Enantioselective reduction of benzoyl derivatives of ferrocene and ruthenocene; Optically active carbinols and carbenium ions
作者:Marina N. Nefedova、Irina A. Mamedyarova、Pavel P. Petrovski、Viatcheslav I. Sokolov
DOI:10.1016/0022-328x(92)80028-v
日期:1992.2
reduced using the LiAlH4 -Chirald complex to afford the corresponding carbinols and diols enantiomerically enriched. Optical yield was 53% for benzoylferrocene and 86% for benzoylruthenocene, (R)-configuration being predominant. Monocations had an opposite sign of rotation and were stable in CF3COOH. On the contrary, diols have lost optical rotation in the same acid that has been explained by formation of
单-和1,1'-二取代的茂金属,XC 5 ħ 4 MC 5 ħ 4 Y,M铁,钌,XH,YCOPH,或XÝCOPH,已使用的LiAlH减少4 -手性配合物,得到对映体富集的相应的甲醇和二醇。苯甲酰基二茂铁的光学产率为53%,苯甲酰基钌茂金属的光学产率为86%,(R)-构型是主要的。单阳离子具有相反的旋转符号,并且在CF 3 COOH中稳定。相反,二醇在相同的酸中失去了旋光性,这已通过形成非手性醚中间体来解释。如1所示,在DSO 3 F中形成了阳离子1 H NMR谱,但即使在低温下也完全消旋。