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Annulation Strategies Based on Anion-Accelerated Vinylcyclopropane and Vinylcyclobutane Rearrangements

The first anion-accelerated vinylcyclopropane rearrangement was reported by our laboratory and in subsequent studies we have applied this chemistry in highly stereoselective [4+1] annulation methods for the synthesis of cyclopentenes. In related work, we have also developed [3+3] and [4+2] annulation routes to cyclohexenols based on oxyanion-accelerated vinylcyclobutane rearrangements.

For a review, see:  "Charge-Accelerated Small Ring Rearrangements", J. J. Bronson and R. L. Danheiser, Comprehensive Organic Synthesis, Vol. 5, L. A. Paquette, Ed.

[4 + 1] Annulation via Oxyanion-Accelerated Vinylcyclopropane Rearrangement

References:

"Synthesis of 3-Cyclopentenols by Alkoxy-accelerated Vinylcyclopropane Rearrangement", R. L. Danheiser, C. Martinez-Davila, and J. M. Morin, J. Org. Chem. 1980, 45, 1340.

"A Stereoselective Synthesis of Cyclopentene Derivatives from 1,3-Dienes", R. L. Danheiser, C. Martinez-Davila, R. J. Auchus, and J. T. Kadonaga, J. Am. Chem. Soc.1981, 103, 2443.

Cyclohexenol Annulation via Oxyanion-Accelerated Vinylcyclobutane Rearrangement

References:

"Cyclohexenol Annulation via the Alkoxy-accelerated Rearrangement of Vinylcyclobutanes", R. L. Danheiser, C. Martinez-Davila, and H. Sard, Tetrahedron 1981, 37, 3943.

[4 + 1] Annulation via Carbanion-Accelerated Vinylcyclopropane Rearrangement

References:

"The Carbanion-Accelerated Vinylcyclopropane Rearrangement. Application in a General, Stereocontrolled Annulation Approach to Cyclopentene Derivatives", R. L. Danheiser, J. J. Bronson, and K. Okano, J. Am. Chem. Soc. 1985, 107, 4579.

[ Home ] [ [2 + 2 + 2] Cycloaddition Strategies ] [ [3 + 2] Annulations of Organosilanes ] [ Vinylcyclopropane Rearrangements ] [ Cycloadditions and Annulations of Vinylketenes ] [ Highly Unsaturated, Conjugated Molecules ] [ [4 + 2] Cycloadditions of Imine Derivatives ] [ Ketene [2 + 2] Cycloadditions ] [ Acylsilanes ] [ B-Lactones ] [ Cyclopropylboranes ] [ Allenylsilanes and Homopropargylic Alcohols ] [ Cationic Cyclizations ] [ Synthesis of Azulenes ] [ Miscellaneous Synthetic Methods ]