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PubMed2004

Lithium hexamethyldisilazide-mediated ketone enolization: the influence of hindered dialkyl ethers and isostructural dialkylamines on reaction rates and mechanisms.

Mechanistic studies of the enolization of 2-methylcyclohexanone mediated by lithium hexamethyldisilazide (LiHMDS; TMS(2)NLi) solvated by hindered dialkyl ethers (ROR') are described. Rate studies using in situ IR spectroscopy show that enolizations in the presence of i-Pr(2)O, 2,2,5,5-tetramethyltetrahydrofuran, and cineole proceed via dimer-based transition structures [(TMS(2)NLi)(2)(ROR')(ketone)]. Comparing the relative solvation energies and the corresponding solvent-dependent activation energies shows that the highly substituted ethers accelerate the enolizations by sterically destabilizing the reactants and stabilizing the transition structures. Comparisons of hindered dialkyl ethers with their isostructural dialkylamines reveal that the considerably higher rates elicited by the amines derive from an analogous relative destabilization of the reactants and relative stabilization of the transition structures.

Ketones↗

PubMed2003

Ketone enolization with lithium dialkylamides: the effects of structure, solvation, and mixed aggregates with excess butyllithium.

The effects of lithium dialkylamide structure, mixed aggregate formation, and solvation on the stereoselectivity of ketone enolization were examined. Of the lithium dialkylamides examined, lithium tetramethylpiperidide (LiTMP) in THF resulted in the best enolization selectivity. The stereoselectivity was further improved in the presence of a LiTMP-butyllithium mixed aggregate. The use of less polar solvents reduced the enolization stereoselectivity. Ab initio calculations predict LDA and LiTMP to form mixed cyclic dimers in ethereal solvents. The calculations also predict LiTMP-alkyllithium mixed aggregates to competitively inhibit the formation of less stereoselective LiTMP-lithium enolate mixed aggregates.

Chemical Phenomena↗

PubMed2004

Halogen- and N-haloimide-promoted homo- and heterocoupling of alpha-(N-carbamoyl)alkylcuprates and alpha-(alkoxy)alkylcuprates.

Both homo- and mixed lithium di-alpha-(heteroatom)alkylcuprates readily dimerize upon addition of halogens (e.g., I(2), Br(2)) or N-halosuccinimides to afford the coupled products in excellent yields. Higher yields result when the requisite alpha-(heteroatom)alkyllithium reagents are generated via deprotonation rather than by transmetalation of the corresponding stannanes. Mixed lithium dialkyl- or alkyl(aryl)cuprate reagents containing one alpha-(heteroatom)alkyl ligand and one simple alkyl or aryl ligand give significantly lower yields of coupled product. Low enantioselectivity has been achieved in the oxidative coupling of lithium (n-Bu)(2-pyrrolidinyl)cuprate.

Copper↗

PubMed2005

Regio- and stereoselective ring opening of 2,3-diaryl oxiranes by LiBr/Amberlyst 15: a new stereocontrolled access to 1,2-diaryl-2-bromo alcohols.

Both symmetrical and nonsymmetrical trans-2,3-diaryloxiranes are regio- and stereoselectively opened by the LiBr/Amberlyst 15 system. In the case of symmetrical trans-stilbene oxide, the syn- versus anti-bromohydrins ratio ranged between 88/12 and 30/70, by varying the reaction temperature from 20 to -30 degrees C. In the case of nonsymmetrical para-substituted trans-2,3-diaryloxiranes, the regioselectivity is determined by electronic effects. If one phenyl bears a strong electron-withdrawing group (as NO2 or CF3), the nucleophilic attack is totally on the beta-carbon with respect to the substituted phenyl ring. With one phenyl bearing a strong electron-releasing group (OCH3), the regioselectivity is reversed. Ab initio calculation at the DFT/B3LYP/6-31G level, run on protonated epoxide structures, supports the formation of a cationic acyclic intermediate. Application of the method on ortho-methoxy and ortho-nitro 2,3-diaryloxiranes afforded the syn-bromohydrins in excellent yield, via regio- and stereoselective opening at either alpha- or beta-carbon, respectively.

Benzyl Alcohols↗

PubMed2004

Highly stereoselective aldol reaction for the synthesis of gamma-lactones starting from tartaric acid.

A simple stereoselective process for the synthesis of highly substituted gamma-lactones was developed based on aldol reactions between the enolate of dioxanes derived from tartaric acid and aldehydes. A range of aromatic and aliphatic aldehydes were reacted, in most cases achieving good yields and stereoselectivity. The limitations of this reaction were identified and a transition state is proposed.

Catalysis↗

PubMed2005

Preparation of vinyl allenes from 1-lithio-1,3-dienyl phosphine oxides and aldehydes by the Wittig-Horner reaction.

[reaction: see text] Vinyl allenes were prepared in high yields by the Wittig-Horner reaction of 1-lithio-1,3-dienyl phosphine oxides with aldehydes. 1-Lithio-1,3-dienyl phosphine oxides were generated in situ from lithiation of 1-iodo-1,3-dienyl phosphine oxides, which were obtained by iodination of alpha-phosphinozirconacyclopentadienes. As a whole, a vinyl allene is synthesized from two different alkynes and one aldehyde.

Aldehydes↗

PubMed2005

Practical synthesis of a neuropeptide Y antagonist via stereoselective addition to a ketene.

[Reaction: see text]. The synthesis of neuropeptide Y antagonist 1, currently under clinical investigation for the treatment of obesity, is described. The convergent synthesis from trans-spirolactone carboxylic acid intermediate 2a and aminopyrazole 3 is predicated on a stereoselective route to the former. The coupling reaction of ethyl 4-oxocyclohexanecarboxylate (10a) with lithiated isonicotinamide 11 was investigated in detail, but even optimized conditions only provided a 45:55 ratio of trans:cis isomers (12a:12b). While selective crystallization schemes were developed to isolate the thermodynamically less stable trans isomer 2a, improved stereocontrol was subsequentially achieved by the application of ketene chemistry. The ketene formation and quench was investigated under a variety of conditions aimed at maximizing the trans:cis ratio. Reacting a mixture of carboxylic acids 2a and 2b with POCl3 in THF, followed by concomitant addition of tert-butyl alcohol in the presence of TMEDA at 35 degrees C provided a 4:1 ratio of trans:cis tert-butyl esters (18a:18b) via in situ ketene formation. Ester hydrolysis, followed by selective crystallization of undesired 2b as the HCl salt, led to isolation of 2a in 47% overall yield. Aminopyrazole intermediate 3 was synthesized via the condensation reaction of 2-fluorophenylhydrazine hydrochloride (4a) with acrylonitrile derivative 5 in 65-70% yield. Coupling of advanced intermediates 2a and 3b via activation with thionyl chloride gave a 92% yield of 1.

Bromides↗

PubMed2005

Regio- and stereoselective reactions of gem-difluorinated vinyloxiranes with heteronucleophiles.

[Reaction: see text]. Regio- and stereoselectivity in reactions of gem-difluorinated vinyloxiranes with heteronucleophiles were successfully controlled. Halogen atoms were introduced regioselectively at the allylic epoxide carbon with an inversion in stereochemistry using MgBr2*Et2O or Li2CuCl4 to produce anti-vic-halohydrine. The other diastereomers were obtained selectively using LiBr/AcOH or BCl3, and SN2' type products were formed selectively with excellent E preference by changing the reaction temperature. Moreover, a further investigation led us to find that a regio- and stereoselective SN2' addition of several Brnsted acids was dependent on the pKa values of the acids. Under strong acidic conditions, we exclusively obtained E allylic alcohols.

Arabinose↗

PubMed2006

Selective removal of the 2'- and 3'-O-acyl groups from 2',3',5'-tri-O-acylribonucleoside derivatives with lithium trifluoroethoxide.

Selective cleavage of O2' and O3' ester groups from ribonucleoside derivatives has been accomplished with Dowex 1 x 2 (CF3CH2O-) in 2,2,2-trifluoroethanol (TFE) or lithium trifluoroethoxide/TFE. Deacylations with Li+ -OCH2CF3/TFE proceed at ambient temperature (or with mild heating) to give the 5'-O-acyl derivatives in superior yields and higher purity than prior approaches for selective O2' and O3' ester deprotection.

Acylation↗

PubMed2006

Functionalization of N-[(silyl)methyl]-beta-lactam carbanions with carbon electrophiles.

Latent acidity of alpha-alkyl-alpha-amino-N-[(silyl)methyl]-beta-lactams enabled a concise entry to lithium nonenolate N-methyl-azetidinone carbanions lithiated alpha' to the beta-lactam nitrogen, owing to the stabilizing "alpha-effect" of one or two trimethylsilyl groups. (n)BuLi/TMEDA and (t)BuLi/TMEDA were the bases of choice for complete deprotonation of di- and monosilylated beta-lactams, respectively. Trapping of the resulting carbanions with alkyl halides provided the corresponding N-[(alpha'-silyl)-alkyl]-beta-lactams, while carbon dioxide and related electrophiles such as benzyl chloroformates or isocyanates, afforded the corresponding silicon-free N-carboxymethyl-, N-benzyloxycarbonylmethyl-, and N-amidomethyl-beta-lactams in a single synthetic step. Likely structures of these unprecedented lithiated N-[(silyl)methyl]-beta-lactams were studied by MO calculations (B3LYP/6-31G**), and the origin of their relative stability was briefly discussed.

Alkylation↗

PubMed2006

Mechanism of acylation of lithium phenylacetylide with a Weinreb amide.

Additions of lithium phenylacetylide to a Weinreb amide are described. Dimeric lithium acetylide reacts via a monosolvated monomer-based transition structure. The robust tetrahedral intermediate forms sequentially a C(1) 2:2 mixed tetramer with the excess lithium acetylide and a 1:3 (alkoxide-rich) mixed tetramer. The stabilities of the mixed tetramers are consistent with a pronounced autoinhibition.

Acylation↗

PubMed1998

2,2,3-Trisubstituted Tetrahydrofurans and 2H-Tetrahydropyrans by Tandem Demethoxycarbonylation-Michael Addition Reactions.

A tandem demethoxycarbonylation-Michael addition reaction has been developed as a synthetic route to highly functionalized five- and six-membered oxygen heterocycles. Methyl esters, activated toward decarboxylation by a C-2 ethoxycarbonyl group and tethered by a three- or four-atom chain to an acrylate Michael acceptor, have been prepared and used as the cyclization substrates. Treatment of these compounds with lithium chloride in DMEU (1,3-dimethyl-2-imidazolidinone) at 120 degrees C for 4-8 h results in chemoselective S(N)2 dealkylation of the methyl esters, decarboxylation, and cyclization of the intermediate enolates by a Michael addition to the pendent acrylate moiety. This affords tetrahydrofuran and 2H-tetrahydropyran derivatives in 60-90% yields with diastereoselectivities up to 7.5:1 in favor of the product having the C-2 ethoxycarbonyl group trans to the C-3 acetic ester side chain. The reaction works best for the preparation of five- and six-membered rings, and cyclizations proceed most cleanly from substrates which cyclize through a tertiary enolate. Synthetic and mechanistic details are presented.

Journal Article↗

PubMed2000

Solvation and structural effects on the stability of 10-X-2 ate-complexes: a computational study.

The structures and energies of a variety of 10-X-2 ate-complexes derived from reaction of alkyllithiums and aryllithiums with the corresponding organohalides have been studied at the B3LYP/6-31+2G** theoretical level. The results of the calculations, which are in good agreement with the available experimental data, indicate that diaryl ate-complexes are more stable than their dialkyl counterparts. Fluorine substitution was found to confer substantial stability to both diaryl and dialkyl ate-complexes, and the calculations suggest that perfluoro dialkyl 10-X-2 ate-complexes should be experimentally observable species. One of the most important factors contributing to stability of a 10-X-2 ate-complex is removal of the formally cationic lithium from the vicinity of the ate-anion via coordination with a Lewis basic solvent.

Hydrocarbons, Halogenated↗

PubMed2005

Conductivities and transport properties of gelled electrolytes with and without an ionic liquid for Li and Li-ion batteries.

Conductivity and transport properties have been determined for gelled polymer electrolytes of three compositions: a base PVdF-polymer gel with organic carbonate solvents as plasticizers and LiN(SO(2)C(2)F(5))(2) electrolyte, a second polymer electrolyte with 5 mass % 1-ethyl-3-methylimidazolium bisperfluoroethylsulfonyl imide (EMI-BETI) added to the base polymer electrolyte, and a third PVdF polymer electrolyte using only EMI-BETI as the plasticizer. Conductivities were studied over the temperature range +25 to -40 degrees C, and for all three gels, the temperature dependence of the conductivities was found to follow the VTF equation, which is consistent with the free volume model for ion transport. For the gel containing 5 mass % EMI-BETI, transport numbers were determined from +50 to -20 degrees C and were found to decrease as the temperature decreased. Although there are no theoretical models to treat and interpret the temperature dependence of transport numbers, we found that a modified VTF equation resulted in an excellent fit to the temperature dependence of the transport number, which is another confirmation of a free volume model for transport in these gelled polymer electrolytes.

Electric Conductivity↗

PubMed2005

Optimization and application of lithium parameters for the reactive force field, ReaxFF.

To make a practical molecular dynamics (MD) simulation of the large-scale reactive chemical systems of Li-H and Li-C, we have optimized parameters of the reactive force field (ReaxFF) for these systems. The parameters for this force field were obtained from fitting to the results of density functional theory (DFT) calculations on the structures and energy barriers for a number of Li-H and Li-C molecules, including Li(2), LiH, Li(2)H(2), H(3)C-Li, H(3)C-H(2)C-Li, H(2)C=C-LiH, HCCLi, H(6)C(5)-Li, and Li(2)C(2), and to the equations of state and lattice parameters for condensed phases of Li. The accuracy of the developed ReaxFF was also tested by comparison to the dissociation energies of lithium-benzene sandwich compounds and the collision behavior of lithium atoms with a C(60) buckyball.

Journal Article↗

PubMed2005

Spectroscopic measurements of ionic association in solutions of LiPF6.

Ionic association in nonaqueous electrolytes containing LiPF6 was investigated with infrared absorption spectroscopy. The spectral intensity of the nondegenerate nu1 mode of the PF6- anion was found to be sensitive to ion pairing. Although the nu(1) mode of an isolated PF6- anion is only Raman active, coordination of Li+ to PF6- destroys the octahedral symmetry of the anion and results in nu1 becoming simultaneously IR and Raman active. When the dielectric constant of the solvent is increased, the IR-intensity of the nu1 band decreases because ion pairing is not favored in high dielectric solvents. Spectroscopic studies of solutions containing LiPF6 in diglyme show that ion pairing is also affected by specific cation-solvent interactions. The diglyme-containing solutions contain significantly fewer ion pairs than expected on the basis of the solvent's dielectric constant. It is thought that diglyme:LiPF6 solutions consist mostly of "spectroscopically free" PF6- anions because the sixfold coordination of Li+ by two diglyme molecules hinders Li+...PF6- ion pairing.

Ions↗

PubMed2006

Postirradiation electron transfer vs differential radical decay in X-irradiated DNA and its mixtures with additives. Electron spin resonance spectroscopy in LiBr glass at low temperatures.

Free radical formation in DNA and in colyophilized mixtures of DNA with the additives mitoxantrone and riboflavin was monitored after X-ray irradiation in frozen aqueous glasses (7 M LiBr/D2O) at 77 K by electron spin resonance (ESR) spectroscopy. Specifically, the postirradiation time course at 77 K of the respective free radical intensity residing on DNA or on the additive was probed in order to test the hypothesis of electron transfer from DNA, e.g., to mitoxantrone after irradiation under these conditions (e.g., Messer, A.; Carpenter, K.; Forzley, K.; Buchanan, J.; Yang, S.; Razskazovskii, Y.; Cai, Z.; Sevilla, M. D. J. Phys. Chem. B 2000, 104, 1128). For both additives, different additive loadings and irradiation doses were employed. The observed relative change in contributions of DNA and of additive radical components to the experimental spectra with time could be ascribed, for both additives, unequivocally to independent, differential fading of component radicals. Transfer from DNA to the additive, e.g., by electron tunneling as proposed before could be ruled out to occur by a detailed, quantitative analysis of the experimental spectra using reconstruction techniques. Additional studies were performed with the nucleotides TMP and dCMP and its mixtures with mitoxantrone in order to describe the time course in systems which are expected to behave independently; the results supported the conclusions arrived at from the analysis of the DNA/additive system. A model was proposed to describe the postirradiation radical fading mechanisms which involve liberation of radiation-induced matrix-trapped defects with time. It was assumed that these defects are ESR-mute and react with radicals by net radical destruction. Some experimental observations are presented concerning influence of temperature and of the matrix on the fading processes. These seem to argue in favor of such a model although a detailed, quantitative description is still not possible.

Bromides↗

PubMed2006

Solid-state phase transition induced by pressure in LiOH x H2O.

When the free energy surface of the lithium hydroxide monohydrate crystal was explored, the high-pressure solid-state phase transition was determined. The high-pressure phase has been obtained through ab initio Car-Parrinello molecular dynamics simulation in the isothermic-isobaric ensemble. The recent metadynamics method has been applied to overcome the high activation energy barriers typical of rare events, like solid-state phase transition at high pressures. In the LiOH x H2O system, there are two kinds of H bonds: water-water and hydroxyl-water. The effect of the pressure has been investigated, to give further insight into the high-pressure phase. The strengthening of the H bonds of the system produces modifications in the water and the hydroxyl ion dipole electronic environment. The infrared spectra of both phases have been calculated and compared with experiments, and the assignment of the external modes has been discussed.

Lithium Compounds↗