23074-59-1Relevant articles and documents
Enantioselective Total Synthesis of Nigelladine A via Late-Stage C-H Oxidation Enabled by an Engineered P450 Enzyme
Loskot, Steven A.,Romney, David K.,Arnold, Frances H.,Stoltz, Brian M.
, p. 10196 - 10199 (2017)
An enantioselective total synthesis of the norditerpenoid alkaloid nigelladine A is described. Strategically, the synthesis relies on a late-stage C-H oxidation of an advanced intermediate. While traditional chemical methods failed to deliver the desired outcome, an engineered cytochrome P450 enzyme was employed to effect a chemo- and regioselective allylic C-H oxidation in the presence of four oxidizable positions. The enzyme variant was readily identified from a focused library of three enzymes, allowing for completion of the synthesis without the need for extensive screening.
Catalytic enantioselective total synthesis of (?)-ar-Tenuifolene
Shaw, Kundan,Niyogi, Sovan,Bisai, Vishnumaya
, (2020/03/23)
First catalytic asymmetric total synthesis of aromatic sesquiterpene, (?)-ar-teunifolene (1) is featured (3 steps, 75% overall yields) from commercially available 3-methyl cyclohex-2-enone 16. The enantioenriched 3,3-disubstituted cyclohexanone 11 is obtained from Pd(II)-catalyzed enantioselective (p-tolyl)boronic acid addition to 3-methyl cyclohex-2-enone 16 in 90% ee, which is found to be the key intermediate. A diastereoselective methyllithium addition of this enantioenriched product followed by dehydration completes straightforward access to (?)-ar-teunifolene (1).
A Unique Skeletal Rearrangement of a Bicyclo[33.1]nonanetrione to a Tetrahydroquinolin-2(1 H)-one System
Shen, Qi,Liu, Fang,Zhang, Yu-Chao,Wang, Jie,Zhang, Lei,Wang, Yue,Xu, Hong-Xi,Shao, Zhuzhou,Cao, Yang,Wu, Jing,Liang, Yong,Li, Jian-Xin
supporting information, p. 1711 - 1716 (2018/07/06)
The unexpected formation of a 4-hydroxytetrahydroquinolin-2(1 H)-one from a bicyclo[3.3.1]nonanetrione system and an amino alcohol in the presence of TsOH is reported. The mechanism of this transformation was studied by DFT calculations. The reaction provides an entry to the synthesis of highly functionalized 4-hydroxytetrahydroquinolin-2(1 H)-ones.
