88023-78-3Relevant articles and documents
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.
[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.
