Homonuclear shift correlated 2D-NMR

Figure 5.69. 2D-Homonuclear shift correlated H-NMR spectrum of nigellicine, a new alkaloid isolated from Nigella sativa ( kalonji ). The circles on the diagonal line correspond to the peaks of the H-NMR shown on the horizontal axis but give a view of them from above. The cross peaks above and below the diagonal establish the connectivities between a and c / d .

Figure 5.70. 2D-Homonuclear shift correlated H-NMR spectrum of 795-vindolinine. The cross peaks establish the connectivities between the protons.

Although we might be able to get all the H-H coupling information through a long series of homonuclear decoupling experiments, there is a much simpler way the 2D NMR technique known as homonuclear shift correlation spectroscopy, or COSY. 

D Correlated NMR Homonuclear Shift Correlation Jeener Two-pulse Expt. H h.Jhh h.Jhh 3,50,52 3,49-52... 

The basic aim of heteronuclear correlation 2D NMR is, as in the homonuclear experiment, to indicate which nuclei are coupled to one another. In heteronuclear NMR the correlation information is doubly useful since it provides chemical shifts for two different nuclear species in a single experiment. In the discussion which follows, the nuclei concerned will be assumed to be protons and carbon-13, although similar experiments have been reported for 31p 1h,53,54 15n-1h55 and correlation. 

Quinting and Cai [62] carried out high-resolution C-NMR and proton NMR measurements to determine the tacticity of poly(n-butyl methacrylate) (PBMA) with particular focus on the peak assignments for the n-butyl side chain. Free-radical and anionic PBMA were examined, with the former being predominantly syndiotactic and the latter isotactic. Proton NMR resonances for the n-alkyl chain of these polyacrylics show a combination of effects from configurational sensitivity and homonuclear scalar interactions. A combination of J-resolved proton NMR and proton- C-heteronuclear correlated 2D-NMR spectra was used to characterise the long-range chemical shift effects due to tacticity. 

Homonuclear shift correlation (HOMCOR) 2D-NMR technique where a two-dimensional map is generated... 

There are basically three main types of 2D NMR experiments J-resolved, shift correlation through bonds (e.g., COSY), and shift correlations through space e.g., NOESY). These spectra may be of homonuclear or heteronuclear type involving interactions between similar nuclei (e.g., protons) or between different nuclear species (e.g., H with C). 

A more useful type of 2D NMR spectroscopy is shift-correlated spectroscopy (COSY), in which both axes describe the chemical shifts of the coupled nuclei, and the cross-peaks obtained tell us which nuclei are coupled to which other nuclei. The coupled nuclei may be of the same type—e.g., protons coupled to protons, as in homonuclear 2D shift-correlated experiments—or of different types—e.g., protons coupled to C nuclei, as in heteronuclear 2D shift-correlated spectroscopy. Thus, in contrast to /-resolved spectroscopy, in which the nuclei were being modulated (i.e., undergoing... 

Multidimensional NMR spectra are not restricted to cases where the separate frequency axes encode signals from different nuclear types. Indeed, much of the early work on the development of 2D NMR was performed on cases where both axes involved chemipal shifts. The main value in such spectra comes from the information content in cross peaks between pairs of protons. In COSY-type spectra (COSY = Correlation SpectroscopY) cross peaks occur only between protons that are scalar coupled (i.e., within 2 or 3 bonds) to each other, whereas in NOESY (NOE Spectroscopy) spectra cross peaks occur for protons that are physically close in space (<5 A apart). A combination of these two types of 2D spectra may be used to assign the NMR signals of small proteins and provides sufficient information on internuclear distances to calculate three-dimensional structures. Figure 12.3 includes a panel showing the COSY spectrum of cyclosporin and highlights the relationships between ID H-NMR spectra and corresponding 2D homonuclear (COSY) and heteronuclear (HSQC) spectra. 

Correlations anticipated in various homonuclear ( H- H) and heteronuclear ( C- H) 2D NMR experiments are conceptualized in Eigure 5.1. A hypothetical model compound (the chemical shifts are not accurate and are for illustrative purposes only) with three aromatic protons and four side-chain protons on its three side-chain carbons is used to illustrate the information available from each experiment. A set of five experiments, in addition to the standard ID proton and carbon spectra, are useful for characterizing any model compound or lignin. The correlation spectroscopy (COSY) experiment correlates directly coupled protons (Figure 5.1a). 

For the determination of the sequence and substitution positions of the different monosaccharides of a saponin, a series of proton and carbon 2D-NMR techniques can provide valuable information about the usually crowded regions of the conventional ID spectra. Thus, integrated approaches including ID or 2D H- H homonuclear NMR shift-correlation experiments (DQF- and TQF-COSY, TOCSY or HOHAHA, NOESY, ROESY or CAMELSPIN), and H-detected H-,3C heteronuclear shift correlation (HMQC, HMBC) have proved to be extremely useful. 

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