Palladium-catalyzed stereospecific epoxide-opening reaction of γ,δ-epoxy-α,β-unsaturated esters with boric acid leading to γ,δ-diol derivatives with double inversion of configuration

Chemistry Letters

Volumn 33, Issue 6, 2004, Pages 764-765

  Yu, Xiao Qiang ^a   Hirai, Atsushi ^a   Miyashita, Masaaki ^a  

^a HOKKAIDO UNIVERSITY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

BORIC ACID; EPOXIDE; ESTER DERIVATIVE; PALLADIUM;

ARTICLE; CATALYSIS; CATALYST; CHEMICAL REACTION; REACTION ANALYSIS; STEREOSPECIFICITY; SYNTHESIS;

EID: 4444344467     PISSN: 03667022     EISSN: None     Source Type: Journal    
DOI: 10.1246/cl.2004.764     Document Type: Article

References (9)

1. B. M. Kim, et al., in "Comprehensive Organic Synthesis, Additions to C-X π-Bonds, Part 2," ed. by C. H. Heathcock, Pergamon Press, Oxford (1991), Vol. 2, Chap. 1.7.
2. H. Hayakawa, N. Okada, and M. Miyashita, Tetrahedron Lett., 40, 3191 (1999).
3. A. Hirai, T. Tonooka, K. Wakatsuki, K. Tanino, and M. Miyashita, Chirality, 15, 108 (2003); A. Hirai, X.-Q. Yu, T. Tonooka, and M. Miyashita, Chem. Commun., 2003, 2482.
4. A. Hirai, T. Tonooka, K. Wakatsuki, K. Tanino, and M. Miyashita, Chirality, 15, 108 (2003); A. Hirai, X.-Q. Yu, T. Tonooka, and M. Miyashita, Chem. Commun., 2003, 2482.
5. trans- and cis-γ,δ-Epoxy unsaturated esters were prepared from the allyl alcohols by the three step reaction sequence: 1) epoxidation with mCPBA; 2) Swern oxidation; 3) Horner-Wadsworth-Emmons reaction with triethyl phosphonoacetate.
6. 4 (12 mg, 0.01 mmol) and the mixture was stirred at room temperature for 10 min. The reaction mixture was passed through a silica gel column by the aid of EtOAc and the eluate was concentrated in vacuo to leave the crude diol. The crude product was purified by silica gel column chromatography (hexane/EtOAc = 7:3) to give the 2a-syn diol (53 mg, 94% yield).
7. Stereochemistry of the products was unambiguously determined by NOE measurements of the acetonides derived from 2b-syn and 2b-anti, respectively.
8. L. Wang and K. B. Sharpless, J. Am. Chem. Soc., 114, 7568 (1992); Asymmetric dihydroxylation of dienes, see: D. Xu, G. A. Crispino, and K. B. Sharpless, J. Am. Chem. Soc., 114, 7570 (1992).
9. L. Wang and K. B. Sharpless, J. Am. Chem. Soc., 114, 7568 (1992); Asymmetric dihydroxylation of dienes, see: D. Xu, G. A. Crispino, and K. B. Sharpless, J. Am. Chem. Soc., 114, 7570 (1992).