An Efficient Total Synthesis of (–)‐(R), (+)‐(S)‐Lavandulol Pheromones and Their Derivatives through Proline Catalyzed Asymmetric α‐Aminooxylation and [3,3] Claisen Rearrangement

Abstract

An efficient total synthesis of the enantiomerically pure lavandulol pheromones viz. (–)‐(R) and (+)‐(S)‐lavandulol, (–)‐(R)‐lavandulyl acetate, (–)‐(R)‐lavandulyl propionate, (+)‐(S)‐lavandulyl 2‐methylbutanoate and (+)‐(S)‐lavandulyl senecioate is accomplished from nonchiral and chiral materials. The strategy utilizes a sequence of proline catalyzed asymmetric α‐aminooxylation and [3,3] Claisen rearrangement for stereodivergent synthesis of chiral C‐2 unit containing 4‐pentenols.

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

“…During this period, the synthesized isoprenoid pheromones were identified from Necrodes surinamensis (Col., Silphidae): 220 , Maconellicoccus hirsutus (Hem., Pseudococcidae): 221 , Anthonomus rubi (Col., Curculionidae) and Planococcus ficus (Hem., Pseudococcidae): 222 , 210,211 Thrips palmi (Thy., Thripidae): 223 , 212 Planococcus kraunhiae (Hem., Pseudococcidae): 224 , 213 Dysmicoccus neobrevipes (Hem., Pseudococcidae): 225 , 214 Leptinotarsa decemlineata (Col., Chrysomelidae): 226 , 215–220 Lasius meridionalis (Hym., Formicidae): 227 , 221,222 Ips confuses (Col., Curculionidae): 228 and 229 , 223 Urolepis rufipes (Hym., Pteromalidae): 230 , 224 Solenopsis invicta (Hym., Formicidae): 231 , 225 Solenopsis invicta (Hym., Formicidae): 231 and 232 ; 226 Astyleiopus variegatus (Col., Cerambycidae): 233 and 234 , 227 Amblypelta lutescens (Hem., Coreidae): 235 , 228 Monomorium pharaonis (Hym., Formicidae): 236 and 237 , 222 Aonidiella aurantia (Hem., Diaspididae): 238 229 Pseudococcus calceolariae (Hem., Pseudococcidae): 239 , 230 Anthonomus grandis (Col., Curculionidae): 240 , 231–233 Aspidiotus nerii (Hem., Diaspididae): 241 , 234 Pseudococcus longispinus (Hem., Pseudococcidae): 242 , 235–237 Dysmicoccus brevipes (Hem., Pseudococcidae): 243 , 238,239 Nipaecoccus viridis (Hem., Pseudococcidae): 244 , 240,241 Pseudococcus baliteus (Hem., Pseudococcidae): 245 , 242 Dolichovespula maculate (Hym., Vespidae): 246 , 243 Tibraca limbativentris (Hem., Pentatomidae): 247 , 244 Oebalus poecilus (Hem., Pentatomidae): 248 , 245 Murgantia histrionica and Halyomorpha halys (Hem., Pentatomidae): 249 , 245,246 Anoplophora malasiaca (Col., Cerambycidae): 250–252…”

“…The Pd-catalysed syn to anti epimerization of a precursor lactone derived from D-glucono-D-lactone was the key step (step d, Scheme 19). The syn-and anti-lactones were separated by column chromatography and further converted to (+)-exo-and (+)-endo-brevicomin (211), respectively (Scheme 19). 198 2.3.3.…”