Mori A, Abe M, Nojima M
Department of Materials Chemistry, Graduate School of Engineering, Osaka University, Suita 565-0871, Osaka, Japan.
J Org Chem. 2001 May 18;66(10):3548-53. doi: 10.1021/jo015562v.
The direct oxygenation of s-trans dienes, silyl dienol ethers (SDEs) 2, by triphenyl phosphite ozonide (TPPO) has been examined in detail. The regioselective oxygenation was found to give hydroperoxide 3, alcohol 4, ketone 5, dimer 6, and peroxy phosphate 7 with concomitant formation of triphenyl phosphate 8 and diphenyl trimethylsilyl phosphate 10. The formation of peroxy phosphate 7 was found for the first time in TPPO oxygenation reactions. The low temperature (31)P and (1)H NMR spectroscopic analyses proved the direct reaction of SDEs with TPPO without generation of singlet oxygen. The formation of the oxygenated products 3-7 is reasonably explained by the intervention of the zwitterion ZI, which can be formed by the nucleophilic attack of SDE to the central oxygen of the ozonide. The regioselective attack of SDE to the central oxygen of the ozonide was supported by the quantum chemical calculation (B3LYP/6-31G).
已对亚磷酸三苯酯臭氧化物（TPPO）对反式二烯、甲硅烷基烯醇醚（SDEs）2的直接氧化反应进行了详细研究。发现区域选择性氧化生成氢过氧化物3、醇4、酮5、二聚体6和过氧磷酸酯7，同时生成磷酸三苯酯8和二苯基三甲基甲硅烷基磷酸酯10。在TPPO氧化反应中首次发现了过氧磷酸酯7的形成。低温磷-31和氢-1核磁共振光谱分析证明了SDEs与TPPO的直接反应，未产生单线态氧。两性离子ZI的介入合理地解释了氧化产物3-7的形成，ZI可由SDE对臭氧化物中心氧的亲核进攻形成。量子化学计算（B3LYP/6-31G）支持了SDE对臭氧化物中心氧的区域选择性进攻。
