Rhenium-catalyzed epoxide deoxygenation: Scope and limitations
Rhenium-catalyzed epoxide deoxygenation: Scope and limitations
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DOI：
10.1055/s-2003-42076
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发表时间：
2003-11-01
期刊：
影响因子：
2
通讯作者：
Brown, EC
中科院分区：
文献类型：
--
作者：
Gable, KP;Brown, EC
在75-105 ℃的苯中，Tp'ReO 3 [Tp' =邻-三-（3，5-二甲基吡唑基）硼酸酯]有效地催化了氧原子从环氧化物到三苯基膦的转移。该反应容许各种各样的官能团，包括酮（与新双键共辄或非共辄）、酯、腈、醚、甲硅烷基醚和邻苯二甲酰亚胺。相对速率随取代模式和电子而变化;一般而言，单取代和2，2-二取代的环氧化物反应最快，顺式-2，3-二取代的系统比反式反应更快。吸电子取代基促进反应。
Transfer of oxygen atoms from epoxides to triphenylphosphine is efficiently catalyzed by Tp'ReO3 [Tp' = hydrido-tris-(3,5-dimethylpyrazolyl)borate] in benzene at 75-105 degreesC. The reaction tolerates a wide variety of functional groups including ketones (conjugated or non-conjugated to the new double bond), esters, nitrites, ethers, silyl ethers and phthalimides. Relative rates vary with substitution pattern and electronics; in general, monosubstituted and 2,2-disubstituted epoxides react fastest, and cis-2,3-disubstituted systems react faster than trans. Electron-withdrawing substituents promote the reaction.