Total Synthesis of Both Enantiomers of Macrocyclic Lactone Aspergillide C

Abstract

A facile approach to the total synthesis of both enantiomers of the 14‐membered macrolactone aspergillide C is described. The strategy employed was also utilized for the synthesis of C4‐epimers of both the enantiomers of aspergillide C. The key reactions include Sharpless kinetic resolution, Achmatowicz reaction, Ferrier type alkynylation, hydrosilylation‐protodesilylation, Corey–Bakshi–Shibata (CBS) mediated reduction, and Yamaguchi macrolactonization.

Stereodivergent Total Synthesis of (+)‐Aspergillide B and (+)‐7‐epi‐Aspergillide A

“…In continuation of our efforts towards the total syntheses of lactone‐containing natural products,8 we recently published the total synthesis of both enantiomers of aspergillide C and their C‐4 epimers through a concise approach 7a. Herein, we describe the total syntheses of (+)‐aspergillide B and (+)‐7‐ epi ‐aspergillide A.…”

E statt Z

“…Ebenso nutzten Fürstner und Mitarbeiter die stereoselektive Semihydrierung des makrozyklischen Alkins (3) , um das Polyketid Tulearin C aufzubauen (Abbildung 5b) 8. Srihari und Sridhar verwendeten den E‐selektiven Reduktionsschritt des Dihydropyranons (4) zu Verbindung (5) für eine effiziente Synthese des Aspergillids C (Abbildung 5c) 9…”

Achmatowicz reaction and its application in the syntheses of bioactive molecules

“…219 These naturally occurring molecules displayed potent cytotoxicity against mouse lymphatic leukaemia cells and toward a number of human cancer cell lines, including HL-60 (promyelocytic leukaemia), MDA-MB-231 (breast carcinoma), and HT1080 (fibrosarcoma) cell lines. 220 Srihari and co-workers described the total syntheses of Aspergillide C. 221 The retrosynthetic strategy shows the key Achmatowicz reaction to construct pyranone derivative 182 .…”