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Synthetic Communications
An International Journal for Rapid Communication of Synthetic Organic Chemistry
Volume 20, 1990 - Issue 22
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Original Articles

Stereoselective Reactions of δ2-Isoxazoline Exo-azaenolates. A Model for Construction of the C-Ring of Sesbanimide A

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Pages 3575-3584 | Received 25 Oct 1990, Published online: 24 Oct 2006

References

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  • Pandit , U. K. 1989 . Pure Appl. Chem. , 61 : 423 Total Syntheses:
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  • For a de novo synthesis of a Ring B fragment, see reference 4a
  • Curran , D. P. and Chao , J.-C. 1987 . J. Am. Chem. Soc. , 109 : 3036
  • Curran , D. P. and Chao , J.-C. in press . Tetrahedron ,
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  • Reaction times were 4–14 h depending on the amount and the activity of the Ra-Ni catalyst
  • Curran , D. P. , Scanga , S. A. and Fenk , C. J. 1984 . J. Org. Chem. , 49 : 3474 Imine derivatives of cis 2-hydroxy-l-acyl cyclopentanes are especially prone to epimerization, but this epimerization is completely suppressed in all but the most difficult cases (t-butyl ketones). See
  • The trans stereochemistry was assigned by preparing the model furans shown below. The 1H NMR (wrong)spectra of furan 14 closely resembled that of the trans isomer, and was significantly different from the cis. See Experimental Section for details
  • The alkylation of 17 is the first of a conjugated isoxazoline azaenolate. About 10% of a single γ-alkylation product, tentatively assigned structure i, was also isolated. Benzylation of the azaenolate derived from 17 (PhCH2Br) gave a virtually identical ratio of the three benzylated products to the methylation reaction
  • Curran , D. P. , Brill , J. F. and Rakiewicz , D. M. 1984 . J. Org. Chem. , 49 : 1654 In our experience, Ra-Ni usually reduces monosubstituted double bonds more rapidly than isoxazolines; however, 1,2-disubstituted and trisubstituted double bonds often survive isoxazoline cleavage. 1,1-Disubstituted double bond reduction is often competitive with isoxazoline cleavage. Deactivation of the Ra-Ni by pretreatment with acetone is sometimes helpful. See

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