[2 + 2 + 2] Cycloadditions
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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 ]

Formal [2 + 2 + 2] Cycloaddition Strategies

Our laboratory has developed metal-free, formal [2 + 2 + 2] cycloaddition strategies based on cascades of pericyclic reactions.  The first step in the cascade involves an unusual propargylic ene reaction to generate a vinylallene or allenylimine intermediate, which then undergoes an inter- or intramolecular Diels-Alder or hetero Diels-Alder reaction.

References:

"Cyano Diels-Alder and Cyano Ene Reactions.  Applications in a Formal [2 + 2 + 2] Cycloaddition Strategy for the Synthesis of Pyridines.", T. Sakai and R. L. Danheiser, J. Am. Chem. Soc. 2010, 132, 13203.
 

"Formal [2 + 2 + 2] Cycloaddition Strategy Based on an Intramolecular Propargylic Ene Reaction/Diels-Alder Cycloaddition Cascade", J. M. Robinson, T. Sakai, K. Okano, T. Kitawaki, and R. L. Danheiser, J. Am. Chem. Soc. 2010, 132, 11039.

 

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 ]

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Last modified: June 23, 2012