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5) generated in this sequence is presumably also able to participate in a [2+2+1] reaction with 5 affording the cyclopentadienone iii, which evidently suffers reduction under the reaction conditions to cyclopentenone 16. The moderate yield observed in the key benzannulation step (31%) presumably reflects the fine balance between the desired transformation and a miriad of other possible pathways in this case. For related group 6-mediated [2+2+1] cycloadditions of eneynes see: Hoye, T. R.; Suriano, J. A. J. Am. Chem. Soc. 1993, 115, 1154.
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The [2+2+1] cycloaddition of ynol ethers with alkynes also has literature precedent (Imbriglio, J. E.; Rainier, J. D. Tetrahedron Lett. 2001, 42, 6987).
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Herndon (Herndon, J. W.; Patel, P. P. Tetrahedron Lett. 1997, 38, 59) has reported the reduction of cyclopentadienones by 'Cr(0)' in the presence of a proton source.
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The formation of cyclopentenones during Dötz reactions also has literature precedent (Yamashita, A.; Toy, A.; Watt, W.; Muchmore, C. R. Tetrahedron Lett. 1988, 29, 3403)
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5) generated in this sequence is presumably also able to participate in a [2+2+1] reaction with 5 affording the cyclopentadienone iii, which evidently suffers reduction under the reaction conditions to cyclopentenone 16. The moderate yield observed in the key benzannulation step (31%) presumably reflects the fine balance between the desired transformation and a miriad of other possible pathways in this case. For related group 6-mediated [2+2+1] cycloadditions of eneynes see: Hoye, T. R.; Suriano, J. A. J. Am. Chem. Soc. 1993, 115, 1154. The [2+2+1] cycloaddition of ynol ethers with alkynes also has literature precedent (Imbriglio, J. E.; Rainier, J. D. Tetrahedron Lett. 2001, 42, 6987). Herndon (Herndon, J. W.; Patel, P. P. Tetrahedron Lett. 1997, 38, 59) has reported the reduction of cyclopentadienones by 'Cr(0)' in the presence of a proton source. The formation of cyclopentenones during Dötz reactions also has literature precedent (Yamashita, A.; Toy, A.; Watt, W.; Muchmore, C. R. Tetrahedron Lett. 1988, 29, 3403).
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0035835953
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For a review of Brook-type rearrangements see: W.H. Moser Tetrahedron 57 2001 2065
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93
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33644840532
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note
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8Cr requires C 46.68%, H 3.36%.
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