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Volumn , Issue 1, 2009, Pages 113-126

Inverse-electron-demand diels-alder reactions of N-(heteroarylsulfonyl)-1- aza-1,3-dienes catalyzed by chiral lewis acids

Author keywords

Asymmetric catalysis; Chiral lewis acids; Diels alder reactions; Imines; N sulfonyl 1 azadienes; Vinyl ethers

Indexed keywords

ASYMMETRIC CATALYSIS; CHIRAL LEWIS ACIDS; DIELS-ALDER REACTIONS; IMINES; N-SULFONYL-1-AZADIENES; VINYL ETHERS;

EID: 63849124210     PISSN: 00397881     EISSN: 1437210X     Source Type: Journal    
DOI: 10.1055/s-0028-1083276     Document Type: Article
Times cited : (31)

References (73)
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    • For a recent review on stereoselective aza-Diels-Alder reactions, see: (a) For a review on catalytic asymmetric aza-Diels-Alder reactions, see: Rowland, G. B.; Rowland, E. B.; Zhang, Q.; Antilla, J. C. Curr. Org. Chem. 2006, 10, 981.
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    • This reaction was first achieved by Yamamoto using a stoichiometric amount of a chiral boron complex. See: Hattori, K, Yamamoto, H. J. Org. Chem. 1992, 57, 3264
    • This reaction was first achieved by Yamamoto using a stoichiometric amount of a chiral boron complex. See: Hattori, K.; Yamamoto, H. J. Org. Chem. 1992, 57, 3264.
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    • 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.
    • 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.
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    • 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
    • 2 after 48 hours at room temperature.
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    • Amounts of dienophile lower than 20 equivalents led to incomplete conversions
    • Amounts of dienophile lower than 20 equivalents led to incomplete conversions.
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    • 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
    • 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).
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    • , or THF).
    • , or THF).
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    • 2O and DBFOX-Ph led to a complex that contains three molecules of water. Kanemasa's group previously observed a decrease of asymmetric induction when the reaction is performed in the presence of molecular sieves. See, for instance: Itoh, S.; Kanemasa, S. J. Am. Chem. Soc. 2002, 124, 13394.
    • 2O and DBFOX-Ph led to a complex that contains three molecules of water. Kanemasa's group previously observed a decrease of asymmetric induction when the reaction is performed in the presence of molecular sieves. See, for instance: Itoh, S.; Kanemasa, S. J. Am. Chem. Soc. 2002, 124, 13394.
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    • 1. 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.
    • 1. 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.
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    • Critical NOE contacts for 54a and 54b are shown in Figure 3 below.
    • Critical NOE contacts for 54a and 54b are shown in Figure 3 below.
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    • The supplementary crystallographic data for 54b can be found in the Supporting Information of ref. 22.
    • The supplementary crystallographic data for 54b can be found in the Supporting Information of ref. 22.
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