Development of Asymmetric Reactions of Diazo Carbonyl Compounds in the Presence of Metal-Catalysts having Axial Chirality

具有轴向手性的金属催化剂存在下重氮羰基化合物的不对称反应的进展

基本信息

批准号：
11640530
负责人：
SUGA Hiroyuki
金额：
$ 2.3万
依托单位：
Shinshu University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
1999
资助国家：
日本
起止时间：
1999 至 2000
项目状态：
已结题

项目摘要

In the presence of 10 mol % of rare earthmetal triflate as catalyst, the reaction of pheriyldiazoacetate with alcohols proceeded smoothly to give desired α, α-substituted products in high yield. Moderate diastereoselectivity was obtained in the reaction of l-menthyl phenyldiazoacetate. The use of the catalysts, which were prepared by mixing the ligands having axial chirality such as binaphthol and binaphthyldiimine derivatives with rare earth metal triflates, did not show satisfactory results in terms of selectivity and chemical yield.Stereocontrol by using Lewis acid in the reaction of 2-benzopyrylium-4-olate, which was generated by Rh_2( OAc )_4-catalyzed decomposition of o-methoxycarbonyl-α-diazbacetophenone, was also investigated. In the reaction with N-substituted maleimide under reflux in benzene showed exo-selectivity, while the reaction in the presence of 10 mol % of Yb( OTf )_3 in CH_2Cl_2 at room temperature proceed with high endo-slectivity. On the other hand, addition of 10 mol % of Yb( OTf )_3 was quite effective in obtaining high exo-selectiyity in the reaction with benzaldehyde, p-substituted benzaldehyde, and benzyloxyacetoaldehyde in Et_2O or CH_2Cl_2. We also found that the use of 10 mol % of lanthanide tris( S )-1,1'-binaphthyl-2,2'-diyl phosphate, known to be an effective catalyst for hetero Diels-Alder reaction of Danishefsky's diene, showed moderate enantioselectivity (endo: 20 - 52 % ee), although almost no diastereoselectivity was observed. Furthermore, in the presence of the chiral catalyst, which was prepared from 2,6-bis[( 4S )-( - )-isopropyl-2-oxazolin-2-yl]pyridine and Sc( OTf )_3, enantioselectivity of the endo-product showed 86 % ee ( endo : exo = 76 : 24 ). To the best of knowledge, this is the first example of asymmetric induction found in the chiral Lewis acid-catalyzed cycloaddition reaction of a carbonyl ylide.

在10 mol%稀土金属三氟甲磺酸盐作为催化剂的情况下，苯基重氮乙酸酯与醇的反应顺利进行，在1-薄荷基苯基重氮乙酸酯的反应中以高收率得到了所需的α,α-取代产物。催化剂的制备方法是将具有轴向手性的配体如联萘酚和联萘二亚胺与稀土金属三氟甲磺酸酯的衍生物在选择性和化学产率方面没有表现出令人满意的结果。利用Lewis酸立体控制Rh_2(OAc)_4催化分解生成的2-苯并吡喃鎓-4-油酸盐的反应还研究了邻甲氧基羰基-α-二氮苯乙酮在回流下与N-取代马来酰亚胺的反应。苯表现出外选择性，而在CH_2Cl_2中室温下10 mol% Yb(OTf)_3存在下反应具有高内选择性；而添加10 mol% Yb(OTf)_3时反应具有高内选择性。在与苯甲醛、对位取代苯甲醛的反应中非常有效地获得高外选择性，我们还发现使用 10 mol% 的镧系元素三(S)-1,1'-联萘基-2,2'-磷酸二酯，它是杂狄尔斯-阿尔德反应的有效催化剂。达尼塞夫斯基的二烯，显示出中等的对映选择性（endo：20 - 52 % ee），尽管此外，在由2,6-双[(4S)-(-)-异丙基-2-恶唑啉-2-基]吡啶和Sc(OTf)制备的手性催化剂存在下，几乎没有观察到非对映选择性。 _3，内产物的对映选择性显示 86 % ee ( endo : exo = 76 : 24 )。在手性路易斯酸催化的羰基叶立德环加成反应中发现了不对称诱导。