Publication: Zwitterion from a Cyclopropane with Geminal Donor and Acceptor Groups.

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Title	Zwitterion from a Cyclopropane with Geminal Donor and Acceptor Groups.
Authors/Editors*	Anna Sliwinska, Wojciech Czardybon, John Warkentin
Where published*	Org. Lett.
How published*	Journal
Year*	2007
Volume	9
Number	4
Pages	695 -698
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Abstract	2,2-Dimethoxy-3,3-dicyanospiro[cyclopropane-1,9'-[9H]fluorene] reacted fast with methanol to afford 9-trimethoxymethyl-9-dicyanomethyl-9H-fluorene. Reaction with benzaldehydes also gave products of cyclopropane ring opening. Strong electron-donor p-substituents or a strong attractor enhanced the rate. Ring opening of the cyclopropane to a zwitterion that recloses or reacts with an aryl aldehyde, to form either a CO or a CC bond first, can explain the result. The former mode of closure is sensitive to p-substituents because they are directly conjugated to the positive charge at the benzylic carbon of the former aldehyde. The latter mode is sensitive to the ground-state electrophilicity of the carbonyl carbon of the former aldehyde. Thus, reaction of the cyclopropane with p-substituted aldehydes is accelerated by either electron-donor or -acceptor substituents.