Study of the -oxygen effect in the Barton-McCombie reaction for the total synthesis of ()-4-hydroxy-γ-decalactone (Japanese orange fly lactone): a carbohydrate based approach

• Published in: RSC advances Vol. 12; no. 39; pp. 2552 - 25527
• Main Authors: Desireddi, Janardana Reddi, Rao, Mora Mallikarjuna, Murahari, Kiran Kumar, Nimmareddy, Rajashekar Reddy, Mothe, Thirupathi, Lingala, Arun Kumar, Maiti, Bhimcharan, Manchal, Ravinder
• Format: Journal Article
• Published: 07-09-2022
• ISSN: 2046-2069
• DOI: 10.1039/d2ra04531a

Efficient and facile synthesis of Japanese orange fly lactone (
1
) was achieved from a commercially available
d
-glucose
by investigating the Barton-McCombie reaction with furanose anomeric isomers (
12
α
,
β
) with an overall yield of 12.6%. During the course of this synthesis, the
β
-oxygen effect was discovered in the deoxygenation step at the
C-3
position using the Barton-McCombie reaction, where the substrate allows the effect to operate in one of the isomers but not in the other. Under the same reaction conditions, xanthate derived from the
β
-furanose isomer affords a high yield of deoxygenated product, whereas the
α
-isomer produces a very low yield. The key transformations used were Wittig olefination, TEMPO mediated oxidation, and Barton-McCombie deoxygenation, resulting in a concise total synthesis of Japanese orange fly lactone (
1
). Our success will allow for further biological studies of this natural product, as well as opportunities for developing new potentially promising pheromones.
The Japanese orange fly lactone was synthesised with a chiral pool approach using commercially available, starting material
d
-glucose. This synthesis encountered a dominant structurally functioning impact in the Barton-McCombie reaction known as the
β
-oxygen effect.