A General Strategy to Enantiomerically Pure Aliphatic and Olefinic Ketone Cyanohydrins by Stereoselective Alkylation of Umpoled Aldehyde Derivatives
摘要:
We present the first general synthesis of optically pure (R)- and (S)-ketone cyanohydrins with olefinic and aliphatic substituents. Consecutive condensations of POCl3 with pseudoephedrine (1) and racemic crotonaldehyde cyanohydrin (3, R = 1-propenyl) lead to the respective cyanohydrin phosphate 4c. Deprotonation, followed by highly stereoselective alkylation and a single chromatographic purification step, afford diastereomerically pure ketone cyanohydrin phosphates 5a-e. From these, enantiomerically pure tertiary cyanohydrins 6a-e can be obtained by mild Lewis acid-assisted hydrolysis. Pseudoephedrine is simultaneously recovered without loss of optical purity. The unsaturated alkylation products 5a-d are readily hydrogenated with diimide to aliphatic cyanohydrin phosphates 5f-i, which can be cleaved to furnish the free optically pure cyanohydrins 6f-i. Thus a broad variety of both saturated and unsaturated ketone cyanohydrins with R > Et becomes accessible in optically pure form for the first time. The free cyanohydrins are easily converted to optically pure alpha-branched alpha-hydroxy acids.
The present invention relates to novel iridium and/or rhodium containing complexes for use as a cytotoxic, such as an anti-cancer agent. There is also provided a method of preparing said compounds.
本发明涉及用作细胞毒性物质,如抗癌药物的新型含铱和/或铑配合物,还提供了一种制备所述化合物的方法。
NOVEL IRIDIUM/RHODIUM ANTI-CANCER COMPOUNDS
申请人:Habtemariam Abraha
公开号:US20130065864A1
公开(公告)日:2013-03-14
The present invention relates to novel iridium and/or rhodium containing complexes for use as a cytotoxic, such as an anti-cancer agent. There is also provided a method of preparing said compounds.
The present invention relates to the use of certain osmium containing complexes such as cytotoxic agents particularly for the treatment of cancer. There is also provided novel osmium containing complexes, as well as pharmaceutical formulations comprising such complexes.
A Convenient Synthesis and Structural Assessment of [Sn(CH<sub>3</sub>)<sub>2</sub>(L<sub>2</sub>)](ClO<sub>4</sub>)<sub>2</sub>
作者:D. Dey、T. S. Basu Baul、E. Rivarola
DOI:10.1246/bcsj.66.1556
日期:1993.5
A general synthesis for a novel class of complexes of the type, [Sn(CH3)2(L2)](ClO4)2 (L = 2-(substituted arylazo) pyridine) is reported. The structure of the complexes have been investigated by 119tin Mössbauer spectroscopy and NMR coupling constant 2J (117/119 Sn–CH). Further, the extent of distortion of tin–methyl groups in octahedral complexes have been calculated from the quadrupole shift (Q.S.) values using Parish’s relationship.
Phenylazo-pyridine and Phenylazo-pyrazole Chlorido Ruthenium(II) Arene Complexes: Arene Loss, Aquation, and Cancer Cell Cytotoxicity
作者:Sarah J. Dougan、Michael Melchart、Abraha Habtemariam、Simon Parsons、Peter J. Sadler
DOI:10.1021/ic061460h
日期:2006.12.1
decomposition of the complexes via hydrolysis and/or areneloss (t(1/2) = 9-21 h for azopyridine complexes, 310 K). The pKa* of the coordinated water in [(eta6-p-cym)Ru(azpyz-NMe2)OH2]2+ (13A) is 4.60, consistent with the increased acidity of the ruthenium center upon coordination to the azo ligand. None of the azpy complexes were cytotoxic toward A2780 human ovarian or A549 human lung cancercells, but several
钌(II)eta6-芳烃配合物,其中含有对苯异丙基(p-cym),四氢萘(thn),苯(bz)或联苯(bip)作为芳烃,苯基偶氮吡啶衍生物(C5H4NN:NC6H5R; R = H(azpy ),已合成作为N,N-螯合配体和氯化物作为配体的OH(azpy-OH),NMe2(azpy-NMe2))或苯基偶氮吡唑衍生物(NHC3H2NN:NC6H5NMe2(azpyz-NMe2))(1-16) 。由于在可见光区域发生的金属到配体的电荷转移Ru 4d6-pi *和配体内pi-> pi *的跃迁(eta = 5000-63 700 M-1 cm-1),所有络合物都显着着色。在[(eta6-p-cym)Ru(azpy)Cl] PF6(1)的晶体结构中,[(eta6-p-cym)Ru(azpy-NMe2Cl)Cl] PF6(5)和[(eta6- bip)Ru(azpy)Cl] PF6(4),相对较长的