Acid-catalyzed rearrangement of α-hydroxycyclopropylsilanes

Tetrahedron Letters

Volumn 39, Issue 24, 1998, Pages 4313-4316

  Sakaguchi, Kazuhiko ^a   Fujita, Masato ^a   Ohfune, Yasufumi ^a  

^a Osaka Prefecture University   (Japan)

Author keywords

hydroxycyclopropylsilane; 1,2 CC bond migration; Acid catalyzed rearrangement; Cyclobutyl cation

Indexed keywords

ACID; CATION; CYCLOPROPANE DERIVATIVE; SILANE DERIVATIVE; TRIMETHYLSILYL DERIVATIVE; VINYL DERIVATIVE;

ARTICLE; CATALYSIS; CHEMICAL BOND; CHIRALITY; DIASTEREOISOMER; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; OPTICAL ROTATION; REACTION ANALYSIS; STEREOCHEMISTRY;

EID: 0032508028     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4039(98)00760-6     Document Type: Article

References (21)

1. [1] Sakaguchi K, Mano H, Ohfune Y. Tetrahedron Lett. 1998;39:4311-4312.
2. [2] For reviews, see: [α-and β-silyl cations] (a) Bassindale AR, Taylor PG. In: Patai S, Rappoport Z, editors. The Chemistry of Organic Silicon Compounds Part 2. Chichester:John Wiley, 1989:Chapter14.
3. (b) Richey Jr HG, Wiberg KB, Hess Jr AB, Ashe III AJ. In: Olah GA, Schleyer PvR, editors. Carbonium Ions. Vol. 3. Chichester:John Wiley, 1976:Chapter25,26.
4. [3] For rearrangement of α-acyl-α-cyclopropyl-carbenium ion, see: Pardo C, Charpentier-Morize M. J. Chem. Soc., Chem. Commun. 1982;1037-1039.
5. 3) from 2.
6. 3CN and drying.
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8. [7] The relationship between the substituents of cyclopropane was assigned to be trans by the observation of NOEs between the corresponding methine protones as shown below. (equation presented)
9. [8] The relative structures of 4a and 5a were confirmed by comparison with rac-5 prepared as shown below. (equation presented)
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11. (R)-MTPA ester) of each MTPA ester is shown below. Ohtani I, Kusumi T, Kashman Y, Kakisawa H. J. Am. Chem. Soc. 1991;113:4092-4093. (equation presented)
12. 3) δ2.80 (ddd, J = 6.1, 6.1, 8.5 Hz, 1 H), 1.50 - 1.58(2 H), 1.67 (br, 1 H), 1.18 - 1.44 (4 H), 0.88 (t, J = 7.1 Hz, 3 H), 0.76 (m, 1 H), 0.47 (ddd, J = 4.5, 4.5, 10.2 Hz, 1 H), 0.42 (ddd, J = 7.1, 7.1, 3.9 H z, 1 H), -0.08 (s, 9 H), -0.51 (ddd, J = 6.8, 6.8, 10.2 Hz, 1 H).
13. 4 gave the same mixture where the total yields were increased (Table). The products 3a - 5a were found to be stable upon further treatment with the same reaction conditions. [19] This result indicates that the interconversion of the products did not occur.
14. 3 in MeOH, respectively.
15. 3 at -78 °C gave several less polar volatile olefinic products whose structures were not identified. The same result was obtained when 2 was employed.
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20. N2-type substitution occurred at C4 of the resulting mesylate 7 under the reaction condition.
21. 2 at -78 °C. Daniels RG, Paquette LA. J. Org. Chem. 1981;46:2901-2910.