Asymmetric synthesis of aminocyclooctenecarbonitriles: Cyclooctene β-lactam and hydroxyaminocyclooctene carboxylic precursors. Issue 3 (17th January 2019)

• Record Type: Journal Article
• Authors: Aydin, Busra Ozturk; Yurtoglu, Emine; Arcelik, Nejat; Sahin, Ertan; Secen, Hasan; Altundas, Ramazan
• Is Part Of: Tetrahedron letters. Volume 60:Issue 3(2019)
• Page Start: 284
• Page End: 287
• Publication Date: 2019-01-17
• Subjects: Aminocyclooctenecarbonitrile -- Hydroxyaminocycloctene nitrile -- Cycloctenelactams; Chemistry, Organic -- Periodicals; 547.005
• DOI: 10.1016/j.tetlet.2018.12.034
• Languages: English
• ISSNs: 0040-4039

Abstract

Graphical abstract: Highlights: Enantiopure aminocyclooctene carbonitriles were accessed in g quantity. New unsaturated β-lactams were achieved. Hydroxyaminocyclooctene carbonitriles were obtained via aziridine ring opening. The absolute stereochemistry of the synthesized compounds was determined by X-ray. Abstract: Enantiopure β-aminocyclooctenenitriles, as precursors of β-amino acids and β-lactams, were synthesized from a readily available chloroalkene nitrile and ( S )-methylbenzylamine via a straightforward substitution reaction and purified by crystallization. Acidic hydrolysis of the nitrile groups to their corresponding amides followed by DCC assisted carbonyl group activation gave novel α, β-unsaturated lactams. The treatment of 3-bromo-8-chlorocyclooctenecarbonitrile with ( S )-methylbenzylamine furnished a diastereomeric mixture of bromoaminocyclooctenecarbonitriles via an S N 2′ pathway rather than bromide substitution via an S N 2 pathway. The diastereomeric mixture of bromoaminocyclooctanecarbonitriles provided two novel aziridines upon heating. TFA catalyzed aziridine ring opening gave γ-hydroxyl-β-aminocyclooctenecarbonitriles and γ-amino-β-hydroxycyclooctenecarbonitriles.