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发展了不对称反应。前手性2，6-二丁烯基色苯铬配合物在手性钯（0）催化剂作用下发生分子内不对称Heck反应，得到光学活性的平面手性茚铬配合物。通过不对称Heck反应和Suzuki-Miyaura交叉偶联反应，得到了具有光学活性的茚满铬配合物，通过[3+2+2]-环加成反应，得到了具有光学活性的环庚三烯铬配合物，并通过α，β-不饱和Fischer卡宾配合物和平面手性芳烃铬配合物与炔反应，得到了具有光学活性的环庚三烯铬配合物。β-不饱和Fischer卡宾配合物与平面手性芳烃铬配合物通过与烯丙基醇盐反应和随后的光氧化脱金属反应得到了高达97%ee的α-烯丙基β-芳基丙酸酯。手性杂双核钨卡宾配合物 ...更多信息 通过1，3-M（CO）_5位移和[3，3]-σ转移重排反应，得到了β-芳基丙酸α-烯丙酯，并通过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。在芳香溶剂中，通过取代反应实现了位阻N-芳基吲哚铬配合物中三羰基铬的立体选择性迁移，并在Au（I）催化剂的催化下，通过环异构化反应合成了具有烯炔键的平面手性芳烃铬配合物。所得的轴手性联芳基铬配合物是手性稳定的反配合物。这些反联芳基铬络合物是显著有用的，因为我们已经报道了平面手性芳基溴铬络合物与芳基硼酸的Suzuki-Miyaura交叉偶联产生顺式联芳基铬压缩物。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