Biologically active glycosides from asteroidea, XV. Asymmetric synthesis of phytosphingosine and phytosphingosine anhydro base: Assignment of the absolute stereochemistry

Abstract

Abstract The first asymmetric synthesis of a phytosphingosine, (2 S ,3 S ,4 R )‐2‐amino‐1,3,4‐hexadecanetriol ( 2 ), was accomplished by kinetic resolution and asymmetric epoxidation. The absolute stereochemistry of the phytosphingosine from starfishes ( Acanthaster planci and Asterina pectinifera ) was established to be the same as for 2 . The phytosphingosine anhydro base 19 was also asymmetrically synthesized, and the structure was determined on the basis of NMR analyses involving 2D‐COSY, NOESY, and difference NOE experiments.