765915-17-1Relevant academic research and scientific papers
Prediction and determination of the stereochemistry of the 1,3,5-trimethyl-substituted alkyl chain in verucopeptin, a microbial metabolite
Yoshimura, Aya,Kishimoto, Shinji,Nishimura, Shinichi,Otsuka, Saori,Sakai, Yuki,Hattori, Akira,Kakeya, Hideaki
, p. 6858 - 6867 (2014/08/18)
For the prediction of the relative stereochemistry of 1,3-dimethyl substitution in alkyl chains, a simple approach based on 1H NMR data was recently proposed; Δδ values of methylene protons located between methyl-substituted methine carbons can
Formal synthesis of dictyostatin and synthesis of two dictyostatin analogues
Gallon, Julien,Esteban, Jorge,Bouzbouz, Samir,Campbell, Matthew,Reymond, Sébastien,Cossy, Janine
supporting information, p. 11788 - 11797 (2012/11/07)
A formal convergent synthesis of dictyostatin from (R)-Roche ester is described. Synthetic highlights include a Ni-catalyzed Nozaki-Hiyama-Kishi coupling between an aldehyde and a Z vinyl iodide to assemble the two main fragments, a diastereoselective Myers alkylation, a stereoselective Evans aldolization, two asymmetric Duthaler crotyltitanations, and a stereoselective Pd-catalyzed Marshall allenylindium addition to install the stereogenic centers of dictyostatin. The synthesis of (9R)-epi-dictyostatin and a new ring-contracted dictyostatin isomer were also achieved. Copyright
Total Synthesis of rapamycin
Ley, Steven V.,Tackett, Miles N.,Maddess, Matthew L.,Anderson, James C.,Brennan, Paul E.,Cappi, Michael W.,Heer, Jag P.,Helgen, Celine,Kori, Masakuni,Kouklovsky, Cyrille,Marsden, Stephen P.,Norman, Joanne,Osborn, David P.,Palomero, Maria A.,Pavey, John B. J.,Pinel, Catherine,Robinson, Lesley A.,Schnaubelt, Juergen,Scott, James S.,Spilling, Christopher D.,Watanabe, Hidenori,Wesson, Kieron E.,Willis, Michael C.
experimental part, p. 2874 - 2914 (2009/12/25)
For over 30 years, rapamycin has generated a sustained and intense interest from the scientific community as a result of its exceptional pharmacological properties and challenging structural features. In addition to its well known therapeutic value as a potent immunosuppressive agent, rapamycin and its derivatives have recently gained prominence for the treatment of a wide variety of other human malignancies. Herein we disclose full details of our extensive investigation into the synthesis of rapamycin that culminated in a new and convergent preparation featuring a macro-etherification/catechol-templating strategy for construction of the macrocyclic core of this natural product.
Highly diastereoselective desymmetrisation of cyclic meso-anhydrides and derivatisation for use in natural product synthesis
Evans, Amanda C.,Longbottom, Deborah A.,Matsuoka, Masato,Davies, John E.,Turner, Richard,Franckeviius, Vilius,Ley, Steven V.
experimental part, p. 747 - 760 (2009/06/19)
A new and efficient desymmetrisation of succinic and glutaric cyclic meso-anhydrides is described, providing excellent yields and diastereoselectivities in most cases. Derivatisation of the desymmetrised products is demonstrated by their conversion into m
Total synthesis of 10-deoxymethynolide and narbonolide
Xuan, Richeng,Oh, Hong-Se,Lee, Younghoon,Kang, Han-Young
, p. 1456 - 1461 (2008/09/16)
(Chemical Equation Presented) A flexible and convenient approach was developed for the synthesis of 10-deoxymethynolide (1) and narbonolide (2), which are aglycones of the methymycin and the pikromycin families of macrolide antibiotics. These lactones are
Total synthesis of rapamycin
Maddess, Matthew L.,Tackett, Miles N.,Watanabe, Hidenori,Brennan, Paul E.,Spilling, Christopher D.,Scott, James S.,Osborn, David P.,Ley, Steven V.
, p. 591 - 597 (2008/02/01)
Rapamycin synthesis all wrapped up: A new convergent synthesis of rapamycin (1) is reported that involves a macroetherification/catechol tethering strategy for construction of the macrocyclic core of this intriguing natural product. Other studies on this commercialized potent immunosuppressant delineate new cell signaling pathways of relevance to cancer chemotherapy. (Chemical Equation Presented).
Iterative deoxypropionate synthesis based on a copper-mediated directed allylic substitution: Formal total synthesis of borrelidin (C3-C11 fragment)
Herber, Christian,Breit, Bernhard
, p. 6684 - 6691 (2008/09/17)
A new iterative strategy for the flexible preparation of any oligodeoxypropionate stereoisomer is presented which relies on an o-DPPB-directed copper mediated allylic substitution employing enantiomerically pure Grignard reagents; the reaction is working with perfect control over all aspects of the reaction selectivity. This key C-C bond-forming step features reversed polarity compared with established enolate alkylation methodology. It thus avoids existing problems of enolate alkylation strategies such as enolate reactivity as well as costs and problems associated with the chiral auxiliary. Practicability of this new method is demonstrated through application in natural product syntheses. Thus, an efficient synthesis of the northern part of the angiogenesis inhibitor borrelidin (28), the deoxypropionate building block 27, could be devised, representing a formal total synthesis.
Iterative deoxypropionate synthesis based on a copper-mediated directed allylic substitution
Breit, Bernhard,Herber, Christian
, p. 3790 - 3792 (2007/10/03)
Can't have too much of a good thing: A flexible, iterative strategy based on a highly selective copper-mediated allylic substitution makes the preparation of any desired oligo(deoxypropionate) stereoisomer possible (see scheme; RDG = reagent-directing group). This approach differs from the established enolate-alkylation methodology through the reversed polarity of the reaction partners and avoids several problems associated with the latter method.
