Synthesis of enantiopure (S)-7-hydroxy-3-amino-3,4-dihydro-2H-1-benzopyran en route to (+)-scyphostatin

(S)-7-Hydroxy-3-amino-3,4-dihydro-2H-1-benzopyran, a key synthetic intermediate towards the total synthesis of (+)-scyphostatin, has been prepared in >98% ee. Key synthetic steps were (i) the oxidative dearomatization of an l-tyrosine derived phenol, (ii) the transformation of the resulting p-quinol acetate to the corresponding resorcinol upon exposure to Thiele reaction conditions and, (iii) the direct formation of the benzopyran ring upon treatment of an N-Boc protected 4-(2-acetoxybenzyl)oxazolidin-2-one with sodium methoxide.