Osmium-catalyzed dihydroxylation of olefins using dioxygen or air as the terminal oxidant

被引:159
作者
Döbler, C [1 ]
Mehltretter, GM [1 ]
Sundermeier, U [1 ]
Beller, M [1 ]
机构
[1] Univ Rostock EV, IfOK, D-18055 Rostock, Germany
关键词
D O I
10.1021/ja000802u
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
The osmium-catalyzed dihydroxylation of various olefins using molecular oxygen or air as the stoichiometric oxidant is reported. Aromatic olefins yield the corresponding diols in good to excellent chemoselectivities under optimized pH conditions (pH = 10.4-12.0), Air can be used under moderate pressures (3-9 bar) instead of dioxygen as the reoxidant. By increasing the oxygen content of the solution, it is possible to achieve highly efficient conversion at low catalyst amount (catalyst/substrate = 1:4000). Tri- and tetrasubstituted olefins are oxidized at pH > 11 to give the corresponding 1,2-diols in good to very good yields without requiring the addition of sulfonamides or other hydrolysis agents. Studies of the dihydroxylation of functionalized olefins demonstrate that the reaction conditions tolerate a variety of functional groups. In the presence of dihydroquinine or dihydroquinidine derivatives (Sharpless ligands), asymmetric dihydroxylations occur with lower enantioselectivities than tose of the classical K-3[Fe(CN)(6)] reoxidation system.
引用
收藏
页码:10289 / 10297
页数:9
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