Collman J P, Brauman J I, Meunier B, Raybuck S A, Kodadek T
Proc Natl Acad Sci U S A. 1984 May;81(10):3245-8. doi: 10.1073/pnas.81.10.3245.
The mechanism of the Mn(III) porphyrin-catalyzed epoxidation of olefins by lithium hypochlorite is examined. The active oxidant is thought to be a high-valent manganese-oxo complex. It is shown that a relatively stable intermediate is reversibly formed upon interaction of the olefin and the oxo complex. The decomposition of this intermediate to Mn(III) porphyrin and epoxide is the rate-determining step of the catalytic cycle. Some analogies to the biochemical epoxidation of olefins catalyzed by cytochrome P-450 are discussed.
研究了锰(III)卟啉催化次氯酸锂对烯烃进行环氧化反应的机理。活性氧化剂被认为是一种高价锰-氧络合物。结果表明,烯烃与氧络合物相互作用时会可逆地形成一种相对稳定的中间体。该中间体分解为锰(III)卟啉和环氧化物是催化循环的速率决定步骤。还讨论了与细胞色素P-450催化的烯烃生化环氧化反应的一些相似之处。