SYNTHESIS OF [R,S-R,S]-BIS[2-[1-(DIMETHYLAMINO)ETHYL]FERROCENYL]DISELENIDES AND [S,R-S,R]-BIS[2-[1-(DIMETHYLAMINO)ETHYL]FERROCENYL]DISELENIDES AND THEIR APPLICATION TO ASYMMETRIC SELENOXIDE ELIMINATION AND [2,3]SIGMATROPIC REARRANGEMENT
SYNTHESIS OF [R,S-R,S]-BIS[2-[1-(DIMETHYLAMINO)ETHYL]FERROCENYL]DISELENIDES AND [S,R-S,R]-BIS[2-[1-(DIMETHYLAMINO)ETHYL]FERROCENYL]DISELENIDES AND THEIR APPLICATION TO ASYMMETRIC SELENOXIDE ELIMINATION AND [2,3]SIGMATROPIC REARRANGEMENT
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DOI：
10.1021/jo00118a031
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发表时间：
1995-06-30
影响因子：
3.6
通讯作者：
UEMURA, S
中科院分区：
文献类型：
--
作者：
NISHIBAYASHI, Y;SINGH, JD;UEMURA, S
通过手性[1-（二甲氨基）乙基]二茂铁的锂化反应，再与硒元素反应，在空气中氧化，合成了具有两个轴向手性元素和两个中心手性元素的新型光学活性双[2-[1-（二甲氨基）乙基]二茂铁基]二硒醚（[R，S;R，S]和[S，R;S，R]），分离产率为77-80%。[S，R;S，R]-双二茂铁基二硒醚的结构已通过X射线晶体学充分表征。通过二硒醚与相应的丙炔酸酯衍生物和烯丙基卤化物反应，新合成了六个手性二茂铁乙烯基硒醚和六个手性烯丙基二茂铁硒醚。在不同的有机溶剂中，间氯过苯甲酸氧化烯硒醚通过不对称硒氧化物消除产生轴向手性丙二烯羧酸酯，化学产率为27-59%，具有高的对映选择性（高达89%ee）。烯丙基硒醚的类似处理通过不对称[2，3] σ转移重排得到相应的手性烯丙基醇，化学产率为28-82%，具有高的对映选择性（高达89%ee）。所观察到的高对映选择性表明，氧化进行高度非对映选择性，所得到的手性硒氧化物是缓慢的外消旋化，以及硒氧化物消除和[2，3]sigmatropic重排进行的光学活性的损失很小。
Novel optically-active bis[2-[1-(dimethylamino)ethyl]ferrocenyl] diselenides ([R,S;R,S] and [S,R;S,R]), each of which possesses two axial and two central elements of chirality, have been prepared by lithiation of commercially available chiral [1-(dimethylamino)ethyl]ferrocenes, followed by reaction with elemental selenium and air oxidation, in 77-80% isolated yields. The structure of the [S,R;S,R]-bisferrocenyl diselenide has been fully characterized by X-ray crystallography. Six chiral ferrocenyl vinylic selenides and six chiral allylic ferrocenyl selenides have been newly prepared by reaction of the diselenides with the corresponding propiolate derivatives and allylic halides. The oxidation of the vinylic selenides with m-chloroperbenzoic acid in various organic solvents produces axially chiral allenecarboxylic esters via asymmetric selenoxide elimination in 27-59% chemical yields with high enantioselectivities (up to 89% ee). Similar treatment of the allylic selenides afforded the corresponding chiral allylic alcohols via asymmetric [2,3]sigmatropic rearrangement in 28-82% chemical yields with high enantioselectivities (up to 89% ee). The observed high enantioselectivities indicate that oxidation proceeds highly diastereoselectively, that the resultant chiral selenoxides are slow to racemize, and also that selenoxide elimination and [2,3]sigmatropic rearrangement proceed with little loss of optical activity.