Zr[bis(salicylidene)ethylenediaminato]-mediated Baeyer-Villiger oxidation: Stereospecific synthesis of abnormal and normal lactones

Akira Watanabe, Tatsuya Uchida, Ryo Irie, Tsutomu Katsuki

研究成果: Contribution to journalArticle査読

76 被引用数 (Scopus)

抄録

Baeyer-Villiger oxidation of racemic bicyclic cyclobutanones with Zr[bis(salicylidene)ethylenediaminato] (salen) complex 1 as catalyst in the presence of a urea-hydrogen peroxide adduct was found to proceed enantiospecifically. The enantiotopos selection in the oxidation was governed primarily by the Zr(salen) catalyst, although migratory aptitude (methine > methylene > methyl) in Baeyer-Villiger oxidation affected the selection to a varied extent, depending on the substrate structures; one enantiomer of cyclobutanones gave exclusively a normal lactone expected from the migratory aptitude, and the other enantiomer gave an abnormal lactone preferentially, the formation of which is counter to the migratory aptitude. Furthermore, the rates of abnormal lactone formation were found to be faster than those of normal lactone formation in most of the oxidations examined. For example, the enantiomer of racemic bicyclo[3.2.0]heptan-6-one giving an abnormal lactone reacted 2.2 times faster than the other enantiomer giving a normal lactone. To our knowledge, this example of chemocatalytic Baeyer-Villiger oxidation giving an abnormal lactone in preference to a normal lactone has been previously unreported. This unusual behavior is likely to be attributable to strict control of stereoelectronic demand in Baeyer-Villiger oxidation and chiral recognition by complex 1.

本文言語英語
ページ(範囲)5737-5742
ページ数6
ジャーナルProceedings of the National Academy of Sciences of the United States of America
101
16
DOI
出版ステータス出版済み - 4 20 2004

All Science Journal Classification (ASJC) codes

  • General

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