Synthesis of 5-Amino-2,5-dihydro-1H-benzo[b]azepines Using a One-Pot Multibond Forming Process

Abstract

Rapid access to allylic trichloroacetimidates bearing a 2-allylaminoaryl group from readily available 2iodoanilines combined with a one-pot multibond forming process has allowed the efficient synthesis of a series of 5amino-2,5-dihydro-1H-benzo[b]azepines. The potential of these compounds as synthetic building blocks was demonstrated by the preparation of a late-stage intermediate of the hyponatremia agent, mozavaptan.

Spiropiperidine Sultam and Lactam Templates: Diastereoselective Overman Rearrangement and Metathesis followed by NH Arylation

“…In the present study, we describe an alternative means of forming the chiral spirocyclic center using the Overman rearrangement of an allylic alcohol followed by a tandem Hoveyda–Grubbs metathesis to construct the spirocyclic pyrrolidinone with good diastereoselectivity as controlled by a remote chiral center. This combination of technology has been used recently but not in the preparation of spirocyclic piperidine systems …”

Synthesis of highly substituted tetrahydroquinolines using ethyl cyanoacetate via aza-Michael–Michael addition

“…Reacting ethyl cyanoacetate, (E)-methyl 3-(2-aminophenyl)acrylate (5), and substituted aromatic aldehydes with DBU yielded 1,2,3,4-substituted tetrahydroquinolines effectively (Scheme 1). 28 Electron rich aldehydes resulted in better conversion compared with the other aldehydes. The corresponding product 3e of 2-anisaldehyde demonstrated improved diastereoselectivity compared with the other substituted benzaldehydes (Scheme 1).…”

Recent Advances in Transition‐Metal‐Catalyzed Oxidative Annulations to Benzazepines and Benzodiazepines

“…In a step further toward more sustainable approaches, catalytic methods have been successfully employed to synthesize both benzazepines and benzodiazepines. Thus, transition-metal-catalyzed Heck type reactions, [25] cycloadditions, [26] metathesis, [27] oxidative couplings, [28] intramolecular C-and N-aryl(alkyl) ations, [29] tandem processes [30] or hydroamin(d)ation of alkynes [31] has been successfully employed. The current challenges in transition-metal-catalysis lies in developing more ecofriendly strategies to access highly valuable benzofused seven-membered azaheterocycles.…”