Enantioselective Synthesis of Azahelicenes through Organocatalyzed Multicomponent Reactions
Enantioselective Synthesis of Azahelicenes through Organocatalyzed Multicomponent Reactions
复制标题
DOI：
10.1002/anie.202303430
复制
发表时间：
2023-05-19
影响因子：
16.6
通讯作者：
Yang, Xiaoyu
中科院分区：
文献类型：
--
作者：
Liu, Wei;Qin, Tianren;Yang, Xiaoyu
我们采用中心到螺旋手性转换策略，通过有机催化的不对称多组分反应，由容易获得的多环芳香胺、醛和（二）烯酰胺开发了一种高效的氮杂螺旋烯模块化不对称合成方法。通过这种一锅连续对映选择性Povarov反应/氧化芳构化过程，可以很容易地得到一系列带有各种取代基的氮杂[5]-和氮杂[4]螺旋烯，具有良好的产率和高对映选择性。手性氮杂氮杂烯产物的丰富多样的衍生化展示了该方法的潜力，并展示了氮杂杂碳烯衍生物作为手性有机催化剂的初步应用。这些氮杂螺旋烯的光物理和手性光学性质，特别是酸/碱触发的这些性质的转换，也得到了很好的研究，这可能会在新型有机光电材料的开发中找到潜在的应用。
We have developed an efficient modular asymmetric synthesis of azahelicenes through an organocatalyzed asymmetric multicomponent reaction from readily available polycyclic aromatic amines, aldehydes, and (di)enamides, by employing a central-to-helical chirality conversion strategy. A series of aza[5]- and aza[4]helicenes bearing various substituents were readily afforded through this one-pot sequential enantioselective Povarov reaction/oxidative aromatization process, with good yields and high enantioselectivities. The fruitful and diverse derivatizations of the chiral azahelicene products demonstrated the potential of this method, and a preliminary application of the azahelicene derivative as a chiral organocatalyst was showcased. The photophysical and chiroptical properties of these azahelicenes, particularly the acid/base-triggered switching of these properties, were also well studied, which may find potential applications in the development of novel organic optoelectronic materials.