88023-83-0Relevant academic research and scientific papers
Total synthesis of the actinoallolides and a designed photoaffinity probe for target identification
Anketell, Matthew J.,Paterson, Ian,Sharrock, Theodore M.
supporting information, p. 8109 - 8118 (2020/11/03)
The actinoallolides are a family of polyketide natural products isolated from the bacterium Actinoallomurus fulvus. They show potent biological activity against trypanosomes, the causative agents of the neglected tropical diseases human African trypanosomiasis (sleeping sickness) and Chagas disease, while exhibiting no cytotoxicity against human cell lines. Herein, we give a full account of our strategy evolution towards the synthesis of this structurally unique class of 12-membered macrolides, which culminated in the first total synthesis of (+)-actinoallolide A in 20 steps and 8% overall yield. Subsequent late-stage diversification then provided ready access to the congeneric (+)-actinoallolides B-E. Enabled by this flexible and efficient endgame sequence, we also describe the design and synthesis of a photoaffinity probe based on actinoallolide A to investigate its biological mode of action. This will allow ongoing labelling studies to identify their protein binding target(s). This journal is
Total synthesis of 10-isocyano-4-cadinene and its stereoisomers and evaluations of antifouling activities
Nishikawa, Keisuke,Nakahara, Hiroshi,Shirokura, Yousuke,Nogata, Yasuyuki,Yoshimura, Erina,Umezawa, Taiki,Okino, Tatsufumi,Matsuda, Fuyuhiko
experimental part, p. 6558 - 6573 (2011/10/05)
The first enantioselective total synthesis of 10-isocyano-4-cadinene, a marine sesquiterpene isolated from nudibranchs of the family Phyllidiidae, and determination of its absolute stereochemistry were achieved. 10-Isocyano-4-cadinene is expected to be a novel nontoxic antifouling agent. In the synthesis, intermolecular Diels-Alder reaction and samarium diiodide induced Barbier-type cyclization were employed as key steps. The absolute configuration of 10-isocyano-4-cadinene was determined as (1S,6S,7R,10S) by comparison of the optical rotations between natural and synthetic samples. In addition, the authors successfully synthesized 10-epi- and di-1,6-epi-10-isocyano-4-cadinene through the same synthetic pathway. Antifouling activities against Balanus amphitrite with the cadinenes were also evaluated.
Total Synthesis of 10-lsocyano-4-cadinene and Determination of Its Absolute Configuration
Nishikawa, Keisuke,Nakahara, Hiroshi,Shirokura, Yousuke,Nogata, Yasuyuki,Yoshimura, Erina,Umezawa, Taiki,Okino, Tatsufumi,Matsuda, Fuyuhiko
supporting information; experimental part, p. 904 - 907 (2010/06/16)
Chemical Equation Presentation The first enantloselective total synthesis of 10-isocyano-4-cadinene, a marine sesquiterpene isolated from nudibranchs of the family Phyllidiidae, was achieved. The cadinene is expected to be a novel nontoxic antifouling agent. In the synthesis, an intermolecular Diels-Alder reaction and a Sml2-induced Barbier-type reaction were employed as key steps. The absolute configuration of 10-isocyano-4-cadinene was determined to be (1S, 6S, 7R, 10S) on the basis of the total synthesis. Antifouling activities against Balanus amphitrite with both enantiomers of 10-isocyano4-cadinene were also evaluated
[1,2]-Wittig rearrangement from chloromethyl ethers
Gómez, Cecilia,Maciá, Beatriz,Lillo, Victor J.,Yus, Miguel
, p. 9832 - 9839 (2007/10/03)
The reaction of different chloromethyl ethers 1 with an excess of lithium powder and a catalytic amount of 4,4′-di-tert-butylbiphenyl (2.5 mol %) in THF at 0 °C leads to the corresponding α-lithiomethyl ether intermediates, through a chlorine-lithium exchange, which spontaneously undergo a clean [1,2]-Wittig rearrangement affording the expected homobenzylic alcohols 2. This is the first version of this rearrangement starting from easily available chloromethyl ethers.
The palladium-catalyzed enyne cycloisomerization reaction in a general approach to the asymmetric syntheses of the picrotoxane sesquiterpenes. Part I. First-generation total synthesis of corianin and formal syntheses of picrotoxinin and picrotin
Trost, Barry M.,Haffner, Curt D.,Jebaratnam, David J.,Krische, Michael J.,Thomas, Andrew P.
, p. 6183 - 6192 (2007/10/03)
The palladium-catalyzed enyne cycloisomerization is used as a key ring-forming process for the obtention of the cis-fused hydrindane carbon skeleton characteristic of the picrotoxanes sesquiterpenes. The enyne cycloisomerization product is suitably functionalized so that each carbon of the hydrindane core can be modified to permit access to many members of the picrotoxane family, not only to picrotoxinin itself. Part I of this report describes our first-generation approach to the picrotoxane sesquiterpenes as illustrated by the asymmetric synthesis of corianin and the asymmetric formal syntheses of picrotoxinin and picrotin. A new catalyst system to effect the cycloisomerization emerged from this study. Subsequent work proved the generality of this catalyst system.
Carbocyclic analogues of D-ribose-5-phosphate: Synthesis and behavior with 5-phosphoribosyl α-1-pyrophosphate synthetases
Parry, Ronald J.,Burns, Mark R.,Skae, Phillip N.,Hoyt, Jeffrey C.,Pal, Biman
, p. 1077 - 1088 (2007/10/03)
The synthesis of cyclopentyl and cyclopentenyl analogues of the α- anomer of D-ribose-5-phosphate from D-ribonolactone and D-ribose is described. These analogues, which have the same absolute configuration as D- ribose-5-phosphate, were incubated with PRPP synthetases in an attempt to prepare the corresponding carbocyclic PRPP analogues. The carbocyclic ribose- 5-phosphate analogues were found to be inhibitors, rather than substrates, for 5-phosphoribosyl α-1-pyrophosphate synthetases of both bacterial and human origin. The inhibitory behavior of the analogues is described.
A MILD METHOD FOR THE CONVERSION OF ALCOHOLS TO METHYLTHIOMETHYL ETHERS
Medina, Julio C.,Salomon, Magalie,Kyler, Keith S.
, p. 3773 - 3776 (2007/10/02)
Alcohols can be easily transformed to their corresponding methylthiomethyl ethers under mild conditions by treatment with methyl sulfide and benzoyl peroxide in acetonitrile.
PROTECTION OF ALCOHOLS AS THEIR (p-METHOXYBENZYLOXY)METHYL ETHERS.
Kozikowski, Alan P.,Wu, Jiang-Ping
, p. 5125 - 5128 (2007/10/02)
Protection of even tertiary alcohols can be accomplished by treatment with p-methoxybenzyl chloromethyl ether.Deprotection can be effected under mild conditions using the DDQ reaction conditions described by Oikawa.
