Stereoselective Reduction of β-Hydroxy α-Ketoesters: A Concise Synthesis of anti-α,β-Dihydroxy Esters

Abstract

A new synthetic route to anti-α,β-dihydroxy esters has been developed. The new method consists of three steps starting from an aldehyde: the nucleophilic condensation with ethyl diazo­acetate, oxidation with dimethyldioxirane, and stereoselective reduction with NaBH₄.

Key words

diazo compounds - diols - nucleophilic addition - oxidation - reduction - diastereoselectivity

References

• 1 For a review, see: Oishi T. Nakata T. Acc. Chem. Res.  1984,  17:  338 
• 2a Stocker JH. Sidisuntlorn P. Benjamin BM. Collins CJ. J. Am. Chem. Soc.  1960,  82:  3913 
• 2b Cram DJ. Wilson DR. J. Am. Chem. Soc.  1963,  85:  1245 
• 2c Katzenellenbogen JA. Bowlus SB. J. Org. Chem.  1973,  38:  627 
• 2d Bowlus SB. Katzenellenbogen JA. J. Org. Chem.  1974,  39:  3309 
• 2e Tokuyama T. Shimada K. Uemura M. Daly JW. Tetrahedron Lett.  1982,  23:  2121 
• 2f Overman LE. McCready RJ. Tetrahedron Lett.  1982,  23:  2355 
• 2g Nakata T. Tanaka T. Oishi T. Tetrahedron Lett.  1983,  24:  2653 
• For reviews, see:
• 3a Schroder M. Chem. Rev.  1980,  80:  187 
• 3b Kolb HC. VanNieuwenhze MS. Sharpless KB. Chem. Rev.  1994,  94:  2483 
• 4a Pearson WH. Cheng M.-C. J. Org. Chem.  1987,  52:  3176 
• 4b Fujita M. Laine D. Ley SV. J. Chem. Soc., Perkin Trans. 1  1999,  1647 
• 4c Andrus MB. Soma Sekhar BBV. Meredith EL. Dalley NK. Org. Lett.  2000,  2:  3035 
• 4d Dixon DJ. Ley SV. Polara A. Sheppard T. Org. Lett.  2001,  3:  2749 
• 5 anti-α,β-Dihydroxy esters were also synthesized through epoxidation of trans-α,β-unsaturated esters followed by hydrolysis and esterification. See: English J. Heywood DL. J. Am. Chem. Soc.  1955,  77:  4661 
• 6 Ihmels H. Maggini M. Prato M. Scorrano G. Tetrahedron Lett.  1991,  32:  6215 
• 7 Jiang N. Wang J. Tetrahedron Lett.  2002,  43:  1285 ; and references cited therein
• 8a Cram DJ. Abd Elhafez FA. J. Am. Chem. Soc.  1952,  74:  5828 
• 8b Cram DJ. Wilson DR. J. Am. Chem. Soc.  1963,  85:  1245 
• 9 Cherest M. Felkin H. Tetrahedron Lett.  1968,  28:  2205 
• 10 Touzin AM. Tetrahedron Lett.  1975,  16:  1477