Download or read book Towards the Total Synthesis of Amphidinolide F written by Daniel A. Mills and published by . This book was released on 2021 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt:
Download or read book Part I Total Synthesis of Marine Macrolide Amphidinolide F and Synthetic Studies Toward Amphidinolide C written by Subham Mahapatra and published by . This book was released on 2013 with total page 639 pages. Available in PDF, EPUB and Kindle. Book excerpt: More than 30 members of the diverse amphidinolide family of biologically active macrolides have been isolated over last three decades. From this family, amphidinolides C and F stand among the most complex and densely functionalized affiliates. Recently, we have accomplished the first total synthesis of amphidinolide F. The all-carbon framework of amphidinolide C has been synthesized. During endeavor toward the total syntheses of amphidinolides F / C, we have uncovered a "hidden symmetry element" present in the northern and southern domains of amphidinolides F / C. The southern C1-C and northern C1-C25 tetrahydrofuran segments were derived from a common intermediate. A scalable silver-catalyzed isomerization / cyclization on propargyl-benzoate / diol furnished the common intermediate in multigram quantity. The common intermediate provided access to over half of carbon backbone of the macrocycle as well as majority of stereochemistry present in amphidinolides F / C. Two strategically different techniques have been developed for the C9-C11 diene preparation. A metal-catalyst free Weinreb amide-vinyl lithium coupling / methylenation sequence furnished the diene motif. Alternately, diastereoselective addition of a dienyl iodide derived 2-lithio-1,3-diene species to an [alpha]-oxy aldehyde installed the C9-C11 diene and secured the C8 stereochemistry in single operation. The dienyl iodide was prepared via a regioselective hydrostannylation on an enyne. A challenging alkylation between an [alpha]-branched sulfone and an [alpha]-silyloxy iodide generated the all-carbon frameworks of amphidinolides F / C. An efficient oxidative desulfurization incorporated the carbonyl moiety at C15. The protecting group on C18 alcohol was found to have significant effect on the sulfone-iodide alkylation / oxidative desulfurization sequence. Installation of chelating ethoxyethyl ether on C18 alcohol helped the successful incorporation of C15 ketone and solved the deprotection problem in advanced stage of synthesis. A detailed analytical and computational study on proline sulfonamide-catalyzed aldol reactions has been performed. The pKa value of a proline sulfonamide catalyst was determined experimentally via NMR titration technique. Computational study revealed the origin of enhanced stereoselectivity by proline sulfonamide catalysts over parent proline. The non-classical hydrogen bonding interactions were found to be responsible for improved diastereoselectivity.
Download or read book Towards the Total Synthesis of Amphidinolides C and F written by Ludovic Decultot and published by . This book was released on 2016 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt:
Download or read book Studies Toward the Total Synthesis of Amphidinolide C written by Robert H. Bates and published by . This book was released on 2009 with total page 394 pages. Available in PDF, EPUB and Kindle. Book excerpt: Amphidinolide C is one of the most biologically potent members of the amphidinolide family of natural products. Detailed in this thesis are studies toward the total synthesis of this complex macrolide. Three distinct syntheses of the C(1)-C(9) fragment are described. The first generation synthesis involves a diastereoselective chelate-controlled [3+2]-annulation reaction to form the C(3)-C(6) trans tetrahydrofuran. The second generation approach takes advantage of the C(4) methyl substituent to induce diastereoselectivity in an intramolecular hetero-Michael cyclization to form the same tetrahydrofuran. The third generation incorporates a non-chelate-controlled [3+2]-annulation reaction to afford the cis tetrahydrofuran product, followed by a base-promoted epimerization to the desired trans tetrahydrofuran. This route was accomplished in fewer steps than the first generation synthesis. Also described are stereoselective syntheses of the C(18)-C(34) C(10)-C(26) fragments of amphidinolide C, and the C(10)-C(29) fragment of amphidinolide F, a closely related natural product. Finally, a clear plan for the completion of the total synthesis of amphidinolide C is presented.
Download or read book Towards the Total Synthesis of Amphidinolide C written by Guang Yang and published by . This book was released on 2013 with total page 213 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Download or read book Progress Towards the Total Synthesis of Amphidinolide E written by Andrew Frederick Nolting and published by . This book was released on 2006 with total page 194 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Download or read book Progress Towards the Total Synthesis of the Potent Antitumor Antibiotic Amphidinolide C written by Jesse D. Carrick and published by . This book was released on 2004 with total page 170 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Download or read book Progress Towards the Total Synthesis of Amphidinolide C written by Nicholas A. Morra and published by . This book was released on 2012 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt: A second generation catalyst for the Mukaiyama oxidative cyclization for the formation of trans-THF rings is described. Co(nmp)2, displays increased stability to the reaction conditions, resulting in lower catalyst loadings, lower reaction temperatures, and significantly higher purity and yields of the products. Three procedures have been developed with this new water-soluble catalyst that greatly simplifies the post-reaction purification, making this procedure the premier method of forming trans-THF rings. This new catalyst has been applied towards the total synthesis of the potently bioactive macrocycle, Amphidinolide C. Herein we report the successful synthesis of several fragments of the natural product, and our attempts at coupling them to complete the synthesis. The C(1)-C(9) was achieved via two routes, both utilizing the highly effective oxidation catalyst Co(nmp)2 to form the methyl substituted trans-THF ring. Synthetic highlights include a regioselective Shi epoxidation, and the design and introduction of a novel Lewis acid (BF2OBn×OEt2) to facilitate a stereoselective reductive epoxide opening. The C(18)-C(34) fragment was also achieved via two routes, culminating in both the shortest (11 steps) and highest yielding (26% overall yield) approaches to this segment. Synthetic highlights of this fragment include a selective methylation of a diyne, and a highly selective alkynylation of a THF aldehyde, achieving excellent dr (>20:1) without the addition of an external chiral compound. Advanced intermediates comprising the entirety of the carbon backbone of the molecule have been synthesized, which in theory could complete the total synthesis in as few as two bond forming steps.
Download or read book Studies Towards the Total Synthesis of Amphidinolides O and P written by Matthew A. Foster and published by . This book was released on 2001 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt:
Download or read book Studies Toward the Synthesis of the Amphidinolides written by Brian J. Myers and published by . This book was released on 2000 with total page 428 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Download or read book Towards a Total Synthesis of amphidinolide K written by Natalie E. Campbell and published by . This book was released on 2014 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt:
Download or read book The Total Synthesis of the Assigned Structure of Amphidinolide A written by Lamont R. Terrell and published by . This book was released on 2002 with total page 530 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Download or read book Total Synthesis of Amphidinolide E and Amphidinolide E Stereoisomers written by Porino J. Va and published by . This book was released on 2007 with total page 472 pages. Available in PDF, EPUB and Kindle. Book excerpt: Detailed in the following thesis are stereocontrolled syntheses of four amphidinolide E stereoisomers: amphidinolide E, 2- epi -amphidinolide E, 19- epi -amphidinolide E, and 2- epi -19- epi -amphidinolide E. Preliminary studies targeting amphidinolide E led to the inadvertent syntheses of 2- epi -amphidinolide E and 2- epi -19- epi -amphidinolide E due to an unexpected and highly selective C2 inversion during the modified Yamaguchi esterification step involving the (2 S, 3 S) (CO) 3 Fe-complexed dienoic acid. Ultimately, this C2 inversion phenomenon was discovered and use of the (2 S, 3 R) (CO) 3 Fe-complexed dienoic acid enabled the syntheses of amphidinolide E and 19- epi -amphidinolide E. Featured in the synthetic route is the synthesis of the tetrahydrofuran core of amphidinolide E through a highly diastereoselective [3+2] annulation reaction. Also noteworthy, are the synthesis of the 19-membered macrocycle via a ring closing metathesis reaction and use of the (CO) 3 Fe-unit as a diene protecting group to enable an efficient esterification of the hindered alcohol substrate.
Download or read book Total Synthesis of amphidinolide W and Efforts Toward Total Synthesis of lasonolide A written by Gangli Gong and published by . This book was released on 2005 with total page 374 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Download or read book The Total Synthesis of the Proposed Structure of Amphidinolide A written by Joseph Samuel Ward and published by . This book was released on 2002 with total page 396 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Download or read book Amphidinolide K written by Athanassios Andreou and published by . This book was released on 2009 with total page 206 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Download or read book Total Synthesis of Amphidinolide X written by Carles Rodríguez Escrich and published by . This book was released on 2008 with total page 392 pages. Available in PDF, EPUB and Kindle. Book excerpt:
