Stereoselective synthesis and transformation of pinane-based 2-amino-1,3-diols

• Published in: Beilstein journal of organic chemistry Vol. 17; no. 1; pp. 983 - 990
• Main Authors: Bajtel, Ákos, Raji, Mounir, Haukka, Matti, Fülöp, Ferenc, Szakonyi, Zsolt
• Format: Journal Article
• Language: English
• Published: Frankfurt am Main Beilstein-Institut zur Föerderung der Chemischen Wissenschaften 03.05.2021; Beilstein-Institut
• Subjects: 2-amino-1,2-diol; Alcohol; Alkylation; Alzheimer's disease; Benzaldehyde; Chemistry; Crystallography; Experiments; Full Research Paper; monoterpene; NMR; Nuclear magnetic resonance; oxazolidin-2-one; Potassium; Spectrum analysis; Stereochemistry; stereoselective; Tautomerism; α-Pinene
• ISSN: 1860-5397; 2195-951X; 1860-5397
• DOI: 10.3762/bjoc.17.80

A library of pinane-based 2-amino-1,3-diols was synthesised in a stereoselective manner. Isopinocarveol prepared from (−)-α-pinene was converted into condensed oxazolidin-2-one in two steps by carbamate formation followed by a stereoselective aminohydroxylation process. The relative stereochemistry of the pinane-fused oxazolidin-2-one was determined by 2D NMR and X-ray spectroscopic techniques. The regioisomeric spiro-oxazolidin-2-one was prepared in a similar way starting from the commercially available (1 R )-(−)-myrtenol ( 10 ). The reduction or alkaline hydrolysis of the oxazolidines, followed by reductive alkylation resulted in primary and secondary 2-amino-1,3-diols, which underwent a regioselective ring closure with formaldehyde or benzaldehyde delivering pinane-condensed oxazolidines. During the preparation of 2-phenyliminooxazolidine, an interesting ring–ring tautomerism was observed in CDCl 3 .