Protecting‐Group‐Free Total Synthesis of (–)‐Pallambins A—D

Abstract

Main observation and conclusion A full account of the total synthesis of (–)‐pallambins A—D (1—6) is described. The strategy was devised by simulating their biosynthetic pathway. The left‐part bicyclo[3.2.1]octane system of pallambins C and D was efficiently constructed via a palladium‐ catalyzed oxidative cyclization. For construction of the right‐part tetrahydrofuran/γ‐lactone moiety (C/D rings), initial attempts to synthesize the allylic alcohol 15 for an one‐step Pd‐mediated alkoxycarbonylation have failed. However, during the course of this work, an unprecedented CH3Li‐mediated method for conversion of bromoisoxazoline to the corresponding β‐hydroxy nitrile has been discovered. Furthermore, a stepwise protocol was designed, namely an Eschenmoser‐Claisen rearrangement/Lactonization to generate the C ring, and a non‐classical Wittig reaction to form the D ring. During the course of this work, a palladium‐catalyzed method for dehydrobromination of bromide ketone was developed. Finally, an individual transformation of pallambins C (3) and D (4) generated pallambins A (5) and B (6) under mild UV irradiation. Thus, the first enantioselective total syntheses of (–)‐pallambins A—D have been achieved in 15 or 16 steps from the known chiral cyclohexenone 8. The described synthesis avoids protecting‐group manipulations by designing highly chemo‐ and stereoselective transformations.

Transfer of Axial Chirality to the Nanoscale Endows Carbon Nanodots with Circularly Polarized Luminescence

“…The presence of binaphthyl units is confirmed by the distinctive strong signals at 815 and 749 cm −1 , assigned to the out‐of‐plane bending of aromatic C−H bonds, which are slightly shifted with respect to the starting diamine [43] . The presence of carbonyl functional groups is indicated by an intense signal at 1707 cm −1 , which originates mainly from citric acid, as revealed by the comparison with CNDs‐1 , obtained in the absence of benzoquinone, which nevertheless show a similar peak at 1709 cm −1 (Figure S19).…”