Direct immobilization of versatile 9‐amino(9‐deoxy)epi‐cinchona alkaloids without molecule modification to achieve heterogeneous organocatalysis is of interest in the low‐cost production of optically active compounds. In this paper, an exquisite “ship‐in‐a‐bottle” strategy for direct and simple immobilization of 9‐amino‐(9‐deoxy)epi‐quinine (QNNH₂) into hollow polystyrene nano‐bowl with imprinted free space around −SO₃H was developed via acid‐base reaction and radical polymerization. The heterogeneous organocatalyst with 0.44 mmol g⁻¹ of QNNH₂ and 0.48 mmol g⁻¹ of residual −SO₃H possessed fast mass transfer due to the characteristic architectural features, such as thin shell thickness, free space around catalytic site, and hollow interior. In heterogeneous acetal hydrolysis/asymmetric aldol tandem reaction, good to excellent catalytic performances (90–95 % yields, anti/syn=88/12–96/4, and 97–99 % ee anti) for acetals bearing electron‐withdrawing substituents (R=o, m, p‐NO₂, Cl) were achieved. The “ship‐in‐a‐bottle” QNNH₂ displayed good stability and reusability with excellent catalytic performances in the reuses.

中文翻译：

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将9-氨基（9-脱氧）表位-金鸡纳生物碱固定为分子印迹固体酸的“瓶装水”策略：缩醛水解/不对称羟醛串联反应

在低成本生产旋光性化合物中，人们感兴趣的是直接固定通用的9-氨基（9-脱氧）表耳金鸡纳生物碱，而无需进行分子修饰即可实现异质有机催化。在本文中，一个精致的“船在-A-瓶”策略的9-氨基- （9-脱氧）直接和简单的固定外延-quinine（QNNH ₂）插入霍洛瓦特聚苯乙烯纳米碗印迹自由空间周围-SO ₃ H通过酸碱反应和自由基聚合反应生成。具有0.44 mmol g ^-1的QNNH ₂和0.48 mmol g ^-1的残留-SO ₃的非均相有机催化剂H具有特征性的建筑特征，例如薄壳厚度，催化部位周围的自由空间和空心内部，因此具有快速的传质能力。在异质乙缩醛水解/不对称醛醇串联反应中，对于带有吸电子取代基的乙缩醛（90-95％收率，anti / syn = 88 / 12-96 / 4和eeanti为97-99％ee）具有良好的催化性能。R =邻，间，对- NO ₂，Cl）的得以实现。“瓶装船” QNNH ₂具有良好的稳定性和可重复使用性，在再利用中具有出色的催化性能。