De NovoAsymmetric Synthesis of Phoracantholide J

Abstract

A de novo asymmetric total synthesis of the macrolide natural product (S)-phoracantholide J has been achieved in 10 steps from the commodity chemicals (1-pentyne, ethyl acrylate, acetaldehyde, and hydrogen). The asymmetry of the route was introduced by a Noyori reduction of a 3-yn-2-one, which makes the route equally amenable to the synthesis of either enantiomer. In addition, this route relies upon an alkyne zipper, a hydroalkynylation, and a macrolactonization to complete the synthesis.

Decarboxylative alkenylation

“…(−)-Phoracantholide J ( 89 ) was previously constructed through either ring-closing metathesis or Ru-catalyzed hydroalkynylation. 47,48 …”

Recent advances in the synthesis of insect pheromones: an overview from 2013 to 2022

“…9 shows the pheromones of Osmoderma eremita (Col., Cetoniidae): 194, 174,175 Nasonia vitripennis (Hym., Pteromalidae): 195, 176 Bactrocera tsuneonis (Dip., Tephritidae): 196, 177 Popillia japonica (Col., Scarabaeidae): (R)-197 and Anomala osakana (Col., Scarabaeidae): (S)-197, 178 Rhagoletis batava (Dipt., Tephritidae): 198, 179 Macrocentrus grandii (Hym., Braconidae): 199, 180 Vespa orientalis (Hym., Vespidae): 200, [181][182][183][184] Culex spp. (Dip., Culicidae): 201, [185][186][187][188][189] Phoracantha synonyma (Col., Cerambycidae): 202, 190 Silvestritermes minutus (Iso., Termitidae): 203, 191 Heliconius erato phyllis (Lep., Nymphalidae): 204 (anti-aphrodisiac). 192 Agrilus planipennis (Col., Buprestidae): 205, 193,194 Oryzaephilus surinamensis (Col., Silvanidae): 206 and 207, 195 Cryptoletes pusillus (Col., Staphylinidae): 208, 47 Oryzaephilus surinamensis (Col., Silvanidae): 209.…”

Total Synthesis and Structural Elucidation of Two Unusual Non‐Methylene‐Interrupted Fatty Acids in Ovaries of the Limpet Cellana toreuma

“…However, this method is applicable only to the synthesis of 1,5-dienic structure and is not suitable for the synthesis for our purpose of fatty acids 20-23 having remote dienic structures. Previously, alkynezipper reaction was often applied to the synthesis of a variety of fatty acids and their derivatives as the key step of preparation of their carbon chains [37][38][39][40][41][42], and these successful results also led us to envision attempts for the synthesis of our target compounds by using the synthetic pathway involving the alkyne-zipper reaction. The retrosynthetic analysis of the target fatty acids in this research work is outlined in Scheme 3, and, especially, both fragment A and fragment B could be synthetized from the common starting compound, i.e., 2-propyn-1-ol [propargyl alcohol (24)], through a similar procedure involving alkylation, isomerization of the internal C-C triple bonds of intermediates D and E into the terminal position by using the alkyne-zipper reaction [36].…”

“…The retrosynthetic analysis of the target fatty acids in this research work is outlined in Scheme 3, and, especially, both fragment A and fragment B could be synthetized from the common starting compound, i.e., 2-propyn-1-ol [propargyl alcohol (24)], through a similar procedure involving alkylation, isomerization of the internal C-C triple bonds of intermediates D and E into the terminal position by using the alkyne-zipper reaction [36]. Previously, alkynezipper reaction was often applied to the synthesis of a variety of fatty acids and their derivatives as the key step of preparation of their carbon chains [37][38][39][40][41][42], and these successful results also led us to envision attempts for the synthesis of our target compounds by using the synthetic pathway involving the alkyne-zipper reaction. Here, we describe an efficient and stereoselective total synthesis of two new unusual dienoic acids, 19:2∆7,18 (20) and 21:2∆7,20 (22), through a common pathway involving the strategic combination of the alkyne-zipper reaction and Lindlar hydrogenation for the construction of their unique carbon chains.…”