@article{oai:kanagawa-u.repo.nii.ac.jp:00013579,
 author = {加部, 義夫},
 journal = {Science Journal of Kanagawa University},
 month = {Oct},
 note = {Organic compounds containing carbon-metal bonds are called organometallic compounds. Such compounds have been known and studied since 19th century and have been widely used to effect synthetic transformation in modern organic chemistry. It seemed that many educational benefits could result in the use of reaction types and discovery episodes for undergraduate and graduate classes in organic and organometallic chemistry. The former half of this report deals with O2 and the related chemistry, the latter half deals with transition metal peroxo- and oxo- complexes. The dangerously explosive properties of hydroperoxide disturbed the development of O2 chemistry, which is primarily a product of autooxidation. However, Criegee successfully isolated hydroperoxide for the first time and also proposed and developed the mechanism of ozonolysis and OsO4 reagent of 1,2-dihydroxylation for alkenes. Then, hydroperoxide was employed in industrial synthesis of phenol and propylene oxide, the so called cumene and oxirane methods respectively. In the chemical laboratory, carbonic peracid is frequently used for the epoxiation of alkenes and Bayer-Villiger reaction of ketones. Instead of carbonic peracid, persulfate (caroate) with ketone resulted in the formation of dioxirane, which is a three membered cyclic peroxide. Singlet oxygen in dye-sensitized photooxygenation was verified as non-radical oxidation, which afforded hydroperoxide as well as four-membered cyclic peroxide via a concerted mecahnism. The four-membered peroxide called 1,2-dioxetanes produced light during decomposition, begging the chemistry of chemiluminescence. In biological systems, O2 serves a central role in aerobic respiration to make energy. Oxygen binding hemoprotein such as Hemoglobin, superoxo-Fe（Ⅲ） complex, transport bound oxygen to cells, which was chemically modeled by Collmann and others. In hem-containing monooxygenase, oxo O=Fe(V) complexes such as the P-450 enzyme catalyzes hydroxylation and epoxidation for the detoxification of metabolites. These were also chemically modeled by Groves and others. In synthetic organic chemistry, many oxo- and peroxometal O=M and O2M have been used in stoichiometric oxidation of alcohol to carbonyl compounds and alkene to epoxide and 1,2-diol. Finally, asymmetric epoxidation and dihydroxylation by Ti-tert-butyl hydroperoxide and OsO4 were achieved by Sharpless and coworkers., Departmental Bulletin Paper, 教育論文},
 pages = {93--102},
 title = {反応のタイプと発見のエピソードで学ぶ有機金属化学(7)},
 volume = {31},
 year = {2020}
}