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Volumn 64, Issue 25, 1999, Pages 8995-9000

PhI(OAc)2-promoted rearrangement of the hydroxyl group: Ring expansion of 4-hydroxy-2-cyclobutenone to 2(5H)-furanone in comparison with ring cleavage of the α-hydroxycycloalkanone to the ω-formyl ester

Author keywords

[No Author keywords available]

Indexed keywords

CYCLOALKANONE; ESTER DERIVATIVE; FURANONE DERIVATIVE; HYDROXYL GROUP;

EID: 0032804090     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo990704v     Document Type: Article
Times cited : (34)

References (41)
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    • For recent examples, see: (a) Sun, L.; Liebeskind, L. S. Tetrahedron Lett. 1997, 38, 3663. (b) Onofrey, T. J.; Gomez, D.; Winters, M.; Moore, H. W. J. Org. Chem. 1997, 62, 5658. (c) Liu, F.; Liebeskind, L. S. J. Org. Chem. 1998, 63, 2835. (d) Heileman, M. J.; Moore, H. W. Tetrahedron Lett. 1998, 39, 3643.
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    • note
    • Liberated acetic acid seemed to play no significant role in the rearrangement, since intentional removal of the acid caused the better yield of the rearranged product (entry 7 in Table 1); thus, a glycol cleavage pathway as depicted below is not likely. (equation presented)
  • 28
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    • note
    • Predominant formation of the (Z)-isomer 17 from 9e was suggested by analogy with the reaction of 9e to 11. In the case of 18, no selectivity was observed because of no stereochemical difference between (Z)- and (E)-isomers. PM3 calculations indicated that 17 was more stable than the corresponding E-isomer by 4.1 kcal/mol but energy difference was only 0.5 kcal/mol between (Z)- and (E)-18.
  • 29
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    • 4,5 = 1.0-1.2 Hz) were nicely correlated with those of 2,5-dihydrofuran: Lozach, R.; Braillon. B. J. Magn. Reson. 1973, 12, 244.
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    • note
    • In this case the opened acyl cation 14 might be trapped with a solvent to give 23, but this possibility could be subdued by preferential cyclization of this cation with a proximate carbonyl end in the cisolefinic configuration
  • 38
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    • note
    • If the ring expansion mechanism was operative also for 27a, a butyrolactone might be produced. However, this is not the case, and the difference in reactivity between cyclobutenone such as 9a and cyclobutanone such as 27a seems to be attributed to ring strain relief of the four-membered rings and stabilization of the opened acyl cations by conjugation, both of which are influenced by double vs single bond nature adjacent to the carbonyl group. These are apparently advantageous for 9a to undergo ring-opening.


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