 21.8461 (6); space group P212121. CCDC 641861 contains the supplementary crystallographic data for this compound. These data can be obtained free of charge from the Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.

33

Critical NOE contacts for 54a and 54b are shown in Figure  [³] below.

Figure 3

34

The supplementary crystallographic data for 54b can be found in the Supporting Information of ref. 22.