97974-23-7Relevant articles and documents
A concise total synthesis of amphidinolide T2
Li, Huoming,Wu, Jinlong,Luo, Jialu,Dai, Wei-Min
supporting information; experimental part, p. 11530 - 11534 (2010/11/24)
RCM+AD=T2: In the presence of the C16-methylene group, regioselective ring-closing metathesis (RCM) formed the (12E)-endocyclic double bond, which underwent Os-catalyzed asymmetric dihydroxylation (AD) to give the desired 12,13-diol intermediate required
Altered transition state for the reaction of an RNA model catalyzed by adinuclear zinc(II) catalyst
Morrow, Janet R.,Richard, John P.,et al.,Humphry, Tim,Iyer, Subashree,Iranzo, Olga
experimental part, p. 17858 - 17866 (2009/08/08)
The cyclization of 2-(hydroxypropyl)-4-nitrophenyl phosphate (HpPNP) catalyzed by the dinuclear zinc complex of 1,3-bis(1,4,7-triazacyclonon-1-yl)-2- hydroxypropane (1) proceeds by a transition state that is different from that of the uncatalyzed reaction. Kinetic isotope effects (KIEs) measured in the nucleophilic atom and in the leaving group show that theuncatalyzed cyclization has a transition state (TS) with little phospho rus-oxygen bond fission to the leaving group 18klg= 1.0064 ± 0.0009 and 15k = 1.0002 ± 0.0002) a nd that nucleophilic bond formation occurs in the rate-determining step (18knuc ) 1.0326 ( 0.0008). In the catalyzed reaction, larger leaving group isotope effects ( 18klg ) 1.0113 ± 0.0005 and 15k = 1.0015 ± 0.0005) and a smaller nucleophile isotope effect (18k nuc = 1.0116 ± 0.0010) indicate a later TS with greater leaving group bond fission and greater nucleophilic bond formation. These observed nucleophile KIEs are the combined effect of the equilibrium effect on deprotonation of the 2′-hydroxyl nucleophile and the KIE on the nucleophilic step. An EIE of 1.0245 for deprotonation of the hydroxyl group of HPpNP was obtained computationally. The different KIEs for the two reactions indicate that the effective catalysis by 1 is accompanied by selection for an altered transition state, presumably arising from the preferential stabilization by the catalyst of charge away from the nucleophile and toward the leaving group. These results demonstrate the potential fora catalyst using biologically relevant metal ions to select for an alte red transition state for phosphoryl transfer.
MACROCYCLIC COMPOUNDS USEFUL AS PHARMACEUTICALS
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Page/Page column 134-135, (2010/02/07)
The present invention provides compounds having formula (I), and additionally provides methods for the synthesis thereof and methods for the use thereof in the treatment of various disorders including inflammatory or autoimmune disorders, and disorders involving malignancy or increased angiogenesis, wherein R1 -R11, t, X, Y, Z, and n are as defined herein.
