53185-12-9Relevant articles and documents
Concise and highly stereoselective syntheses of D-fagomine and 2-epi-fagomine
Kallam, Srinivasa Reddy,Datrika, Rajender,Khobare, Sandip R.,Gajare, Vikas S.,Rajana, Nagaraju,Mohan, H. Rama,Babu, J. Moses,Siddaiah,Pratap
, p. 1351 - 1353 (2018/03/23)
Highly stereoselective total syntheses of polyhydroxylated piperidines D-fagomine and 2-epi-fagomine have been developed starting from 3,4,6-tri-O-benzyl-D-glucal which is a derivative of D-Glucose. Key steps in the synthesis of these azasugars involved N-Boc-protected amine preparation from oxime followed by stereo specific iodination of alcohol and cascade cyclization triggered by N-Boc deprotection.
Transforming flask reaction into cell-based synthesis: Production of polyhydroxylated molecules via engineered Escherichia coli
Wei, Mohui,Li, Zijie,Li, Tiehai,Wu, Baolin,Liu, Yunpeng,Qu, Jingyao,Li, Xu,Li, Lei,Cai, Li,Wang, Peng George
, p. 4060 - 4065 (2015/11/11)
Dihydroxyacetone phosphate (DHAP)-dependent aldolases have been intensively studied and widely used in the synthesis of carbohydrates and complex polyhydroxylated molecules. However, strict specificity toward donor substrate DHAP greatly hampers their synthetic utility. Here, we transformed DHAP-dependent aldolases-mediated by in vitro reactions into bioengineered Escherichia coli (E. coli). Such flask-to-cell transformation addressed several key issues plaguing in vitro enzymatic synthesis: (1) it solves the problem of DHAP availability by in vivo-hijacking DHAP from the glycolysis pathway of the bacterial system, (2) it circumvents purification of recombinant aldolases and phosphatase, and (3) it dephosphorylates the resultant aldol adducts in vivo, thus eliminating the additional step for phosphate removal and achieving in vivo phosphate recycling. The engineered E. coli strains tolerate a wide variety of aldehydes as acceptor and provide a set of biologically relevant polyhydroxylated molecules in gram scale.
Applications and limitations of the I2-mediated carbamate annulation for the synthesis of piperidines: Five-versus six-membered ring formation
Corkran, Hilary M.,Munneke, Stefan,Dangerfield, Emma M.,Stocker, Bridget L.,Timmer, Mattie S. M.
, p. 9791 - 9802 (2013/10/22)
A protecting-group-free synthetic strategy for the synthesis of piperidines has been explored. Key in the synthesis is an I2-mediated carbamate annulation, which allows for the cyclization of hydroxy-substituted alkenylamines into piperidines, pyrrolidines, and furans. In this work, four chiral scaffolds were compared and contrasted, and it was observed that with both d-galactose and 2-deoxy-d-galactose as starting materials, the transformations into the piperidines 1-deoxygalactonorjirimycin (DGJ) and 4-epi-fagomine, respectively, could be achieved in few steps and good overall yields. When d-glucose was used as a starting material, only the furan product was formed, whereas the use of 2-deoxy-d-glucose resulted in reduced chemo- and stereoselectivity and the formation of four products. A mechanistic explanation for the formation of each annulation product could be provided, which has improved our understanding of the scope and limitations of the carbamate annulation for piperidine synthesis.
