3020-28-8Relevant articles and documents
Electron-Catalyzed Aminocarbonylation: Synthesis of α,β-Unsaturated Amides from Alkenyl Iodides, CO, and Amines
Picard, Baptiste,Fukuyama, Takahide,Bando, Takanobu,Hyodo, Mamoru,Ryu, Ilhyong
supporting information, p. 9505 - 9509 (2021/12/09)
Aminocarbonylation of alkenyl iodides with CO and amines proceeded under heating to produce α,β-unsaturated amides in good yields (23 examples, 71% average yield). This catalyst-free method exhibited good functional-group tolerance, and open a straightforward access to functionalized acrylamides, as illustrated by the synthesis of Ilepcimide. A hybrid radical/ionic mechanism involving chain electron transfer is proposed for this transformation.
A Condensed, Scalable Synthesis of Racemic Koningic Acid
Barbe, Guillaume,Chai, David,Chen, Bin,Dechristopher, Brian,Guay, Daniel,Levesque, Eric,Mancuso, John
, p. 6788 - 6793 (2020/07/14)
The natural product koningic acid (KA) is a selective covalent inhibitor of glyceraldehyde-3-phosphate dehydrogenase (GAPDH), a critical node in the glycolysis pathway. While KA is available commercially, sources are limited and its cost becomes rapidly prohibitive beyond the milligram scale. Additionally, a practical and flexible synthetic route to KA and analogs remains to be developed. Here we detail a new route that is operationally safer, scalable and offers a five-step reduction in the previously reported longest linear sequence.
Protecting group free, stereocontrolled synthesis of β-halo-enamides
Pasqua, Adele E.,Crawford, James J.,Long, De-Liang,Marquez, Rodolfo
experimental part, p. 2149 - 2158 (2012/05/20)
Enamides, dienamides, and enynamides are important building blocks in synthetic, biological, and medicinal chemistry as well as materials science. Despite the extensive breath of their potential utility in synthetic chemistry, there is a lack of simple, high-yielding methods to deliver them efficiently and as single isomers. In this paper, we present a novel, protecting group free, efficient, and stereoselective approach to the generation of β-halo-enamides. The methodology presented provides a robust synthetic platform from which E- or Z-enamides can be generated in good yields and with complete stereocontrol.
Total synthesis of (-)-goniotrionin
Dias, Luiz C.,Ferreira, Marco A. B.
experimental part, p. 4046 - 4062 (2012/06/29)
A stereoselective total synthesis of the reported structure of goniotrionin (4) has been accomplished. The key steps involved the opening of a chiral epoxide, a highly diastereoselective Mukaiyama aerobic oxidative cyclization, a selective 1,2-syn Mukaiyama aldol reaction, and a Noyori reduction.
Total synthesis of iso- and bongkrekic acids: Natural antibiotics displaying potent antiapoptotic properties
Francais, Antoine,Leyva-Perez, Antonio,Etxebarria-Jardi, Gorka,Pena, Javier,Ley, Steven V.
supporting information; experimental part, p. 329 - 343 (2011/03/21)
For over five decades, owing to their antiapoptotic activities, bongkrekic and isobongkrekic acids have generated interest from the scientific community. Here, we disclose full details of our investigation into the synthesis of isobongkrekic acid, which culminated in its first preparation and features various palladium-catalysed cross-couplings and Takai olefination reactions. Access to bongkrekic acid is also reported by this route. These syntheses involve the preparation and use of new general building blocks which could find wider applications. Iso-bong: A versatile first synthesis of isobongkrekic acid (IBA) has been developed. Key steps include three different palladium cross-couplings and an asymmetric homopropargylation. In-depth synthetic studies reveal the challenges faced in generating the right geometry of each diene.
DIYNE COMPOSITIONS
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Page/Page column 39, (2011/02/24)
A novel class of diyne compounds and diyne salts provided herein are effective and potent Olel protein inhibitors, useful for treating fungal pathogens. Compounds, fungicides and methods are provided as novel, potent and broad spectrum antifungal agents for treatment against a wide variety of fungal pathogens in humans and animals, and in the agricultural setting.
Stereoselective total synthesis of etnangien and etnangien methyl ester
Li, Pengfei,Li, Jun,Arikan, Fatih,Ahlbrecht, Wiebke,Dieckmann, Michael,Menche, Dirk
supporting information; experimental part, p. 2429 - 2444 (2010/07/06)
A highly stereoselective joint total synthesis of the potent polyketide macrolide antibiotics etnangien and etnangien methyl ester was accomplished by a convergent strategy and proceeds in 23 steps (longest linear sequence). Notable synthetic features include a sequence of highly stereoselective substrate-controlled aldol reactions to set the characteristic assembly of methyl- and hydroxyl-bearing stereogenic centers of the propionate portions, an efficient diastereoselective Heck macrocyclization of a deliberately conformationally biased precursor, and a late-stage introduction of the labile side chain by means of a high-yielding Stille coupling of protective-group-free precursors. Along the way, an improved, reliable protocol for a Z-selective Stork?Zhao?Wittig olefination of aldehydes was developed, and an effective protocol for a 1,3-syn reduction of sterically particularly hindered β-hydroxy ketones was devised. Within the synthetic campaign, a more detailed understanding of the intrinsic isomerization pathways of these labile natural products was elaborated. The expedient and flexible strategy of the etnangiens should be amenable to designed analogues of these RNA-polymerase inhibitors, thus enabling further exploration of the promising biological potential of these macrolide antibiotics.
Streamlined syntheses of (-)-dictyostatin, 16-desmethyl-25,26- dihydrodictyostatin, and 6- epi -16-desmethyl-25,26-dihydrodictyostatin
Zhu, Wei,Jimenez, Maria,Jung, Won-Hyuk,Camarco, Daniel P.,Balachandran, Raghavan,Vogt, Andreas,Day, Billy W.,Curran, Dennis P.
supporting information; experimental part, p. 9175 - 9187 (2010/08/22)
The dictyostatins are a promising class of potential anti-cancer drugs because they are powerful microtubule-stabilizing agents, but the complexity of their chemical structures is a severe impediment to their further development. On the basis of both synt
Total synthesis of etnangien
Li, Pengfei,Li, Jun,Arikan, Fatih,Ahlbrecht, Wiebke,Dieckmann, Michael,Menche, Dirk
supporting information; experimental part, p. 11678 - 11679 (2009/12/08)
(Chemical Equation Presented) The first total synthesis of the potent RNA-polymerase inhibitor etnangien is described, which establishes unequivocally the relative and absolute configuration of this sensitive macrolide antibiotic. Key features of the expe
Terminal alkynes from aldehydes via dehydrohalogenation of (Z)-1-iodo-1-alkenes with TBAF
Beshai, Mira,Dhudshia, Bhartesh,Mills, Ryan,Thadani, Avinash N.
supporting information; experimental part, p. 6794 - 6796 (2009/04/07)
Terminal alkynes were prepared in near quantitative yields via dehydrohalogenation of (Z)-1-iodo-1-alkenes with tetrabutylammonium fluoride (TBAF) under mild conditions. The methodology was expanded to include a one-pot, direct synthesis of terminal alkynes from aldehydes without the necessity of isolating and purifying the intermediate iodoalkene.
