Acid-catalyzed rearrangement of α-hydroxytrialkylsilanes

Tetrahedron

Volumn 59, Issue 34, 2003, Pages 6647-6658

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

^a Osaka Prefecture University   (Japan)

Author keywords

Acid catalyzed rearrangement; Tandem 1,2 shift; hydroxysilane; silyl cation

Indexed keywords

1 (2 TERT BUTYLDIMETHYLSILYLCYCLOPROPYL)ETHANOL; 1 TERT BUTYLDIMETHYLSILYL 1 BUTANOL; 1 TERT BUTYLDIMETHYLSILYL 1 MESYLOXY 2 BUTYNE; 1 TERT BUTYLDIMETHYLSILYL 2 BUTEN 1 OL; 1 TERT BUTYLDIMETHYLSILYL 3 MESYLOXY 1,2 BUTADIENE; 2 METHYLCYCLOPROPYL TERT BUTYLDIMETHYLSILYL KETONE; 4 TERT BUTYLDIMETHYLSILYL 3 BUTEN 2 OL; 5 TERT BUTYLDIMETHYLSILYL 4 PENTEN 2 OL; ALCOHOL DERIVATIVE; ALLENE DERIVATIVE; ALLYL COMPOUND; ALPHA HYDROXYCYCLOPROPYLSILANE; KETONE DERIVATIVE; SILANE DERIVATIVE; SULFURIC ACID; UNCLASSIFIED DRUG; VINYL DERIVATIVE; VINYLSILANE;

ARTICLE; CATALYSIS; CHEMICAL BOND; ENANTIOMER; ISOMER; PRIORITY JOURNAL;

EID: 0041701543     PISSN: 00404020     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4020(03)00952-9     Document Type: Article

References (29)

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18. Hydrogenation of (R)-6 using 10% Pd-C afforded the silyl ketone 35 in good yield.
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20. 4 (20 equiv.) in THF at rt for more than 20 h resulted in a recovery of 15 accompanied with a trace amount of 14.
21. The carbocationic rearrangement such as the ring expansion of a cyclopropylacylsilane to a cyclobutanone has been reported. (a) Danheiser R.L., Fink D. Tetrahedron Lett. 26:1985;2513-2516 (b) Nakajima T., Segi M., Mitsuoka T., Fukute Y., Honda M., Naitou K. Tetrahedron Lett. 36:1995;1667-1670.
22. The carbocationic rearrangement such as the ring expansion of a cyclopropylacylsilane to a cyclobutanone has been reported. (a) Danheiser R.L., Fink D. Tetrahedron Lett. 26:1985;2513-2516 (b) Nakajima T., Segi M., Mitsuoka T., Fukute Y., Honda M., Naitou K. Tetrahedron Lett. 36:1995;1667-1670.
23. 1H NMR.
24. The alcohol (S,Z)-24 was prepared from α-hydroxyalkynylsilane (S)-32 by hydrogenation using the Lindlar catalyst.
25. 8 and the allylic chloride 36 (32%).
26. The absolute configuration of the allene 27 was not determined.
27. Burgess K., Jennings L.D. J. Am. Chem. Soc. 113:1991;6129-6139.
28. (R)-2-Octanol (>95% ee) is commercially available from Kawaken Fine Chemicals Co. Ltd.
29. 2, rt, 2.5 h, quant} On the other hand, the reaction of the propargylic alcohol (S)-32 under the same conditions did not give its mesylate but gave the propargylic chloride 37 (68%).