Desireddi Janardana Reddi, Rao Mora Mallikarjuna, Murahari Kiran Kumar, Nimmareddy Rajashekar Reddy, Mothe Thirupathi, Lingala Arun Kumar, Maiti Bhimcharan, Manchal Ravinder
Aragen life sciences Private Limited (formerly known as GVK Biosciences Private Limited), Medicinal Chemistry Division 28A, IDA Nacharam Hyderabad-500076 Telangana India
Department of Chemistry Chaitanya (Deemed to be University) Warangal-506001 Telangana India
RSC Adv. 2022 Sep 7;12(39):25520-25527. doi: 10.1039/d2ra04531a. eCollection 2022 Sep 5.
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 ( , ) 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.
通过研究呋喃糖异头异构体（α，β）的巴顿-麦康比反应，以市售的d-葡萄糖为原料，高效简便地合成了日本桔小实蝇内酯（1），总收率为12.6%。在该合成过程中，发现在使用巴顿-麦康比反应进行C-3位脱氧步骤时存在β-氧效应，底物使得该效应在一种异构体中起作用而在另一种异构体中不起作用。在相同反应条件下，β-呋喃糖异构体衍生的黄原酸酯能高产率地得到脱氧产物，而α-异构体的产率极低。所采用的关键转化反应为维蒂希烯烃化反应、TEMPO介导的氧化反应和巴顿-麦康比脱氧反应，从而实现了日本桔小实蝇内酯（1）的简洁全合成。我们的成功将有助于对该天然产物进行进一步的生物学研究，也为开发新的潜在有前景的信息素提供了机会。
