Asymmetric Reactions Utilizing Planar Chiral Transition Metal Complexes

我们利用平面手性芳烃过渡金属配合物开发了不对称反应。采用手性钯(0)催化剂对2,6-二丁基氯苯铬配合物进行分子内不对称Heck反应，得到具有光学活性的平面手性铬配合物。通过串联不对称Heck反应，再与芳基硼酸进行Suzuki-Miyaura交叉偶联，得到具有光学活性的茚铬配合物。双核α，β-不饱和菲舍尔碳配合物与平面手性芳烃铬配合物通过[3+2+2]环加成反应与具有光学活性的环庚三烯铬配合物反应，具有高非对映选择性。此外，双核α，β-不饱和菲舍尔卡宾配合物与平面手性芳烃铬配合物通过与烯丙醇的反应和随后的光氧化脱金属，使α-烯丙基β-芳基丙酸酯的ee高达97%。反应产物α-烯丙基β-羟基β-芳基丙酸酯通过1,3- m (CO)_5移位和随后的[3,3]-异位重排得到α-烯丙基β-芳基丙酸酯。采用平面手性芳烃铬配合物的立体选择性亲核取代反应合成了具有轴向手性N-C键的n -芳基吲哚。通过在芳香溶剂中回流，在位阻n -二烷基吲哚铬配合物中实现了三羰基铬的立体选择性迁移。在Au(I)催化剂的催化下，通过环异构化反应得到轴向手性双芳基铬配合物。所制得的轴手性联芳基铬配合物是热力学稳定的反配合物。这些抗联芳基铬配合物是非常有用的，因为我们已经报道了平面手性芳基溴铬配合物与芳基硼酸的Suzuki-Miyaura交叉偶联产生了联芳基铬压缩物。少

We have developed asymmetric reactions by utilizing planar chiral arene transition metal complexes. Prochiral 2,6- dibutenylchrorobenzene chromium complex was subjected intramolecular asymmetric Heck reaction by treatment with chiral palladium(0) catalyst to give optical active indene chromium as planar chiral chromium complex. Furthermore, tandem asymmetric Heck reaction followed by Suzuki-Miyaura cross coupling with arylboronic acid gave optically active indane chromium complex.Binuclear α,β-unsaturated Fischer carbene complexes with planar chiral arene chromium complexes were reacted with alkynes gave optically active cycloheptatriene chromium complexes via [3+2+2]-cycloaddition with high diastereoselectivity.Moreover, binuclear α,β-unsaturated Fischer carbene complexes with planar chiral arene chromium complexes gave α- allyl β-arylpropionates up to 97% ee by reaction with allyl alkoxide and subsequent photo-oxidative demetalation. The chiral hetero-binuclear tungsten carbene compl … More exes afforded anti α-allyl β-hydoxy β-arylpropionates as a major product up to 92/8 dr. The reaction products, α-allyl β-arylpropionates were derived by 1,3-M(CO)_5 shift and subsequent [3,3]-sigmatropic rearrangement.N-Aryl indoles with axially chiral N-C bonds were synthesized by stereoselective nucleophilic substitution reactions of planar chiral arene chromium complexes. Stereoselective chromium tricarbonyl migration was achieved in the sterically hindered N-ary indole chromium complex by refluxing in aromatic solvent.Planar chiral arene chromium complexes with enyne bond were catalyzed by Au(I) catalyst to give axially chiral biaryl chromium complexes by cycloisomerization reactions. The obtained axially chiral biaryl chromium complexes are thermodynamically stable anti-complexes. These anti-biaryl chromium complexes are significant useful, since we have already reported that Suzuki-Miyaura cross coupling of planar chiral aryl bromide chromium complexes with arylboronic acids produced syn-biaryl chromium compresses. Less