Search results for "racemization"
showing 10 items of 32 documents
Synthesis and structural properties of hexaaza[5]helicene containing two [1,2,3]triazolo[1,5-a]pyridine moieties
2013
Abstract We have synthesized a novel hexaaza[5]helicene in a straightforward way from neocuproine. The crystal structure has been elucidated with direct-space strategy TALP which demonstrates the power of the powder X-ray diffraction technique. In this crystal structure it is possible to see an interplanar angle of 33(1)° between the two triazolopyridine rings. The centrosymmetric crystal structure is a racemic mixture, but the resolution was not possible due to a ring-chain isomerization in a solution that produces a dynamic racemization.
ChemInform Abstract: Asymmetric Synthesis of Fluorinated Isoindolinones Through Palladium-Catalyzed Carbonylative Amination of Enantioenriched Benzyl…
2015
The asymmetric synthesis of fluorinated isoindolinones has been achieved by a palladium-catalyzed aminocarbonylation reaction of the corresponding α-fluoroalkyl o-iodobenzylamines. A base-mediated anti β-hydride elimination process was suggested to explain the partial erosion of the optical purity observed in some cases. This mechanistic rationale enabled the minimization of this partial racemization by fine-tuning the pKa of the base.
Improved synthesis of Bn5CpRu(CO)2Cl and its application as racemization catalyst in preparative-scale metalloenzymatic dynamic kinetic resolution of…
2010
An improved gram-scale synthesis of Bn5CpRu(CO)2Cl is reported based on heating of pentabenzylcyclopentadiene with Ru3(CO)12 at 160 °C under argon atmosphere in mesitylene followed by addition of chloroform, continued heating, and evaporation of the solvents. Subsequent washing of unreacted ligand precursor with hexane provided pure title compound in 77 % yield. In combination with Candida antarctica lipase B (CAL-B) (Novozym 435), this complex forms a highly active racemization catalyst for metallo-enzymatic dynamic kinetic resolution (DKR) of secondary alcohols as demonstrated in the present work by converting 100 g of racemic 1-phenylethanol to (R)-1-phenylethanol in >99 % ee and 93 %…
From Symmetry Breaking to Unraveling the Origin of the Chirality of Ligated Au13 Cu2 Nanoclusters
2018
A general method, using mixed ligands (here diphosphines and thiolates) is devised to turn an achiral metal cluster, Au13 Cu2 , into an enantiomeric pair by breaking (lowering) the overall molecular symmetry with the ligands. Using an achiral diphosphine, a racemic [Au13 Cu2 (DPPP)3 (SPy)6 ]+ was prepared which crystallizes in centrosymmetric space groups. Using chiral diphosphines, enantioselective synthesis of an optically pure, enantiomeric pair of [Au13 Cu2 ((2r,4r)/(2s,4s)-BDPP)3 (SPy)6 ]+ was achieved in one pot. Their circular dichroism (CD) spectra give perfect mirror images in the range of 250-500 nm with maximum anisotropy factors of 1.2×10-3 . DFT calculations provided good corre…
A theoretical and experimental study of the racemization process of hexaaza[5]helicenes
2014
A dynamic 1H NMR study, together with DFT calculations, of bis-([1,2,3]triazolo)[1,5-a:5′,1′-k][1,10]phenanthroline 2 has allowed to identify the ring and open forms of a new example of ring/chain tautomerism, as well as their interconversion barriers (ring/ring and ring/open). The barrier of the exchange process between the chain forms and the ring form was found higher than the 'racemization' process in the closed form, so the ring opening does not contribute to the 'racemization'. The di-1,10-methyl and di-1,10-iodo derivatives have been prepared and their properties calculated.
Synthesis of chiral β-disulfoxides and their racemization with strong bases
1997
Abstract β-Disulfoxides can be obtained from different α-sulfunylcarbanions and sulfinates. While α-unsubstituted and monosubstituted β-disulfoxides are configurationally stable in the presence of strong bases, α,α-disubstituted β-disulfoxides epimerize through an intermolecular mechanism.
Cyclopenta[l]phenanthrenyl and Cyclopenta[a]acenaphthylenyl Half-Sandwich Complexes of Ruthenium as Racemization Catalysts for Secondary Alcohols
2008
Several half-sandwich complexes of ruthenium with cyclopenta[l]phenanthrenyl and cyclopenta[a]acenaphthylenyl ligands containing fused aromatic ring substituents on the cyclopentadienyl ring were p...
Chiral complexes of titanium containing a linked amido-cyclopentadienyl ligand: synthesis, structure, and asymmetric imine hydrogenation catalysis
2000
Abstract A series of mono- and disubstituted derivatives (−)-(S)-Ti(η5:η1-C5Me4SiMe2NCHMePh)(X)Cl (X=CH2SiMe3, BH4) and (−)-(S)-Ti(η5:η1-C5Me4SiMe2NCHMePh)X2 (X=OSO2CF3, OiPr, Me, CH2Ph) was prepared from (−)-(S)-Ti(η5:η1-C5Me4SiMe2NCHMePh)Cl2 without significant racemization at the stereogenic center. The monosubstituted complexes are formed as mixtures of diastereomers. One diastereomeric monoalkyl (STi, SC)-Ti(η5:η1-C5Me4SiMe2NCHMePh)(CH2SiMe3)Cl was characterized by X-ray single crystal structure analysis. When the (−)-(S)-NCHMePh group is attached to planar chiral ring moieties 3-tBuC5H3, C9H6, and C9H5(SiMe3)-3 and coordinated at the titanium center, diastereomeric mixtures are formed…
Conservation of optical purity of amino acids: a principal problem in biochemical and proto-biochemical systems.
1981
Dor L-amino acids, regardless of their state (peptide-bound or free, in the solid state or in aqueous solution), tend to racemize. In a living cell this racemization is usually compensated by specific degradation and replacement of the unwanted polypeptides that contain the wrong enantiomers. But a few long-lived proteins that are synthesized at or near birth are never replaced. Well investigated is the racemization of L-aspartic acid at a rate of 0.1 to 1.14 per cent per year in proteins from lenses and dentine. Increased racemization of eye lens proteins has been related to a form of human eye disease known as brunescent cataracts. Also quite well investigated is the racemization of amino…
Ring-opening polymerization of lactides using heterobimetallic yttrocene complexes
1999
Structurally characterized, chiral heterobimetallic yttrocene derivatives Li[Y(η 5 :η 1 -C 5 R 4 Si-Me 2 NCH 2 CH 2 OMe) 2 ] (R = Me, H) have been shown to be active in the controlled ring-opening polymerization of L-lactide to give poly(L-lactide)s with high molecular weights and moderately narrow molecular weight distributions (M w /M n < 1.50). Both transesterification and racemization appear to be less prominent. 'H NMR spectroscopic tetrad analysis of copolymers prepared using a mixture of L- and D-lactide demonstrates the absence of any preference for one enantiomer during the polymerization.