Aminohydroxylation of divinylcarbinol and its application to the synthesis of bicyclic hydroxypyrrolidine and aminotetrahydrofuran building blocks

Abstract

Dedicated to Professor Štefan Toma on the occasion of his 75th birthdayAminohydroxylation of prochiral divinylcarbinol and subsequent Pd(II)-catalysed oxy-/amidocarbonylation of aminopentenediols is reported. The method was applied to the preparation of useful building blocks for syntheses of cytotoxic jaspines and glycosidase inhibitor DLX-homologues. The key intermediates, tetrahydrofuranolactones (l-arabino-II) and pyrrolidinolactones (l-arabino-IX and l-xylo-IX), were prepared in a short 2-step sequence from divinylcarbinol.

An Overview of Catalytic Carbonylative Double Cyclization Reactions

“…Scheme 11. Synthesis of (a) benzyl (3aR,6R,6aS)-6-hydroxy-2-oxohexahydro-4H-furo[3,2-b]pyrrole-4-carboxylate (a precursor for the formation of glycosidase inhibitor derivatives)[40] and (b) benzyl (3aR,6S,6aS)-6-hydroxy-2-oxohexahydro-4H-furo[3,2-b]pyrrole-4-carboxylate[41].…”

“…Synthesis of 2-oxo-N-phenylhexahydrofuro[3,2-b]pyridine-4(2H)-carboxamide from 1-(4-hydroxyhex-5-en-1-yl)-3-phenylurea [39].Later on, Jäger et al reported the carbonylation of benzyl ((2R,3S)-2,3-dihydroxypent-4-en-1-yl)carbamate (Scheme 11a) as a key step in the synthesis of novel 1,4-iminoglycitol derivatives as potential glycosidase inhibitors[40]. On the other hand, the PdCl 2 -catalyzed carbonylation of benzyl ((2S,3S)-2,3-dihydroxypent-4-en-1-yl)carbamate gave benzyl (3aR,6S,6aS)-6-hydroxy-2-oxohexahydro-4H-furo[3,2-b]pyrrole-4-carboxylate in a 14% yield (Scheme 11b)[41].…”