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Rearrangement of a Cyclohexyl Radical to a Cyclopentylmethyl Radical on the Avermectin Skeleton.

  作者 Kessabi, Fiona Murphy;Winkler, Tammo;Luft, Jennifer A. R.;Houk, K. N.;  
  选自 期刊  Organic Letters;  卷期  2008年10-11;  页码  2255-2258  
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[摘要]The rearrangement of a substituted cyclohexyl radical to a cyclopentylmethyl radical on the skeleton of avermectin B1 was obsd. exptl. and explored computationally. The Stork-Nishiyama methodol. was applied to the macrocycle of interest followed by a Tamao oxidn. The expected 5-6 fused ring product was obsd. in minor amts. The major product was a 5-5 fused ring resulting from apparent conversion of the initially formed cyclohexyl radical to a cyclopentylmethyl radical. Preliminary computational results indicate that substituents in the macrocycle induce the rearrangement.

 
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