Search results for "Enantiopure drug"
showing 10 items of 54 documents
Rational Synthesis of Chiral Metal-Organic Frameworks from Preformed Rodlike Secondary Building Units.
2017
The lack of rational design methodologies to obtain chiral rod-based MOFs is a current synthetic limitation that hampers further expansion of MOF chemistry. Here we report a metalloligand design strategy consisting of the use, for the first time, of preformed 1D rodlike SBUs (1) for the rational preparation of a chiral 3D MOF (2) exhibiting a rare eta net topology. The encoded chiral information on the enantiopure ligand is efficiently transmitted first to the preformed helical 1D building block and, in a second stage, to the resulting chiral 3D MOF. These results open new routes for the rational design of chiral rod-based MOFs, expanding the scope of these unique porous materials.
Organocatalytic Oxidation of Secondary Alcohols Using 1,2-Di(1-naphthyl)-1,2-ethanediamine (NEDA)
2014
Diamine, 1,2-di(1-naphthyl)-1,2-ethanediamine (NEDA), efficiently catalyzes the oxidation of alcohols by using TBHP as an oxidant. Notably, secondary benzyl alcohols are oxidized in almost quantitative yields, and the catalyst also displays high activity towards even hindered cycloaliphatic secondary alcohols. With enantiopure (R,R)-NEDA, oxidative kinetic resolution can be realized and depending on the alcohol ee up to 99 % are achieved.
Amino-phosphanes in Rh(I)-catalyzed hydroformylation: new mechanistic insights using D2O as deuterium-labeling agent
2005
International audience; In previous work, we have demonstrated that the dangling amino group in amino-phosphane ligands increases the rate of Rh-catalyzed styrene hydroformylation as a function of the amino group basicity and of the distance between the P and N functions. We now report additional stereochemical and mechanistic insights resulting from new catalytic experiments performed with Rh-α-P,N catalytic systems in the presence of D2O. In addition to the expected D0 product, the formation of the β-D1 aldehyde, PhCH(CH2D)CHO was observed in all cases by 1H and 13C NMR spectroscopy, indicating that H/D exchange occurs for the rhodium-hydride complex. Minor amounts of a β-D2 product, PhCH…
Chiral Monofluorobenzyl Carbanions: Synthesis of Enantiopure β‐Fluorinated β‐Phenylethylamines
2011
The preparation of a stabilized monofluorobenzyl carbanion by means of a remote homochiral sulfinyl group and its completely stereoselective reactions with N-p-tolylsulfinylimines are described. The use of these reactions followed by the simultaneous removal of both chiral auxiliaries with tBuLi, which occurs without epimerization at the benzylic position, provides the quickest entry to enantiomerically pure β-fluorinated β-phenylethylamines.
Novel [6]- and [7]Helicene-Like Quinones via Mono- and Bidirectional Chromium-Templated Benzannulation of Bridged Binaphthyl Carbene Complexes
2005
A new organometallic approach to novel, functionalised, helicene-like quinones and bisquinones has been developed based on the chromium-templated [3+2+1] benzannulation reaction. The [5]helicene-analogous monocarbene chromium complexes 4, 5, 17 and 19, derived from dibromo-substituted methylene- or silylene-tethered binaphthols 2 and 3, react with various alkynes to give [6]helicene-like quinones 6–13 and 20–29 after oxidative work-up. A rare competition of angular vs. linear annulation is observed for the incorporation of phenylacetylene that affords quinones 21/22 and 28/29. Protection of the phenolic benzannulation product with camphanic acid chloride 14, followed by chromatographic sepa…
Rational enantioselective design of chiral heterobimetallic single-chain magnets: synthesis, crystal structures and magnetic properties of oxamato-br…
2011
A new series of neutral oxamato-bridged M(II)Cu(II) chiral chains of general formula [MCuL(x)(S)(m)(H(2)O)(n)]·aS·bH(2)O [L(1)=(M)-1,1'-binaphthalene-2,2'-bis(oxamate) with M=Mn (1a) and Co (1b); L(2)=(P)-1,1'-binaphthalene-2,2'-bis(oxamate) with M=Mn (2a) and Co (2b)] and the analogous racemic chains of formula [MCuL(3)(S)(m)(H(2)O)(n)]·aS·bH(2)O [L(3)=1,1'-binaphthalene-2,2'-bis(oxamate) with M=Mn (3a) and Co (3b)] have been prepared by reaction of the corresponding dianionic oxamatocopper(II) complex [Cu(L(x))](2-) with Mn(2+) or Co(2+) cations in either dimethylformamide (DMF) or dimethyl sulfoxide (DMSO). Solid circular dichroism (CD) spectra of the bimetallic chain compounds were reco…
ChemInform Abstract: Enantioselective Synthesis of Herbertane Sesquiterpenes: Synthesis of (-)-α-Formylherbertenol.
2010
Abstract The synthesis of 4-hydroxy-3-[(1 S )-1,2,2-trimethylcyclopentyl]benzaldehyde [(−)-α-formylherbertenol 1 ], a herbertane-type sesquiterpene isolated from the leafy liverwort Herberta adunca , from β-cyclogeraniol is described. The synthesis is based on the previously described preparation of an enantiopure 1,2,2-trimethylcyclopentane synthon from which the characteristic aromatic moiety of 1 is elaborated, using a Robinson annulation and a palladium-catalysed methoxycarbonylation of an aryl triflate as key synthetic steps. The synthesis of the natural sesquiterpene (−)-α-herbertenol, also a natural sequiterpene, using the same methodology is also described.
Microbiological transformations. 30. Enantioselective hydrolysis of racemic epoxides: the synthesis of enantiopure insect juvenile hormone analogs (b…
1993
Abstract The enantioselective epoxide biohydrolysis of the racemic benzodioxole 6,7-epoxygeraniol derivative 1 has been achieved using the fungus A. niger . This new type of preparative scale bioconversion allows the synthesis of both enantiomers of Bower's compound, an analogue of insect juvenile hormone. Biological tests showed that the 6(R) enantiomer was about ten times more active than the 6(S) enantiomer against the yellow meal worm Tenebrio molitor .
Syntheses, Structures and Reactivity of New Intramolecularly Coordinated Tin Alkoxides Based on an Enantiopure Ephedrine Derivative
2011
The syntheses of the tin compounds [LSn]2 (2), spiro-L2Sn (3), [LSnW(CO)5]2 (4), [LSnBr2]2 (5), spiro-L2Sn·SnBr4 (6) and LSn[OC(O)Ph]2 (8), where L = MeN(CH2CMe2O)[(S)-CH(Me)-(R)-CH(Ph)O], and (Ph4P)2SnBr6 (7) are reported. The compounds were characterized by elemental analysis, multinuclear NMR spectroscopy including 119Sn cross polarisation–magic angle spinning NMR (CP–MAS) (2, 3–6), electrospray ionization mass spectrometry (2–4) and single crystal X-ray diffraction analysis (2, 2·C7H8, 3a, 3b, 4·C7H8, 5, 6·C7H8, 7).
Synthesis and characterisation of a new class of phosphine-phosphonite ferrocenediyl dinuclear rhodium complexes
2004
We previously reported the easy access to mixed ferrocenediyl ligands bearing phosphine and phosphonite moieties. Using this strategy, a new enantiopure phosphine-menthylphosphonite ferrocenediyl has been synthesised. This mixed ligand leads to original unsymmetrical dinuclear rhodium coordination-complexes. One example of this new class of “quasi-close bridging A frame” dinuclear rhodium complexes, fully characterised by multinuclear 1H, 13C, 31P and 103Rh NMR and optical rotation measurements, is presented. Preliminary tests have shown an activity improvement in the hydroformylation of oct-1-ene using the phosphine-menthylphosphonite ferrocenediyl auxiliary compared to known phosphine-pho…