129083-32-5Relevant academic research and scientific papers
Deletion of the C26 Methyl Substituent from the Bryostatin Analogue Merle 23 Has Negligible Impact on Its Biological Profile and Potency
Zhao, Xiguang,Kedei, Noemi,Michalowski, Alexandra,Lewin, Nancy E.,Keck, Gary E.,Blumberg, Peter M.
, p. 1049 - 1059 (2018)
Important strides are being made in understanding the effects of structural features of bryostatin 1, a candidate therapeutic agent for cancer and dementia, in conferring its potency toward protein kinase C and the unique spectrum of biological responses that it induces. A critical pharmacophoric element in bryostatin 1 is the secondary hydroxy group at the C26 position, with a corresponding primary hydroxy group playing an analogous role in binding of phorbol esters to protein kinase C. Herein, we describe the synthesis of a bryostatin homologue in which the C26 hydroxy group is primary, as it is in the phorbol esters, and show that its biological activity is almost indistinguishable from that of the corresponding compound with a secondary hydroxy group.
Synthesis of trisaccharides by hetero-diels-alder welding of two monosaccharide units
Himanen, Jatta A.,Pihko, Petri M.
supporting information; experimental part, p. 3765 - 3780 (2012/09/25)
A new strategy for the synthesis of di- and trisaccharides based on the de novo synthesis of the linking saccharide unit is presented. In this strategy, functionalized monosaccharide building blocks already incorporating the glycosidic linkages are welded together using a metal-catalyzed hetero-Diels-Alder (HDA) reaction to generate a new monosaccharide unit between them. The highest yields and selectivities in the HDA reaction were obtained by using chiral Schiff base chromium complexes. Disaccharide products were accessible by reaction of Danishefsky's diene with acetyl- and benzyl-protected galactoside aldehydes. For the synthesis of trisaccharide products, acetyl-protected glucose or galactose-derived dienes were fused with monosaccharide-derived aldehydes using chromium catalysts for the HDA reaction. The desired trisaccharide products were obtained in moderate to good yields with excellent stereoselectivity. The central pyranulose-ring generated in the process possessed an L-cis-enulose configuration according to NMR spectroscopy and modeling studies. 1 + 1 equals 3! The hetero-Diels-Alder union of two functionalized monosaccharide building blocks - one bearing an aldehyde and the other a readily accessible diene moiety - affords functionalized trisaccharide structures in moderate to good yields and excellent stereoselectivities when β-anomers of the aldehydes are used. Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
Intramolecular opening of β-lactams with amines as a strategy toward enzymatically or photochemically triggered activation of lactenediyne prodrugs
Banfi, Luca,Guanti, Giuseppe,Rasparini, Marcello
, p. 1319 - 1336 (2007/10/03)
In order to develop a general strategy for selective activation of designed enediyne prodrugs belonging to the "lactenediyne" family, we studied the scope of intramolecular transamidation of simple monocyclic β-lactams bearing a tethered amine. The effect of substituents, of reaction media, and of the type of tether, on the rate of transamidation is disclosed. The possibility of triggering the transamidation event under mild conditions by the action of suitable enzymes or UV light was demonstrated on model monocyclic β-lactams. Finally, the strategy of intramolecular opening of the β-lactam leading to a larger seven-membered ring was employed on a lactenediyne, demonstrating that ring enlargement could unleash the reactivity of the enediyne moiety. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003.
SELECTIVE REDUCTION OF ALKYNES TO CIS-ALKENES BY HYDROMETALLATION USING 6
Daeuble, John F.,McGettigan, Colleen,Stryker, Jeffrey M.
, p. 2397 - 2400 (2007/10/02)
Selective reduction of alkynes to the corresponding alkenes is reported using the stable, readily prepared copper(I) hydride reagent, 6.Terminal alkynes are reduced at room temperature, unactivated internal alkynes react only at elevated temperature.Disubstituted alkynes with propargyl activation are also reduced, giving cis-olefins selectively.Protection of propargylic alcohol functionality is unnecessary, although fragmentation is sometimes competitive in sterically hindered cases.A tertiary propargyl acetate gave displacement to the allene exclusively.
