催化不对称[8+2]环加成反应构建环庚三烯并吡咯烷-3,3’-吲哚酮

doi:10.6023/A13121253

摘要/Abstract

设计了azaheptafulvenes作为偶极子与N-Boc-3-烯基吲哚酮反应，用来构建螺环[吡咯烷-3，3’-吲哚酮]衍生物. 在1 mol%手性氮氧-Ni（Ⅱ）配合物催化剂条件下，该不对称[8+2]环加成反应以高的收率（90%～99%收率），好的非对映选择性（高达97：3 dr）和优异的对映选择性（92%～99% ee）得到手性环庚三烯并螺环[吡咯烷-3，3'-吲哚酮]衍生物.

关键词: 手性氮氧, 镍, [8+2]环加成, 螺环, 不对称催化

The spiro pyrrolidin-3,3'-oxindole core is a privileged skeleton that is found in many natural products and biologically active molecules. For its construction, the [3+2] cycloaddition of 2π component 3-alkenyl-oxindoles with 3π component azomethine ylides is one of the most effective strategies. Since the pioneering work of Gong and co-workers, great effort has been devoted to the development of asymmetric [3+2] cycloadditions with azomethine ylides as the dipole synthon, and impressive progress has been achieved. In contrast, there is no report about higher-order [8+2] cycloaddition of 3-alkenyl-oxindoles with azaheptafulvenes as the 8π dipole synthons, which is an effective way to build cycloheptatriene-fused pyrrolidin-3,3'-oxindole derivatives with three contiguous stereocenters, including a spiro-quaternary chiral carbon atom. Herein, the azaheptafulvenes is developed as a new dipole synthon with 3-alkenyl-oxindoles to construct pyrrolidin-3,3'-oxindoles derivatives for the first time. In the presence of 1 mol% of chiral N,N'-dioxide L6-Ni(Ⅱ) complex, the asymmetric [8+2] cycloaddition performs well, affording functionalized cycloheptriene-fused pyrrolidin-3,3'-oxindoles derivatives in excellent yields (90%～99%), diastereoselectivities (up to 97:3 dr), and enantioselectivities (92%～99% ee) under mild conditions. A representative procedure for the asymmetric [8+2] cycloaddition is as follows: to a test tube, the catalyst solution (1 mol%, in THF) was added, and the THF was evaporated by oil pump. N-Boc-3-alkenyl-oxindole 2a and 0.5 mL of CH₂Cl₂ were added sequentially under air (N₂ atmosphere is not necessary). The reaction solution was stirred at 35 ℃ for 0.5 h, then the 8π component azaheptafulvene 1a (1.05 equiv.) was added. The mixture continued stirring at 35 ℃ until N-Boc-3-alkenyl-oxindole 2a was consumed (detected by TLC). Finally, the corresponding product 3a was purified by flash chromatography on basic Al₂O₃ [V(petroleum)/V(CH₂Cl₂)/V(EtOAc)=8:8:1].

Key words: chiral N,N'-dioxide, Ni(Ⅱ), [8+2] cycloaddition, spiro, asymmetric catalysis

引用此文

谢明胜, 武晓霞, 王刚, 林丽丽, 冯小明. 催化不对称[8+2]环加成反应构建环庚三烯并吡咯烷-3,3’-吲哚酮[J]. 化学学报, 2014, 72(7): 856-861.

Xie Mingsheng, Wu Xiaoxia, Wang Gang, Lin Lili, Feng Xiaoming. Catalytic Asymmetric [8+2] Cycloaddition for the Construction of Cycloheptatriene-Fused Pyrrolidin-3,3’-Oxindoles[J]. Acta Chimica Sinica, 2014, 72(7): 856-861.

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