Asymmetric Reactions Utilizing Planar Chiral Transition Metal Complexes

我们利用平面手性芳烃过渡金属络合物进行了不对称反应。前手性2，6-二丁烯基氯苯铬络合物在手性钯(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铬配合物。此外，不对称Heck反应后与芳基硼酸发生交叉偶联反应得到光学活性的吲哚铬配合物。通过[3+2+2]-环加成反应得到具有高非对映选择性的平面手性芳香铬配合物双核α，β-不饱和Fischer卡宾配合物，得到具有光学活性的环庚三烯铬配合物。此外，双核α，β-不饱和Fischer卡宾与平面手性芳烃铬配合物反应得到α-烯丙基β-芳基丙酸酯，其ee高达97%。手性异双核钨卡宾化合物…更多的前驱物提供了抗α-烯丙基β-羟基β-芳基丙酸酯作为主要产品，直到92/8 DR。反应产物α-烯丙基β-芳基丙酸酯通过1，3-M(CO)_5位移和随后的[3，3]-Sigmatrotic重排反应得到。在芳香族溶剂中回流，实现了空间位阻的N元吲哚铬配合物的立体选择性铬三羰基迁移。平面手性芳香铬配合物在Au(I)催化下，通过环异构化反应得到了轴向手性联芳基铬配合物。得到的轴向手性联芳基铬配合物是热力学稳定的反配合物。由于我们已经报道了平面手性芳基溴铬络合物与芳基硼酸的交叉偶联，从而产生了合成联芳基铬压缩，所以这些反联芳基铬络合物是非常有用的。较少

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