New and Convenient Chemoenzymatic Syntheses of (S)-2-Hydroxy-3-octanone, the Major Pheromone Component of Xylotrechus spp., and Its R-Enantiomer

Abstract

New and efficient chemoenzymatic approaches for the synthesis of both enantiomers of 2-hydroxy-3-octanone in good yields and excellent enantioselectivity are presented. The S-enantiomer is a pheromone component of economically important pests in Japan, India, China, and other Asian countries. The enzymatic approaches involve transesterification of the racemic acyloin with vinyl acetate in the presence of Candida antarctica lipase B (CAL B) in 99% ee of both enantiomers (E = 167-618), or hydrolysis of the acetylated acyloin by double kinetic resolution with CAL B and C. antarctica lipase A (CAL A) in 96-98% ee of either enantiomer (E = 458). CAL A and CAL B induce reverse enantioselectivity.

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

“…5 shows the pheromones of Xylotrechus spp. (Col., Cerambycidae): 111 , 86 Cnaphalocrocis medinalis (Lep., Pyralidae): 112 , 113 , 46 Chilo suppressalis (Lep., Pyralidae): 114 , 115 , 87 Actias luna (Lep., Saturniidae): 112 , 116 and 129 , 88 Aromia bungii (Col., Cerambycidae): 117 , 89 Trogoderma spp. (Col., Dermestidae): ( E )- and ( Z )- 118 , 90 Carposina niponensis (Lep., Carposinidae): 119 , 120 , 91,92 Diatraea saccharalis (Lep., Crambidae): 121 , 93 Chlorida festiva and C. costata (Col., Cerambycidae): 122 , 94 Cameraria ohridella (Lep., Gracillariidae): 123 , 95,96 notodontid moths (Lep., Notodontidae): 124 , 68 Micromelalopha siversi (Lep., Notodontidae): 125 , 97 Teia anartoides (Lep., Erebidae): 126 , 98 Corimelaena extensa (Hem., Thyreocoridae): 127 , 99 Chilecomadia valdiviana (Lep., Cossidae): 128 , 100,101 Rhodinia fugax (Lep., Saturniidae): 129 , 75 Phyllocnistis citrella (Lep., Gracillariidae), 130 and 131 , 29,102 Elaphidion mucronatum (Col., Cerambycidae): 132 , 103 Callosamia promethea (Lep., Saturniidae): 133 , 104 Apomyelois ceratoniae (Lep., Pyralidae): 134 , 105 Phyllocnistis citrella (Lep., Gracillariidae): 135 .…”

Synthesis of α-hydroxy ketones and vicinal (R,R)-diols by Bacillus clausii DSM 8716T butanediol dehydrogenase

“…The BcBDH reduction product of 5-methyl-2,3-hexanedione was additionally analysed by 1 H and 13 C nuclear magnetic resonance (NMR; NMR spectrometer Spinsolve 60 carbon (60 MHz) (Magritek)). The sample was solved in 1 ml CDCl 3…”

“…They can be used either as natural avours, pheromones, or as building blocks in organic syntheses. 3,4,48 Oen, it is benecial to synthesize these molecules through biocatalysis, because of the helpful properties of enzymes (e.g. regio-and stereoselectivity) as biocatalysts.…”

“…as avouring compounds, pheromones or as precursors for ne chemicals. [1][2][3][4] Additionally, the development of efficient syntheses for enantiomerically enriched a-hydroxy ketones is an important research focus in the pharmaceutical industry. These compounds can be found in antidepressants and fungicides, in selective inhibitors of amyloid protein production (used in the treatment of Alzheimer's disease), in farnesyl transferase inhibitors (Kurasoin A and B), and in antitumor-antibiotics (Olivomycin A and Chromomycin A3 and Taxol).…”