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101.
Dr. Malte Brasholz Dr. James M. Macdonald Dr. Simon Saubern Dr. John H. Ryan Prof. Dr. Andrew B. Holmes 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(37):11471-11480
The total synthesis of the spiropiperidine alkaloid (?)‐perhydrohistrionicotoxin (perhydro‐HTX) 2 has been accomplished on a gram scale by employing both conventional batch chemistry as well as microreactor techniques. (S)‐(?)‐6‐Pentyltetrahydro‐pyran‐2‐one 8 underwent nucleophilic ring opening to afford the alcohol 10 , which was elaborated to the nitrone 13 . Protection of the nitrone as the 1,3‐adduct of styrene and side‐chain extension to the unsaturated nitrile afforded a precursor 17 , which underwent dipolar cycloreversion and 1,3‐dipolar cycloaddition to give the core spirocyclic precursor 18 that was converted into perhydro‐HTX 2 . The principal steps to the spirocycle 18 have successfully been transferred into flow mode by using different types of microreactors and in a telescoped fashion, allowing for a more rapid access to the histrionicotoxins and their analogues by continuous processing. 相似文献
102.
Tony W. J. Cooper Ian B. Campbell Dr. Simon J. F. Macdonald 《Angewandte Chemie (International ed. in English)》2010,49(44):8082-8091
Synthetic organic reactions are a fundamental enabler of small‐molecule drug discovery, and the vast majority of medicinal chemists are initially trained—either at universities or within industry—as synthetic organic chemists. The sheer breadth of synthetic methodology available to the medicinal chemist represents an almost endless source of innovation. But what reactions do medicinal chemists use in drug discovery? And what criteria do they use in selecting synthetic methodology? Why are arrays (small focused libraries) so powerful in the lead‐optimization process? In this Minireview, we suggest some answers to these questions and also describe how we have tried to expand the number of robust reactions available to the medicinal chemist. 相似文献
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Yang J Cyr PW Wang Y Soong R Macdonald PM Chen L Manners I Winnik MA 《Photochemistry and photobiology》2006,82(1):262-267
We describe experiments that determine the quenching kinetics by poly(ferrocenylsilane) (PFS) for platinum octaethylporphine (PtOEP) phosphorescence in toluene solution. The phosphorescence quenching process was interpreted in terms of diffusion-controlled kinetics. Pulsed-gradient spin-echo nuclear magnetic resonance (PGSE NMR) and dynamic light scattering (DLS) were used to characterize the diffusion behavior of PFS and PtOEP in toluene solution. We found that the ferrocene group present in the repeat unit of polymer backbone is a good quencher for PtOEP phosphorescence. Quenching by the polymer involves the entire PFS polymer chain instead of individual ferrocene groups. The intrinsic quenching ability of PFS was found to be higher than that of a model compound, Bu-FS, that contains a single ferrocene group. 相似文献
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Varrot A Macdonald J Stick RV Pell G Gilbert HJ Davies GJ 《Chemical communications (Cambridge, England)》2003,(8):946-947
A cellobio-derived isofagomine glycosidase inhibitor (Ki approximately 400 nM) displays an unusual distorted 2,5B (boat) conformation upon binding to cellobiohydrolase Cel6A from Humicola insolens, highlighting the different conformational itineraries used by various glycosidases, with consequences for the design of therapeutic agents. 相似文献
108.
J. R. Macdonald 《Applied Physics A: Materials Science & Processing》1994,59(2):181-188
Nowick and his associates have stated that many ionic crystals and glasses exhibit a loss per cycle which is independent of frequency over an appreciable range and have suggested that such behavior constitutes a new universality. Furthermore, much such data seem to approach an asymptotic, nearly temperature-independent ac loss at sufficiently low temperatures. In order to further evaluate these conclusions, small-signal ac relaxation data for a CaTiO3:30% Al3+ ceramic material are analyzed in detail and the results compared to those published by Nowick and associates for the same material. It is found that a plausible conducting-system dispersion model based on the effective-medium approximation for hopping charges yields results globally similar to, but somewhat different in detail from, those of Nowick et al. But a response model which includes both such conducting-system response and dielectric-system dispersion well fits the data over a wide temperature range. To do so, it requires the presence of a non-zero high-frequency-limiting resistivity probably arising from localized charge motion. No constant-loss individual dispersions appear in the model, but it nevertheless yields approximately constant loss over a limited frequency range at low temperatures. It suggests that asymptotic behavior is associated with the nearly temperature-independent dielectric-dispersion contribution to the response at low temperatures, and it does not verify the Nowick conclusion that the slope of the ac conductivity approaches a constant value near 0.6 at high temperatures. 相似文献
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New and existing data on the ground and excited CS torsional states of the stable rotamers of ethene thiol have been analysed to give a potential function for internal rotation around the CS bond. The barrier between the syn and anti rotamers is found to be 800 cm?1 and that at the planar anti conformation itself to be 12 cm?1. the syn conformation is 50 cm?2 more stable than the ‘quasi-planar’ anti conformation Satisfactory reproduction of the observed trends in rotational constants with torsional excitations has been achieved by introducing extensive relaxation of the CCS angle and the CS bond length during internal rotation. The CCS angle reduces by up to 5° v'hilst the CS bond length increases by up to 0.02 A during rotation from the syn to anti conformation. The use of ab initio M.O. calculations to provide an indication of the most significant aspects of structure relaxation is described. 相似文献