The Development and Application of a New Class of Monodentate Optically Active Phosphines (MOP's). Asymmetric Hydrosilylation of Olefins Catalyzed by Palladium-MOP Complexes
The Development and Application of a New Class of Monodentate Optically Active Phosphines (MOP's). Asymmetric Hydrosilylation of Olefins Catalyzed by Palladium-MOP Complexes
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一类新型单齿光学活性膦（MOP）的开发和应用。
DOI：
10.5059/yukigoseikyokaishi.51.1087
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发表时间：
1993
影响因子：
0.2
通讯作者：
Tamio Hayashi
中科院分区：
文献类型：
--
作者：
Y. Uozumi;Tamio Hayashi
制备了轴手性单齿光活性膦1，(S)-2-（二苯基膦）-2'-甲氧基- 1,1，-联萘基（MOP, 1b）及其类似物。简单末端烯烃6 （RCH=CH2）的反应。R=n-C4H9, n-C6H13, n-C13H21, PhCH2CH2，环- c6h11)与三氯硅烷在0.1或0.01 mol %的钯催化剂存在下，在40°C下，由[PdCl (π-C3H5)]2和(S)-1b原位制备，以异常的区域选择性（高达94%）和高对映选择性得到高产率的2-（三氯硅基）烷烃7a和少量的1-（三氯硅基）烷烃7b。碳硅键氧化得到具有光学活性的醇9 (RCH(OH)CH3)，其对映体纯度在94% ~ 97% ee之间。在MOP/钯的催化下，降冰片烯（19）和相关的介环双环烯烃的对映选择性氢化反应中也观察到高的对映选择性，该反应使外显-2-降冰片纳米醇（21）及其相关醇的ee含量高达96%。
Axially chiral monodentate optically active phosphines 1, (S)-2-(diphenylphosphino)-2'-methoxy-1, 1, -binaphthyl (MOP, 1 b) and its analogs were prepared. Reaction of simple terminal alkenes 6, (RCH=CH2. R=n-C4H9, n-C6H13, n-C13H21, PhCH2CH2, cyclo-C6H11) with trichlorosilane at 40°C in the presence of 0.1 or 0.01 mol % of palladium catalyst, prepared in situ from [PdCl (π-C3H5)]2 and (S)-1b, proceeded with unusual regioselectivity (up to 94%) and with high enantioselectivity to give high yields of 2-(trichlorosilyl) alkanes 7a together with a minor amount of 1-(trichlorosilyl) alkanes 7b. Oxidation of the carbon-silicon bond gave optically active alcohols 9 (RCH(OH)CH3), with the enantiomeric purity ranging between 94% and 97% ee. The high enantioselectivity was also observed in the enantioposition-selective hydrosilylation of norbornene (19) and related meso bicyclic olefins catalyzed by the MOP/palladium, which gave exo-2-norbornanol (21) and the related alcohols with up to 96% ee.