72036-52-3Relevant academic research and scientific papers
Total synthesis of (+)-ar -macrocarpene
Khatua, Arindam,Niyogi, Sovan,Bisai, Vishnumaya
, p. 7140 - 7143 (2019/08/07)
This report features the first catalytic asymmetric total synthesis of a sesquiterpene, (+)-ar-macrocarpene (1), in 7 steps with 42.1% overall yields from commercially available inexpensive 5,5-dimethylcyclohexane 1,3-dione. This strategy relies on a key [3,3]-sigmatropic rearrangement effecting reductive transposition through allylic diazene rearrangement (ADR) in a single step from intermediate allylic alcohol (+)-12 under the Mitsunobu reaction conditions with o-nitrobenzenesulfonyl hydrazide (o-NBSH). Enantioselective reduction of α-bromo vinylogous ester 16 under the Corey-Bakshi-Shibata reduction conditions forges the required stereocenter in the allylic alcohol (+)-12 in a highly enantioenriched manner (95% ee).
