144754-24-5Relevant academic research and scientific papers
Total synthesis of ent-pavettamine
Bode, Moira L.,Fernandes, Manuel A.,Rousseau, Amanda L.,Zimuwandeyi, Memory
, p. 1440 - 1446 (2021/06/16)
Pavettamine, a plant toxin first isolated from Pavetta harborii in 1995, was previously identified as a polyamine with C2 symmetry and a 1,3-syn-diol moiety on a C10 carbon backbone – one of very few substituted polyamines to be isolated from nature. Its absolute configuration was later established by our first reported total synthesis in 2010. Herein we report the first total synthesis of the enantiomer of pavettamine, ent-pavettamine. The symmetrical structure of the molecule allows for the synthesis of a common C5 fragment that can be divergently transformed into two synthons for later convergent coupling to furnish the target carbon framework. Based on the success of the protocol we employed for the synthesis of the naturally occurring pavettamine, (S)-malic acid was again the starting material of choice for the synthesis of the two individual C5 fragments, with strategic differences in terminal-group manipulation allowing for the synthesis of ent-pavettamine rather than pavettamine. Chain extension and stereoselective ketone reduction were achieved using the (R)-methyl p-tolyl sulfoxide chiral auxiliary to give the desired 1,3-syn-diol C5 unit. A protecting-group strategy was also developed for the orthogonal protection of the alcohol and amine functional groups as they were unveiled. The functionalized C5 fragments were coupled via reductive amination revealing the C10 carbon backbone. Deprotection of the alcohol and amine functional groups successfully provided ent-pavettamine as a TFA salt.
Total Synthesis of (-)-Marinisporolide C
Dias, Luiz C.,De Lucca, Emilio C.
, p. 3019 - 3045 (2017/03/23)
The first total synthesis of (-)-marinisporolide C is described, which establishes unequivocally the relative and absolute configuration of this oxopolyene macrolide. Key features of this synthesis include a series of highly stereoselective aldol reactions followed by directed reductions to build the polyol domain, a Stille cross-coupling reaction to assemble the polyene, and an intramolecular Horner-Wadsworth-Emmons olefination to forge the macrocyclic ring. Despite the initial approach to marinisporolide A using a Yamaguchi macrolactonization reaction that was unsuccessful due to steric hindrance of the oxygen at the C33 position, we were able to prepare a known derivative of marinisporolide A and consequently confirm its stereochemical assignment.
Total Synthesis of the Oxopolyene Macrolide (-)-Marinisporolide C
Dias, Luiz C.,De Lucca, Emílio C.
supporting information, p. 6278 - 6281 (2016/01/09)
The first total synthesis of (-)-marinisporolide C was performed in 25 steps (longest linear sequence) and an overall yield of 1%. Due to the high degree of convergence and robustness, the C9-C35 fragment that corresponds to the polyol portion was obtaine
Total synthesis of solandelactones A, B, E, and F exploiting a tandem petasis-claisen lactonization strategy
White, James D.,Lincoln, Christopher M.,Yang, Jongtae,Martin, William H. C.,Chan, David B.
, p. 4139 - 4150 (2008/09/20)
(Chemical Equation Presented) Solandelactones A, B, E, and F were synthesized using Nozaki-Hiyama-Kishi coupling of iododiene 13 with aldehydes 14 and 99 obtained by oxidation of alcohols 92 and 94. Key steps in the synthesis of 92 and 94 were (i) a Nagao asymmetric acetate aldol reaction of aldehyde 77 with thionothiazolidine 78 to set in place an alcohol that becomes the (75) lactone center of solandelactones, (ii) a Simmons-Smith cyclopropanation of 80 directed by this alcohol, and (iii) Petasis methylenation of cyclic carbonate 90 in tandem with a Claisen rearrangement that generates the octenalactone portion of solandelactones. Synthesis of solandelactones A, B, E, and F confirmed their gross structure and absolute configuration at C7, 8, 10, and 14 but showed that alcohol configuration at C11 must be reversed in pairs, A/B and E/F, from the previous assignment made to these hydroid metabolites. Thus, solandelactones A and B are correctly represented by 2 and 1, respectively, whereas solandelactones E and F are 6 and 5. A biogenesis of solandelactones is proposed for these C22 oxylipins that parallels a hypothesis put forward previously to explain the origin of C20 cyclopropane-containing algal products.
Total synthesis of solandelactones E and F, homoeicosanoids from the hydroid Solanderia secunda
White, James D.,Martin, William H.C.,Lincoln, Christopher,Yang, Jongtae
, p. 3481 - 3483 (2008/02/12)
Asymmetrie total syntheses of solandelactones E and F confirmed that hydroxyl configuration at C11 in these oxylipins had been misassigned and that the stereochemistry at this center should be reversed. Key steps in the synthesis involved a Nagao asymmetr
Novel boronate esters
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Page/Page column 11, (2008/06/13)
The present invention relates to optically active boronate derivatives which are useful as intermediates for the synthesis of HMG-CoA enzyme inhibitors such as atorvastatin, cerivastatin, rosuvastatin, pitavastatin, and fluvastatin.
Total synthesis of marine oxylipin bacillariolides I-III
Miyaoka, Hiroaki,Tamura, Masahide,Yamada, Yasuji
, p. 8083 - 8094 (2007/10/03)
Marine oxylipin bacillariolides I-III were synthesized from (R)-malic acid, using diastereoselective one-pot formation of the chiral cyclopentane derivative from the anion of allyl phenyl sulfone and chiral epoxymesylate as the key reaction. (C) 2000 Elsevier Science Ltd.
Synthetic studies toward ansatrienines: Application of the Evans- Tishchenko reaction to chiral enones
Schoening, Kai-Uwe,Hayashi,Powell, Douglas R.,Kirschning, Andreas
, p. 817 - 820 (2007/10/03)
Practical syntheses of the C9-C14 sterotriade 5 and the C1-C8 polyene unit 6 in ansatrienine A (mycotriene) (1a), and other ansamycin antibiotics is described. A key step for controlling the configuration of the stereogenic center at C13 involves the stereoselective reduction of enone 10 using the Evans-Tishchenko reaction.
The absolute configuration and total synthesis of korormicin
Uehara, Hisatoshi,Oishi, Tohru,Yoshikawa, Kazuhiro,Mochida, Kenichi,Hirama, Masahiro
, p. 8641 - 8645 (2007/10/03)
The marine antibiotic korormicin, isolated from the culture filtrate of marine bacterial strain Pseudoalteromonas sp. F-420, specifically inhibits the growth of marine Gram-negative bacteria without affecting terrestrial species. The absolute configuration of korormicin was determined by the combination of a CD exciton chirality method and chemical degradation. Convergent total synthesis of korormicin has been also achieved.
Synthesis of cyclopentane-containing marine eicosanoid bacillariolide II
Miyaoka, Hiroaki,Tamura, Masahide,Yamada, Yasuji
, p. 621 - 624 (2007/10/03)
Marine eicosanoid bacillariolide II was synthesized from (R)-malic acid, involving the diastereoselective one-pot formation of chiral cyclopentane derivative 12 from the anion of allyl phenyl sulfone and chiral epoxymesylate 11 as the key step.
