三苯基膦对饱和内过氧化物的还原作用。
Triphenylphosphine reduction of saturated endoperoxides.
作者信息
Erden Ihsan, Gärtner Christian, Azimi M Saeed
机构信息
San Francisco State University, Department of Chemistry and Biochemistry, 1600 Holloway Avenue, San Francisco, California 94132, USA.
出版信息
Org Lett. 2009 Sep 3;11(17):3986-9. doi: 10.1021/ol901652u.
Triphenylphosphine reduction of saturated endoperoxides derived from 6,6-dimethylfulvene and spiro[2.4]hepta-4,6-diene in the presence of nucleophiles results in the formation of products that mainly stem from deoxygenation followed by carbocation formation. Nucleophilic attack by solvent proceeds by an S(N)1 like mechanism; allyl shifts and cyclopropylcarbinyl-cyclobutyl rearrangements also occur. With the systems lacking carbocation-stabilizing groups, the deoxygenation step is preceded by attack of H(2)O at the phosphorus.
在亲核试剂存在的情况下，用三苯基膦还原由6,6 - 二甲基富烯和螺[2.4]庚 - 4,6 - 二烯衍生的饱和内过氧化物，会生成主要源于脱氧随后形成碳正离子的产物。溶剂的亲核进攻通过类似S(N)1的机理进行；还会发生烯丙基迁移和环丙基甲基 - 环丁基重排。对于缺乏碳正离子稳定基团的体系，脱氧步骤之前是H₂O对磷的进攻。
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