7184-60-3Relevant academic research and scientific papers
Total synthesis of borrelidin
Nagamitsu, Tohru,Takano, Daisuke,Marumoto, Kaori,Fukuda, Takeo,Furuya, Kentaro,Otoguro, Kazuhiko,Takeda, Kazuyoshi,Kuwajima, Isao,Harigaya, Yoshihiro,Omura, Satoshi
, p. 2744 - 2756 (2008/02/05)
(Chemical Equation Presented) The total synthesis of borrelidin has been achieved. The best feature of our synthetic route is macrocyclization at C11-C12 for the construction of an 18-membered ring after esterification between two segments. A detailed examination of the macrocyclization led us to the samarium(II) iodide-mediated intramolecular Reformatsky-type reaction as the most efficient synthetic approach. The two key segments were synthesized through regioselective methylation, directed hydrogenation, stereoselective Reformatsky-type reaction, and MgBr2·Et2O-mediated chelation-controlled allylation.
Stereoselective total synthesis of (-)-borrelidin
Vong, Binh G.,Kim, Sun Hee,Abraham, Sunny,Theodorakis, Emmanuel A.
, p. 3947 - 3951 (2007/10/03)
A convergent synthesis of (-)-borrelidin (1) is reported based on the retrosynthetic disconnections indicated in the picture. Highlights of the strategy include the construction of a strained enynone-containing macrolide and the installation of a cyano group in a regioselective manner by a novel molybdenum-catalyzed hydrostannation of the alkyne.
Total synthesis of (-)-borrelidin
Nagamitsu, Tohru,Takano, Daisuke,Fukuda, Takeo,Otoguro, Kazuhiko,Kuwajima, Isao,Harigaya, Yoshihiro,Omura, Satoshi
, p. 1865 - 1867 (2007/10/03)
Matrix presented. The total synthesis of borrelidin has been achieved. The best feature of our synthetic route is Sml2-mediated intramolecular Reformatsky-type reaction for macrocyclization after esterification between two segments. The two key segments were synthesized through chelation-controlled carbotitanation, chelation-controlled hydrogenation, stereoselective Reformatsky reaction, and MgBr2·Et2O-mediated chelation-controlled allylation.
Enantioselective total synthesis of borrelidin
Duffey, Matthew O.,LeTiran, Arnaud,Morken, James P.
, p. 1458 - 1459 (2007/10/03)
The first total synthesis of the natural product borrelidin is described. The propionate fragment of the molecule was concisely synthesized through catalytic enantioselective reductive aldol reactions, a catalytic Negishi coupling, and a catalytic directed hydrogenation. The propionate segment was then fused to the vinyl iodide fragment through a catalytic Sonogashira coupling. Subsequent catalytic hydrostannylation and catalytic cyanation allowed access to the target structure. Copyright
Application of Conformation Design in Acyclic Stereoselection: Total Synthesis of Borrelidin as the Crystalline Benzene Solvate
Hanessian, Stephen,Yang, Yang,Giroux, Simon,Mascitti, Vincent,Ma, Jianguo,Raeppel, Franck
, p. 13784 - 13792 (2007/10/03)
The total synthesis of (-)-borrelidin (treponemycin), a structurally distinct 18-membered macrolide antibiotic, has been achieved. It was isolated as the crystalline benzene solvate, and its structure was confirmed by a single-crystal X-ray analysis. The deoxypropionate subunit consisting of four alternating C-methyl groups with a C4-C10 syn/syn/anti orientation was elaborated by a new method of iterative cuprate additions to acyclic α,β-unsaturated esters relying on two consequtive 1,3-inductions and starting with D-glyceraldehyde as the chiral progenitor. The unique Z/E cyanodiene unit was obtained as a single isomer by application of the Still-Gennari olefination protocol. The γ-hydroxycyclopentane carboxylic acid subunit was prepared from L-malic acid utilizing a sequential introduction of C-vinyl and C-allyl groups, capitalizing on 1,2-induction in an acyclic α,β-unsaturated ester and carbocyclization by a Grubbs ring closure metathesis reaction. The prevalence of 1,3-syn-disposed deoxypropionate triads in the cuprate additions is rationalized on the basis of minimized syn-pentane interactions in the transition states. A virtual diamond lattice was used as a visual tool to portray the low-energy conformations of the acyclic substrates, and corroborated by 1H NMR homodecoupling studies.
