Modular Access to the Stereoisomers of Fused Bicyclic Azepines: Rhodium-Catalyzed Intramolecular Stereospecific Hetero-[5+2] Cycloaddition of Vinyl Aziridines and Alkenes

• Published in: Angewandte Chemie International Edition Vol. 54; no. 52; pp. 15854 - 15858
• Main Authors: Feng, Jian-Jun, Lin, Tao-Yan, Wu, Hai-Hong, Zhang, Junliang
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 21.12.2015; WILEY‐VCH Verlag; Wiley; Wiley Subscription Services, Inc
• Edition: International ed. in English
• Subjects: Alkenes; Chemistry; Chemistry, Multidisciplinary; chirality; Cycloaddition; heterocycles; Physical Sciences; Rhodium; Science & Technology; Stereochemistry; Stereoisomerism; Stereoisomers; Stereoselectivity; Substrates; chirality; RING EXPANSIONS; REACTIVITY; VINYLCYCLOPROPANES; ALKYNES; ALLENES; SUBSTITUTED CYCLOPROPANES; cycloaddition; stereoselectivity; heterocycles; 7-MEMBERED RINGS; METAL; ASYMMETRIC TOTAL-SYNTHESIS; SELECTIVITY; rhodium
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.201509185

The first rhodium‐catalyzed intramolecular hetero‐[5+2] cycloaddition reaction of vinyl aziridines and alkenes was realized, wherein both internal and terminal alkenes were applicable. With this method, a variety of unique substituted chiral fused bicyclic azepines, bearing multiple contiguous stereogenic centers, were facilely accessed in a straightforward, high‐yielding, and highly stereoselective manner under mild reaction conditions. Notably, the E/Z geometry of the CC bonds in the vinyl aziridine‐alkene substrates impact the cis/trans stereochemistry of the cycloadducts and up to six stereoisomers could be delivered. E/Z access: The title reaction was realized and a range of chiral fused bicyclic azepines bearing multiple contiguous stereogenic centers can be obtained in a high‐yielding and stereoselective manner. The E/Z geometry of the CC bonds in the substrates affect the stereochemistry of the cycloadducts and up to six stereoisomers can be obtained.