Indium-Bipyridine Catalyzed, Enantioselective Aminolysis of meso-Epoxides

Abstract

The enantioselective aminolysis of meso-epoxides is efficiently catalyzed by an indium(III)-bipyridine catalyst to furnish highly enantiomerically enriched 1,2-amino alcohols in good yields and up to 98% ee.

amine - asymmetric catalysis - bipyridine - epoxides - ­indium

References and Notes

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12 For the first synthesis and application of ligand 2a in asymmetric catalysis, see: Bolm C. Zehnder M. Bur D. Angew. Chem., Int. Ed. Engl.  1990,  29:  191 ; Angew. Chem. 1990, 102, 206

13

We have made the same observation in the related indium(III)-bipyridine 2a catalyzed thiolysis of meso-epoxides (ref. 9).

14

Typical Experimental Procedure
In an oven-dried flask and under inert atmosphere In(OTf)₃ (28 mg, 0.05 mmol) and bipyridine 2a (20 mg, 0.05 mmol) were dissolved in CH₂Cl₂ (1 mL) and treated with epoxide (0.50 mmol) and amine (1.00 mmol) at r.t. The reaction mixture was stirred for 48 h at r.t. whereupon it was concentrated in vacuo and purified by silica gel chromatography. For analytical and spectroscopic details of the products, see ref. 8b.

15 Ishikawa S. Hamada T. Manabe K. Kobayashi S. J. Am. Chem. Soc.  2004,  126:  12236