Aldehydes as one of the most widely building blocks, have been frequently utilized as privileged C1 electrophile units and exhibited versatile applications to construct carbon‐heteroatom and carbon‐carbon bond. We herein described a novel Brønsted‐acid catalyzed aldehydes insertion reaction with maleimide‐based 1, n‐C, O/N‐synthons, involving a high regio‐ and chemoselectivity [6/7 + 1] or [3 + 1 + 1 + 1] manner. The maleimide‐based 1, n‐C, O/N‐synthons (n = 3, 6, 7) were originally designed and developed by our group which were used as flexible bisnucleophiles. By this tandem annulations approach, two types of structurally diverse medium‐sized heterocycles were synthesized in good to excellent yields (74‐91%) and with excellent selectivity, including dihydrobenzo[1,5]oxazocines (24 examples) and pyrrolo[3,4‐d]tetrahydropyrimidines (22 examples). Significantly, formaldehyde, long‐chain aliphatic aldehydes and aromatic aldehydes can act as C1 electrophile units catalyzed by racemic BINOL‐derived phosphoric acid catalyst in these transformations, which then selectively attacked the OH or NH group bearing in functionalized maleimides and underwent the formation of C–C, C–O or C–N bond in a short time under microwave irradiation conditions.

中文翻译：

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Brønsted-acid 催化的醛插入构建 C-X 键：二氢苯并[1,5]恶唑孪和吡咯并[3,4-d]四氢嘧啶的高区域和化学选择性合成


醛作为最广泛的构建单元之一，经常被用作特权 C1 亲电单元，并表现出构建碳-杂原子和碳-碳键的多种应用。我们在这里描述了一种新型 Brønsted-acid 催化的醛插入反应与基于马来酰亚胺的 1， n-C， O/N-synthons，涉及高区域选择性和化学选择性 [6/7 + 1] 或 [3 + 1 + 1 + 1] 方式。基于马来酰亚胺的 1， n-C， O/N-synthons （n = 3， 6， 7） 最初由我们小组设计和开发，用作灵活的亲核试剂。通过这种串联环化方法，以良好到极好的产量 （74-91%） 和极好的选择性合成了两种类型的结构多样化的中型杂环，包括二氢苯并[1,5]恶唑孪（24 个实例）和吡咯并[3,4-d]四氢嘧啶（22 个实例）。值得注意的是，甲醛、长链脂肪醛和芳香醛可以作为 C1 亲电单元，在这些转化中由外消旋 BINOL 衍生的磷酸催化剂催化，然后选择性地攻击功能化马来酰亚胺中的 OH 或 NH 基团，并在微波照射条件下在短时间内形成 C-C、C-O 或 C-N 键。