51116-92-8Relevant articles and documents
Enantioselective Total Synthesis of Berkeleyone A and Preaustinoids
Franzoni, Ivan,Guo, Chuning,Hong, Benke,Ji, Yunpeng,Jia, Hongli,Li, Houhua,Zhang, Yang
supporting information, p. 14869 - 14874 (2021/05/27)
Herein we report the first enantioselective total synthesis of 3,5-dimethylorsellinic acid-derived meroterpenoids (?)-berkeleyone A and its five congeners ((?)-preaustinoids A, A1, B, B1, and B2) in 12–15 steps, starting from commercially available 2,4,6-trihydroxybenzoic acid hydrate. Based upon the recognition of latent symmetry within D-ring, our convergent synthesis features two critical reactions: 1) a symmetry-breaking, diastereoselective dearomative alkylation to assemble the entire carbon core, and 2) a Sc(OTf)3-mediated sequential Krapcho dealkoxycarbonylation/carbonyl α-tert-alkylation to forge the intricate bicyclo[3.3.1]nonane framework. We also conducted our preliminary biomimetic investigations and uncovered a series of rearrangements (α-ketol, α-hydroxyl-β-diketone, etc.) responsible for the biomimetic diversification of (?)-berkeleyone A into its five preaustinoid congeners.
Biomimetic Synthesis of Complex Flavonoids Isolated from Daemonorops “Dragon's Blood”
Schmid, Matthias,Trauner, Dirk
supporting information, p. 12332 - 12335 (2017/09/25)
The dragonbloodins are a pair of complex flavonoid trimers that have been isolated from the palm tree Daemonorops draco, one of the sources of the ancient resin known as “dragon's blood”. We present a short synthesis that clarifies their relative configur
Total Synthesis and Biological Evaluation of Irciniastatin A (a.k.a. Psymberin) and Irciniastatin B
Uesugi, Shun-Ichiro,Watanabe, Tsubasa,Imaizumi, Takamichi,Ota, Yu,Yoshida, Keisuke,Ebisu, Haruna,Chinen, Takumi,Nagumo, Yoko,Shibuya, Masatoshi,Kanoh, Naoki,Usui, Takeo,Iwabuchi, Yoshiharu
, p. 12333 - 12350 (2016/01/09)
Irciniastatin A (a.k.a. psymberin) and irciniastatin B are members of the pederin natural product family, which have potent antitumor activity and structural complexity. Herein, we describe a full account of our total synthesis of (+)-irciniastatin A and (-)-irciniastatin B. Our synthesis features the highly regioselective Eu(OTf)3-catalyzed, DTBMP-assisted epoxide ring opening reaction with MeOH, which enabled a concise synthesis of the C1-C6 fragment, extensive use of AZADO (2-azaadamantane N-oxyl) and its related nitroxyl radical/oxoammonium salt-catalyzed alcohol oxidation throughout the synthesis, and a late-stage assembly of C1-C6, C8-C16, and C17-C25 fragments. In addition, for the synthesis of (-)-irciniastatin B, we achieved the C11-selective control of the oxidation stage via regioselective deprotection and AZADO-catalyzed alcohol oxidation. The synthetic irciniastatins showed high levels of cytotoxic activity against mammalian cells. Furthermore, chemical footprinting experiments using synthetic compounds revealed that the binding site of irciniastatins is the E-site of the ribosome.