Angewandte Chemie, International Edition published new progress about Biomimetic synthesis. 30095-98-8 belongs to class esters-buliding-blocks, and the molecular formula is C9H9NO4, Reference of 30095-98-8.
Delayre, Bastien; Piemontesi, Cyril; Wang, Qian; Zhu, Jieping published the artcile< TiCl3-Mediated Synthesis of 2,3,3-Trisubstituted Indolenines: Total Synthesis of (+)-1,2-Dehydroaspidospermidine, (+)-Condyfoline, and (-)-Tubifoline>, Reference of 30095-98-8, the main research area is titanium chloride mediated synthesis indolenine; dehydroaspidospermidine total synthesis; condyfoline total synthesis; tubifoline total synthesis; 1,2-rearrangements; indole alkaloids; natural products; titanium trichloride; total synthesis.
2,3,3-Trisubstituted indolenine constitutes an integral part of many biol. important monoterpene indole alkaloids. We report herein an unprecedented access to this skeleton by a TiCl3-mediated reductive cyclization of tetrasubstituted alkenes bearing a 2-nitrophenyl substituent. The proof of concept is demonstrated firstly by accomplishing a concise total synthesis of (+)-1,2-dehydroaspidospermidine (I) featuring a late-stage application of this key transformation. A sequence of reduction of nitroarene to nitrosoarene followed by 6π-electron-5-atom electrocyclization and a 1,2-alkyl shift of the resulting nitrone intermediate was proposed to account for the reaction outcome. A subsequent total synthesis of (+)-condyfoline (II) not only illustrates the generality of the reaction, but also provides a mechanistic insight into the nature of the 1,2-alkyl shift. The exclusive formation of (+)-condyfoline indicates that the 1,2-alkyl migration follows a concerted Wagner-Meerwein pathway, rather than a stepwise retro-Mannich/Mannich reaction sequence. Conditions for almost quant. conversion of (+)-condyfoline to (-)-tubifoline (III) by way of a retro-Mannich/1,3-prototropy/transannular cyclization cascade are also documented.
Angewandte Chemie, International Edition published new progress about Biomimetic synthesis. 30095-98-8 belongs to class esters-buliding-blocks, and the molecular formula is C9H9NO4, Reference of 30095-98-8.
Referemce:
Ester – Wikipedia,
Ester – an overview | ScienceDirect Topics