Chemoselectivity and enantiocontrol in catalytic intramolecular metal carbene reactions of diazo acetates linked to reactive functional groups by naphthalene-1,8-dimethanol

Abstract

The use of chiral dirhodium(II) carboxamidate catalysts for metal carbene transformations of diazo acetates linked to a reactive functionality through naphthalene-1,8-dimethanol produces chemoselective and enantioselective reaction either at the remote functionality or by addition to the 1,2-position of the naphthalene ring; enantioselectivities up to 84% ee have been obtained for the Büchner reaction.

References

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12. Enantiomeric excesses for 3, 8 and 10 were determined with baseline separation on a WHELK-O column operated at 2 ml min^–1 in hexanes– PrⁱOH (9:1). Selected data for 10: δ_H(300 MHz, CDCl₃) 7.51 (d, J 7.1, 1H), 7.39–7.22 (m, 3H), 6.53 (d, J 9.5, 1H), 6.34 (dd, J 9.5, 4.6, 1H), 5.13 (d, J 9.5, 1H), 4.35 (d, J 9.5, 1H), 2.45 (dd, J 4.6, 2.4, 1 H), and 1.08 (d, J 2.4, 1H)δ_C(75 MHz, CDCl₃) 176.5, 133.1, 130.7, 128.9, 128.3, 128.2, 127.5, 124.7, 124.1, 69.2, 34.2, 30.9 and 21.2; V_max(CHCl₃)/ cm^–1 1789 and 1752; mp 82–84 °C (Calc. for C₁₃H₁₀O₂: C, 78.77; H, 5.08. Found: C, 77.95; H, 5.14%).