Synthesis of Chiral Aminocyclopropanes by Rare-Earth-Metal-Catalyzed Cyclopropene Hydroamination

• Published in: Angewandte Chemie International Edition Vol. 55; no. 49; pp. 15406 - 15410
• Main Authors: Teng, Huai-Long, Luo, Yong, Wang, Baoli, Zhang, Liang, Nishiura, Masayoshi, Hou, Zhaomin
• Format: Journal Article
• Language: English
• Published: WEINHEIM Blackwell Publishing Ltd 05.12.2016; Wiley; Wiley Subscription Services, Inc
• Edition: International ed. in English
• Subjects: Amines; aminocyclopropanes; asymmetric catalysis; Chemistry; Chemistry, Multidisciplinary; cyclopropenes; hydroamination; lanthanide complexes; Metal complexes; Physical Sciences; Science & Technology; cyclopropenes; ASYMMETRIC-SYNTHESIS; CYCLOPROPANATION; asymmetric catalysis; ALKYNES; hydroamination; UNACTIVATED ALKENES; TERMINAL ALLENES; DESYMMETRIZATION; BRANCHED ALLYLIC AMINES; lanthanide complexes; INTERMOLECULAR HYDROAMINATION; aminocyclopropanes; ENANTIOSELECTIVE HYDROAMINATION; BELACTOSIN-A
• ISSN: 1433-7851; 1521-3773; 1521-3773
• DOI: 10.1002/anie.201609853

The search for efficient and selective routes for the synthesis of chiral aminocyclopropane derivatives is of great interest and importance as these structures are important components of biologically active natural products and pharmaceuticals. We herein report the enantioselective intermolecular hydroamination of substituted cyclopropenes with various amines catalyzed by chiral half‐sandwich rare‐earth‐metal complexes. This method constitutes a 100 % atom‐efficient route for the synthesis of a variety of chiral α‐aminocyclopropane derivatives in high yields (up to 96 %) and excellent stereoselectivity (up to >20:1 d.r. and 99 % ee) under mild reaction conditions (25 °C). A rare reaction: The enantioselective intermolecular hydroamination of cyclopropenes with amines was achieved by using chiral half‐sandwich rare‐earth‐metal catalysts. A range of chiral aminocyclopropane derivatives were thus obtained in high yields and with excellent stereoselectivity under mild conditions.