Short path syntheses of α-diozonides by sequential ozonolyses of acetylenes and O-methyl oximes
作者:Yuxiang Dong、Karl Griesbaum、Kevin J. McCullough
DOI:10.1039/a700989e
日期:——
Ozonolyses of but-2-yne 1 in the presence of added carbonyl compounds
3 afford α-oxo ozonides 4. Subsequent cycloadditions
between ozonides 4 and cyclohexanone oxide 6, generated in situ
by ozonolysis of O-methylcyclohexanone oxime, yield in turn
α-diozonides 7 into which have been incorporated the
carbon skeletons of all three substrates involved. Ozonolyses of
acyloxy-substituted but-2-ynes 9 yield the corresponding bicyclic
α-oxo ozonides 11 which subsequently participate in
analogous cycloadditions with 6 to produce the corresponding
α-diozonides 12. X-Ray crystallographic analysis of the
crystalline diozonide 12a shows that it has been formed exclusively by
exo-addition of 6 to 11a.
在添加了羰基化合物 3 的情况下,丁-2-炔 1 发生臭氧分解,生成 δ-oxo 臭氧化合物 4。随后,臭氧化物 4 与 O-甲基环己酮肟的臭氧分解在原位生成的环己酮氧化物 6 发生环加成反应,生成δ-±-二臭氧化物 7,其中包含了所涉及的所有三种底物的碳骨架。酰氧基取代的丁-2-炔 9 的臭氧分解生成相应的双环δ-氧代臭氧化物 11,随后与 6 发生类似的环化反应,生成相应的δ-二臭氧化物 12。对结晶二氮杂环酰胺 12a 的 X 射线晶体分析表明,它完全是由 6 与 11a 进行外加生成的。