Asymmetric Methanolysis of Cyclic meso-Anhydrides with Tripodal 2,6-trans-1,2,6-Trisubstituted Piperidine as Chiral Amine Catalyst

Abstract

An optically active tripodal amine, (2S,6S)-2,6-bis(o-hydroxyphenyl)-1-(2-pyridylmethyl)piperidine, was proven to be a potent chiral catalyst (1-5 mol%) for methanolytic asymmetric desymmetrization of cyclic meso-anhydrides to hemiesters. A good level of enantioselectivities (up to 81% ee) was achieved for various substrates, some of which were reported to be poor substrates for methanolysis using known chiral amines as catalysts.

Key words

chiral amine catalyst - cyclic meso-anhydrides - asymmetric desymmetrization - methanolysis - organocatalysis

References and Notes

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1

Current address: Department of Chemistry, Graduate School of Science and Technology, Kumamoto University, 2-39-1 Kurokami, Kumamoto 860-8555, Japan. E-mail: [e-mail]

5

Bolm et al. also devised a catalytic system with a stoichiometric amount of sacrificial achiral amine.^4e

13

Although we used the (R,R)-isomer of 1 in our previous report (ref. 8), this work was performed with (S,S)-1.

14

Typical Procedure for Catalytic Asymmetric Methanolysis of Cyclic meso-Anhydrides: To a solution or suspension of cyclic meso-anhydride (0.1 mmol) and 1 (1.8 mg, 5 µmol) in dist. toluene (1-2.5 mL) was added MeOH (20-81 µL, 0.5-2.0 mmol) at the temperature specified in Table 1 and Table 2. After being stirred at the temperature for 24 h, an aliquot of the reaction mixture was concentrated and subjected to ¹H NMR analysis. The chemical yield was estimated from the ratio of the unreacted anhydride and the hemiester produced, which were the only two components in the crude reaction mixture. Then, whole the mixture was acidified with aq HCl (1 M, 1.0 mL) to extract 1 into the aqueous phase. The phases were separated and the product in the organic layer was extracted with sat. NaHCO₃ (2 × 1.0 mL), leaving the starting material in the organic layer. After the organic layer was discarded, the aqueous layer was acidified with aq HCl (1 M, 2.0 mL) and extracted with EtOAc (3 × 2.0 mL). The combined organic layer was dried over Na₂SO₄ and concentrated in vacuo to give the desired hemiester in almost pure form judged by the ¹H NMR analysis.

15

The conditions for the HPLC analysis of each compound are as follows: 3a: DAICEL CHIRALCELL AS-H, hexane-2-propanol-CF₃COOH = 95:5:0.1, 0.3 mL/min. Carboxanilide of 3b: DAICEL CHIRALCELL AD-H, hexane-2-pro-
panol = 90:10, 0.5 mL/min. Carboxanilide of 3c: DAICEL CHIRALCELL OD-H, hexane-2-propanol = 90:10, 0.5 mL/min. p-Bromophenyl ester of 3d: DAICEL CHIRALCELL OD-H, hexane-2-propanol = 98:2, 0.5 mL/min. p-Bromo-phenyl ester of 3e: DAICEL CHIRALCELL OD-H, hexane-2-propanol = 98:2, 0.5 mL/min. Carboxanilide of 3f: DAICEL CHIRALCELL OD-H, hexane-2-propanol = 92:8, 0.5 mL/min. 3g: DAICEL CHIRALCELL AD-H, hexane-2-propanol-CF₃COOH = 90:10:0.1, 0.5 mL/min. Carboxanilide of 3h: DAICEL CHIRALCELL AS-H, hexane-2-propanol = 70:30, 0.5 mL/min. Carboxanilide of 3i: DAICEL CHIRALCELL OJ-H, hexane-2-propanol = 90:10, 0.5 mL/min.

18

The authors are grateful to a reviewer for useful suggestions about the mechanism of this reaction that is now under investigation in our laboratory.