Mechanism of 1,2-cycloaddition of singlet oxygen to alkenes. Trapping a perepoxide intermediate
Mechanism of 1,2-cycloaddition of singlet oxygen to alkenes. Trapping a perepoxide intermediate
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单线态氧与烯烃的 1,2-环加成机理。
DOI：
10.1021/ja00791a051
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发表时间：
1973
期刊：
影响因子：
--
通讯作者：
G. Faler
中科院分区：
文献类型：
--
作者：
A. Schaap;G. Faler
(10)R.Hiatt在《氧化》第2卷，R.L.Augustine和D.J.Trecker，Ed.，Marcel Dekker，New York，NY，第113页。(11)C.OvannéS和T.Wilson，J.Amer。化学。Soc.，90,6528(1968)。将1，3和四苯基卟啉的脱气溶液放入频那科酮中，不产生环氧化物4。乙酸叔丁酯不是通过制备性GC纯化的四苯基卟啉在频那科酮中的氧饱和溶液的光解而产生的。此外，在CH2C12中用四苯基膦光氧化1可以定量地得到3，其含量为-0.1%。在频那酮中1的光氧化反应中生成4和5的反应可以用公式2所示的Baeyer-Villiger型机理进行。我们得出结论：环氧化物4来自于环氧化物2。我们认为2也是生成二氧杂环己烷3的关键中间体。然而，我们还不能排除3是由单线态氧与1交替地同时反应而形成的可能性。这方面的进一步实验正在进行中。
(10) R. Hiatt in" Oxidation,” Vol. 2, R. L. Augustine and D. J. Trecker, Ed., Marcel Dekker, New York, NY, p 113.(11) C. Ovannés and T. Wilson, J. Amer. Chem. Soc., 90, 6528 (1968). tion of a degassed solution of 1, 3, and tetraphenylporphine in pinacolone yields no epoxide 4. tert-Butyl acetate (5) is not produced by photolysis of an oxygen saturated solution of tetraphenylporphine in pinacolone purified by preparative gc. Further, photooxidation of 1 in CH2C12 with tetraphenylporphine yields 3 quantitatively with< 0.1% of 4. The formation of 4 and 5 in the photooxidation of 1 in pinacolone can be accommodated by the Baeyer-Villiger type mechanism shown in eq 2.We conclude that epoxide 4 is derived from the perepoxide 2. It is proposed that 2 is also the key intermediate in the generation of dioxetane 3. How-ever, we cannot yet exclude the possibility that 3 is formed by an alternate, concurrent reaction of singlet oxygen with 1. Further experiments in this regard are in progress.