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A satellite-selective 1D-TOCSY method is developed for measuring long-range heteronuclear coupling constants between proton and proton bearing carbons. The comparison of two 1D-TOCSY spectra generated by selective inversion of each [super 13]C satellite of a certain proton signal, Hi, has helped in measuring the long-range heteronuclear couplings between protons of the same spin system as Hi and the carbon bonded to Hi.

The mechanism of highly enantioselective electrophilic amination and Michael addition of cyclic [beta]-ketoesters induced by lanthanides and (S,S)ip-pybox was studied. Intermediates based on simultaneous coordination of the lanthanide to both (S,S)-ip-box and [beta]-ketoester were detected by ESI mass spectrometry and NMR experiments.

Nitrogen containing 15-membered triacetylenic macrocycles known as 1,6,11-tris(arylsulfonyl)-1,6,11-triazacyclopentadeca-3,8,13-triynes and enediynic macrocycles called 1,6,11-tris(arylsulfonyl)-1,6,11-triazacyclopentadeca-3-ene-8,13-diynes were prepared to test [2+2+2] cycloisomerization processes catalyzed by transition metals. The RhCl(CO)(PPh3)2 complex was found to catalyze the cycloisomerization reaction giving the desired cycloadducts in high yields.

Research describes the stereoselective synthesis of unique dehydro amino acids that are employed in the synthesis of alpha-amino acids. Results reveal that (-)-alpha-pinene serves as the starting raw material to obtain cyclobutane ring and chiral centers for preparing chiral cyclobutane synthons.

The reaction of n-cinnamylpyridinium tetrafluoroborates with Pd(dba)2 and the respective ligand leads to (1-{dimethylamino}-2-{diphenylphosphino}ethane)- (eta3-1-arylallyl)palladium tetrafluoroborates (3). The trans form of the compounds 3 predominates. For the compounds 3, the NMR chemical shifts (delta{sub X}-delta{sub H}) where X ranges between NO2 to OMe, are comparable to the delta Hammett substitution constants. The C-3 atom is trans to the positive charge of the amine ligand.

The preparation of new polypyridylic chiral ligands having either [C.sub.3] or lower symmetry via a de novo construction of the pyridine nucleus by means of Krohnke methodology is presented. The preliminary catalytic results performed with the Ru complex (-)-21 show moderate enantioselectivities in styrene epoxidation with PhI[(AcO).sub.2].

The productive synthesis of tetrapeptide containing cyclobutane and beta-alanine sediments is explained. Analytical computations predict a most stable folded conformation corresponding to a 14-helix stabilized by a hydrogen bond.

Herein, we perform for the first time a preliminary NMR and computational study of the spiroglycol structure. Spiroglycol is a highly symmetrical molecule, but it should be chiral due to the presence of a chiral axis. The presence of two enantiomers was demonstrated performing NMR enantiodifferentiation experiments using α,α'-bis(trifluoromethyl)-9,10-anthracenedimethanol (ABTE) as a chiral solvating agent (CSA). The addition of 0.6 equiv of ABTE allows the differentiation of several spiroglycol proton signals. The lack of resolution observed in the proton spectrum can be tackled through the corresponding 13 C NMR spectrum where a significant enantiodifferentiation at the spirocarbon atom was observed. In order to physically separate both enantiomers, a SPG derivatization with camphorsulfonic acid and Mosher's acid was performed affording the corresponding diastereoisomeric ester mixtures. Computations performed with the Gaussian16 package showed that the enantiodifferentiation is mainly due to the different compound thermodynamics stability.

A user-friendly NMR interface for the visual and accurate determination of experimental one-bond proton-carbon coupling constants ( 1 J CH ) in small molecules is presented. This intuitive 1 J CH profile correlates directly to δ( 1 H), and 1 J CH facilitates the rapid identification and assignment of 1 H signals belonging to key structural elements and functional groups. Illustrative examples are provided for some target molecules, including terminal alkynes, strained rings, electronegative substituents, or lone-pair-bearing heteronuclei.

The photoactivated evolution of a series of enantiomerically pure 5-oxymethyl-2(5H)-furanones has been investigated. The observed intramolecular photoreactions have proven to be a straightforward entry to diverse and stereochemically rich fragment-molecules, most of which contain the privileged tetrahydropyran (THP) scaffold. The formation of the THP involves a 1,5-hydrogen atom transfer process, leading to a diradical intermediate that recombines to form a new σ C-C bond. These reactions take place under both sensitized and nonsensitized conditions, and they are highly stereoselective. When the substrate contains an allyl residue, the intramolecular [2 + 2] cycloaddition leading to cyclobutanes competes advantageously. When the substrate contains a THP residue, the cyclization involves the concomitant formation of [6,6]-spiroketals with nonanomeric relationships.

This study presents a simple method for measuring long-range heteronuclear coupling constants between protons and proton-bearing carbons. The approach involves recording two conventional 1D-TOCSY experiments in which the offset of the selective proton pulse is set on the low- and high-frequency 13C satellites of an isolated proton signal, Hi. Long-range heteronuclear coupling values between the 13Ci bonded to Hi and the protons Hj,k...n that belong to the same spin system were easily determined from the relative displacement of the relayed Hj,k...n signals in the satellite-selective TOCSY spectra. The sense of the displacement indicated the sign of the coupling constants.

High enantioselection is obtained in Michael additions of cyclic beta-ketoesters in the presence of lanthanium triflates and (S,S)-ip-pybox. Intermediates based on simultaneous coordination of the lanthanide to both (S,S)-ip-box and beta-ketoester (in keto and enolate forms) are detected by means of ESI mass spectrometry and NMR experiments, and a possible mechanism is proposed through theoretical calculations.

[Chemical reaction: See text] Several derivatives of (+)- and (-)-2-aminocyclobutane-1-carboxylic acid, 1, have been prepared through enantiodivergent synthetic sequences. The stereoselective synthesis of free amino acid (+)-1 has been achieved, and this product has been fully characterized for the first time. Stereocontrolled alternative synthetic methodologies have been developed for the preparation of bis(cyclobutane) beta-dipeptides in high yields. Among them, enantio and diastereomers have been synthesized. beta,beta- and beta,delta-Dimers resulting from the coupling of a cyclobutane residue and a linear amino acid have also been prepared. The ability of the cyclobutane ring as a structure-promoting unit both in the monomers and in the dimers has been manifested. The NMR structural study and DFT theoretical calculations evidence the formation of strong intramolecular hydrogen bonds giving rise to cis-fused [4.2.0]octane structural units that confer high rigidity on these molecules both in solution and in the gas phase. The contribution of a cis-trans conformational equilibrium derived from the rotation around the carbamate N-C(O) bond has also been observed, the trans form being the major conformer. In the solid state, this equilibrium does not exist, and moreover, intermolecular hydrogen bonds are present.

13C NMR differences of chemical shifts (delta(X) - delta(H)) of allyl carbon atoms in a series of trans-(1-(diphenylphosphino)-2-(dimethylamino)ethane)(eta(3)-1-arylallyl)palladium tetrafluoroborates, X ranging from NO(2) to OMe, correlate very well with sigma Hammett constants for C-1 and with sigma(+) for C-3, this carbon atom being in a trans relationship with the positively charged nitrogen atom.