On the Peculiarities of the Ring Contraction Reactions of Homodrimanes via Acid Mediated Epoxide Rearrangement

Author:

Kulciţki Veaceslav,Sîrbu Tatiana,Ungur Nicon

Abstract

A selective rearrangement of a epoxy-homodrimanic substrate is described. Using fluorosulfonic acid at low temperature leads by ring contraction to a perhydrindanic structure. On the contrary, using boron trifluoride-diethyl ether at r.t. selectively brings about angular methyl migration.

Publisher

Institute of Chemistry of Academy of Science of Moldova

Subject

Process Chemistry and Technology,Environmental Chemistry,General Chemistry

Reference4 articles.

1. Synthesis and absolute stereochemistry of marine nor-sesquiterpene austrodoric acid

2. Diastereoselective routes towards the austrodorane skeleton based on pinacol rearrangement: synthesis of (+)-austrodoral and (+)-austrodoric acid

3. Compound 3. 1H NMR (CDCl3, 300MHz): 4.31 (t., 2H, J=6Hz), 2.6-2.9 (m., 2H); 2.15-2.25 (m., 1H); 2.00 (s.,3H); 1.17 (s., 3H); 0.87 (s., 3H); 0.86 (s., 3H); 0.84 (s., 3H). IR (liquid fi lm, cm-1): 1734, 1695. Compound 5. 1H NMR (CDCl3, 300MHz): 5.00 (s., 1H); 4.83 (s., 1H); 3.96-4.15 (m., 2H); 2.02 (s., 3H); 1.10 (s., 3H); 1.04 (s., 3H); 1.03 (s., 3H). IR (liquid fi lm, cm-1): 2925, 1742, 1460, 1364, 1234, 1034, 880. Compound 6. 1H NMR (CDCl3, 300MHz): 4.08-4.27 (m., 2H); 2.03 (s., 3H); 1.14 (s., 3H); 1.00 (s., 3H); 0.99 (s., 3H); 0.97 (s., 3H). IR (liquid fi lm, cm-1): 3460; 2927; 1737; 1461; 1364; 1239; 1142; 1082; 1031. Compound 7. 1H NMR (CDCl3, 300MHz): 3.69 (t., 2H, J9Hz); 1.29 (s., 3H); 1.10 (s., 3H); 1.01 (s., 3H); 0.76 (s.,3H). IR (liquid fi lm, cm-1): 3400; 2932; 2870; 1452; 1386; 1073; 1041

4. Rearrangement of epoxides. Part I. Preparation and rearrangement of the α- and β-epoxides of 14,15-bisnorlabd-8-en-13(R and S)-yl acetates and of related epoxides

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