Abstract
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 (1R)-(−)-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 CDCl3.
Highlights
The best known 2-amino-1,3-diol derivative sphingosine (1) plays a crucial role in intracellular signaling as second messenger, and its derivatives called sphingolipids are critical for cell growth, cell differentiation, cell recognition, and apoptosis [1,2,3,4,5,6,7]
We have extensively studied the stereoselective synthesis, as well as catalytic and pharmacological applications of monoterpene-based 3-amino-1,2-diols, which are the regioisomers of potential monoterpenic 2-amino-1,3-diols [29,30,31,32,33]
The first step was the stereoselective epoxidation of (−)-α-pinene (6), carried out with meta-chloroperoxybenzoic acid (MCPBA), followed by a base-catalyzed allylic rearrangement mediated by aluminium isopropoxide (Al(OiPr)3)
Summary
The best known 2-amino-1,3-diol derivative sphingosine (1) plays a crucial role in intracellular signaling as second messenger, and its derivatives called sphingolipids are critical for cell growth, cell differentiation, cell recognition, and apoptosis [1,2,3,4,5,6,7]. Due to its involvement in a wide range of cellular processes, significant efforts have been made in the last two decades targeting sphingosine analogues signalling as a therapeutic strategy. FTY720-P (3), the phosphate of FTY720 (2, fingolimod), proved to be a very good agonist for the S1P1 receptor (Figure 1). Sphingosine 1-phosphate (S1P, 4), in turn, performed critical regulator functions in many physiological and pathological treatments, such as Alzheimer’s disease.
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