Hay E Ben, Zhang Hanmo, Curran Dennis P
Department of Chemistry, University of Pittsburgh , Pittsburgh, Pennsylvania 15260, United States.
J Am Chem Soc. 2015 Jan 14;137(1):322-7. doi: 10.1021/ja510608u. Epub 2014 Dec 22.
1,1-Divinyl-2-phenylcyclopropanes are entry points to a rich area of rearrangement chemistry. With N,N-diallyl amide substrates, tandem radical cyclizations can be initiated at room temperature. Warming provides products of pure thermal rearrangements with acids, ester, and amides. These isomerizations give vinylcyclopentenes resulting from divinylcyclopropane rearrangements and more deeply rearranged tricyclic spirolactams resulting from aromatic Cope rearrangements followed by ene reactions. Conversion of the carbonyl group to an alcohol or ether opens retro-ene pathways followed by either tautomerization or Claisen rearrangement.
1,1 - 二乙烯基 - 2 - 苯基环丙烷是丰富的重排化学领域的切入点。对于N,N - 二烯丙基酰胺底物，串联自由基环化反应可在室温下引发。加热可得到与酸、酯和酰胺发生纯粹热重排的产物。这些异构化反应产生由二乙烯基环丙烷重排得到的乙烯基环戊烯，以及由芳香族科普重排随后进行烯反应得到的更深层次重排的三环螺内酰胺。将羰基转化为醇或醚会开启逆烯反应途径，随后进行互变异构或克莱森重排。
