18331-31-2Relevant academic research and scientific papers
Redox divergent synthesis of fawcettimine-type lycopodium alkaloids
Zaimoku, Hisaaki,Taniguchi, Tsuyoshi
, p. 9613 - 9619 (2014)
A new approach for synthesis of fawcettimine-type Lycopodium alkaloids is described. A divergent strategy was achieved by applying stereoselective Diels-Alder reaction followed by redox-controlled elaboration. Eventually, (-)-8-deoxyserratinine, (+)-fawcettimine, (-)-lycopoclavamine-A, (-)-serratine, (-)-lycopoclavamine-B and (-)-serratanidine were successfully accessed. A class reunion: The divergent synthesis of fawcettimine-type Lycopodium alkaloids is reported. The present synthetic study features stereoselective Diels-Alder reactions to construct carbon cores of alkaloids. Subsequently, (-)-8-deoxyserratinine, (+)-fawcettimine, (-)-lycopoclavamine-A, (-)-serratine, (-)-lycopoclavamine-B and (-)-serratanidine were synthesized from the common synthetic intermediate via stereoselective reduction or oxygenation.
Structure elucidation and synthesis of lycoposerramine-B, a novel oxime-containing lycopodium alkaloid from Lycopodium serratum thunb
Katakawa, Kazuaki,Kitajima, Mariko,Aimi, Norio,Seki, Hiroko,Yamaguchi, Kentaro,Furihata, Kazuo,Harayama, Takashi,Takayama, Hiromitsu
, p. 658 - 663 (2005)
(Chemical Equation Presented) A new alkaloid, lycoposerramine-B (1), containing an oxime function, was isolated from the club moss Lycopodium serratum Thunb. The structure of 1 was elucidated by spectroscopic analysis, including J-resolved HMBC spectroscopy, and confirmed by its synthesis from the known alkaloid, serratinine (3).
Collective synthesis of lycopodium alkaloids and tautomer locking strategy for the total synthesis of (-)-lycojapodine A
Li, Houhua,Wang, Xiaoming,Hong, Benke,Lei, Xiaoguang
, p. 800 - 821 (2013/04/23)
The collective total synthesis of Lycopodium alkaloids (+)-fawcettimine (1), (+)-fawcettidine (2), (+)-alopecuridine (4), (-)-lycojapodine A (6), and (-)-8-deoxyserratinine (7) has been accomplished from a common precursor (15) based on a highly concise route inspired by the proposed biosynthesis of the fawcettimine- and serratinine-type alkaloids. An intramolecular C-alkylation enabled efficient installation of the challenging spiro quaternary carbon center and the aza-cyclononane ring. The preparation of the tricyclic skeleton as well as the establishment of the correct relative stereochemistry of the oxa-quaternary center were achieved by hydroxyl-directed SmI2- mediated pinacol couplings. An unprecedented tandem transannular N-alkylation and removal of a Boc group was discovered to realize a biosynthesis-inspired process to furnish the desired tetracyclic skeleton. Of particular note is the unique and crucial tautomer locking strategy employed to complete the enantioselective total synthesis of (-)-lycojapodine A (6). The central step in this synthesis is the late-stage hypervalent iodine oxidant (IBX or Dess-Martin periodinane)/TFA-mediated tandem process, which constructed the previously unknown carbinolamine lactone motif and enabled a biomimetic transformation to generate (-)-lycojapodine A (6) in a single operation.
Divergent and efficient syntheses of the Lycopodium alkaloids (-)-Lycojaponicumin C, (-)-8-deoxyserratinine, (+)-fawcettimine, and (+)-fawcettidine
Hou, Si-Hua,Tu, Yong-Qiang,Liu, Lin,Zhang, Fu-Min,Wang, Shao-Hua,Zhang, Xiao-Ming
supporting information, p. 11373 - 11376 (2013/11/06)
Four from one: The four title alkaloids (structures shown in blue box) have been synthesized by using a common versatile intermediate with a 6/5/5 tricyclic skeleton. This tricyclic intermediate could be easily assembled by using an intramolecular carbene addition/cyclization and a Dieckmann condensation/Tsuji-Trost allylation as key steps. Copyright
Total syntheses of lycopodium alkaloids (+)-fawcettimine, (+)-fawcettidine, and (-)-8-deoxyserratinine
Li, Houhua,Wang, Xiaoming,Lei, Xiaoguang
supporting information; experimental part, p. 491 - 495 (2012/02/16)
A shared story: Three fawcettimine- and serratinine-type Lycopodium alkaloids are prepared from a common tetracyclic spirodiketone intermediate in concise total syntheses (see scheme). The intermediate was constructed by a remarkable biosynthesis-inspired
Application of the helquist annulation in lycopodium alkaloid synthesis: Unified total syntheses of (-)-8-deoxyserratinine, (+)-fawcettimine, and (+)-lycoflexine
Yang, Yu-Rong,Shen, Liang,Huang, Jiu-Zhong,Xu, Tao,Wei, Kun
, p. 3684 - 3690 (2011/07/09)
A unified strategy for total synthesis of the Lycopodium alkaloids (-)-8-deoxyserratinine (7), (+)-fawcettimine (1), and (+)-lycoflexine (4) is detailed. The key features include a highly efficient Helquist annulation to assemble the cis-fused 6/5 bicycle
Total synthesis of (-)-8-deoxyserratinine via an efficient helquist annulation and double N-alkylation reaction
Yang, Yu-Rong,Lai, Zeng-Wei,Shen, Liang,Huang, Jiu-Zhong,Wu, Xing-De,Yin, Jun-Lin,Wei, Kun
supporting information; experimental part, p. 3430 - 3433 (2010/09/08)
(Equation Presented). The first enantioselective total synthesis of (-)-8-deoxyserratinine has been achieved in 15 steps from enone 4 with 7% overall yield. The key features include a highly efficient Helquist annulation to furnish the cis-fused 6/5 bicycle, facile construction of the aza nine-membered ring system employing double N-alkylation strategy, as well as asymmetric Shi epoxidation, delivering the desired β-epoxide stereospecifically.
