Ruzicka, Frank published the artcileMethane monooxygenase catalyzed oxygenation of 1,1-dimethylcyclopropane. Evidence for radical and carbocationic intermediates, COA of Formula: C5H10O, the publication is Biochemistry (1990), 29(7), 1696-700, database is CAplus and MEDLINE.
Methane monooxygenase of Methylosinus trichosporium catalyzes the oxygenation of 1,1-dimethylcyclopropane in the presence of O2 and NADH to (1-methylcyclopropyl)methanol(81%), 3-methyl-3-buten-1-ol (6%), and 1-methylbutanol (13%). Oxygenation by 18O2 using the purified enzyme proceeds with incorporation of 18O into the products. Inasmuch as methane monooxygenase catalyzes the insertion of O from O2 into a C-H bond of alkanes, (1-methylcyclopropyl)methanol appears to be a conventional oxygenation product. 3-Methyl-3-buten-1-ol is a rearrangement product that can be rationalized on the basis that enzymic oxygenation of 1,1-dimethylcyclopropane proceeds via the (1-methylcyclopropyl)carbinyl radical, which is expected to undergo rearrangement with ring opening to the homoallylic 3-methyl-3-buten-1-yl radical in competition with conventional with ring opening to the homoallylic 3-methyl-3-butenyl-1-yl radical in competition with conventional oxygenation. Oxygenation of the latter radical gives 3-methyl-3-buten-1-ol. 1-Methylcyclobutanol is a ring-expansion product, whose formation is best explained on the basis that the 1-methylcyclobutyl tertiary carbocation is an oxygenation intermediate. This cation would result from rearrangements of carbocations derived by 1-electron oxidation of either radical intermediate. The fact that both 3-methyl-3-buten-1-ol and 1-methylcyclobutanol are produced suggests that the oxygenation mechanism involves both radical and carbocationic intermediates. Radicals and carbocations can both be intermediates if they are connected by an electron-transfer step. A reasonable reaction sequence is one in which the cofactor (μ-oxo)diiron reacts with O2 and 2-electrons to generate a H atom-abstracting species and an oxidizing agent. The H-abstracting species might be the enzymic radical or another species generated by the Fe complex and O2. Oxygenation then could proceed by abstraction for a H atom from the substrate to form a radical, followed by electron transfer from the radical to the oxidizing species to form a carbocation. The carbocation would be quenched by O associated with the oxygenation cofactor to generate the product.
Biochemistry published new progress about 20117-47-9. 20117-47-9 belongs to alcohols-buliding-blocks, auxiliary class Aliphatic cyclic hydrocarbon,Alcohol, name is 1-Methylcyclobutan-1-ol, and the molecular formula is C5H10O, COA of Formula: C5H10O.
Referemce:
https://en.wikipedia.org/wiki/Alcohol,
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