Single-Handed Helical Poly(quinoxaline-2,3-diyl)s Bearing Achiral 4-Aminopyrid-3-yl Pendants as Highly Enantioselective, Reusable Chiral Nucleophilic Organocatalysts in the Steglich Reaction.
Single-Handed Helical Poly(quinoxaline-2,3-diyl)s Bearing Achiral 4-Aminopyrid-3-yl Pendants as Highly Enantioselective, Reusable Chiral Nucleophilic Organocatalysts in the Steglich Reaction.
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DOI：
10.1021/jacs.6b12349
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发表时间：
2017-02
影响因子：
15
通讯作者：
Takeshi Yamamoto;R. Murakami;M. Suginome
中科院分区：
文献类型：
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作者：
Takeshi Yamamoto;R. Murakami;M. Suginome
合成了具有螺旋手性的4-氨基吡啶-3-基链链，作为新型的螺旋聚合物手性亲核有机催化剂。所制得的手性亲核聚合物催化剂在碳酸恶唑酯非对称Steglich重排制c -羧基内酯反应中具有较高的催化活性、对映选择性和可重复使用性。基于多喹啉的螺旋手性DMAP催化剂选择性地介导分子内酰基转移，与已知的小分子手性有机催化剂不同，小分子手性有机催化剂也介导分子间酰基转移。
Helically chiral poly(quinoxaline-2,3-diyl)s bearing 4-aminopyrid-3-yl pendants were synthesized as new helical-polymer-based chiral nucleophilic organocatalysts. The obtained chiral nucleophilic polymer catalysts exhibited high catalytic activity, enantioselectivity, and reusability in asymmetric Steglich rearrangement of oxazolyl carbonate to C-carboxyazlactone. The polyquinoxaline-based, helically chiral DMAP catalyst mediated intramolecular acyl transfer selectively, by contrast with known small-molecule-based chiral organocatalysts, which also mediate intermolecular acyl transfers.