HMQC Lactose

The common theme so far in our correlation experiments has been to allow spins to evolve during q under the influence of directly coupled nuclear spins. We have seen the power of COSY, HMQC, HMBC, and INADEQUATE to provide us with detailed structural information for ipsenol, caryophyllene oxide, and lactose. In this section, we will develop another method for showing correlations and apply it to molecules with distinct, isolated proton spin systems such as carbohydrates, peptides, and nucleic acids. 

FIGURE 5.23 The HMQC spectrum for lactose. See text for an explanation of the notation. Assignments are given as an aid. 

The HMQC-TOCSY spectrum for lactose is given in Figure 5.28 with all of the proton and carbon resonances labeled. The overall appearance of this spectrum is reminiscent of an HMBC but the correlations are quite different. It is equally interesting and useful to start on the proton axis (F2) or the carbon axis (FI). If we start on the proton axis at 5.23 ppm, the anomeric proton for the a-anomer of glucose (ad), and proceed downward vertically, we find six correlations to the six carbons of this glucose residue. If we refer back to the simple HMQC spectrum for lactose, we find only one correlation for this proton. Likewise, the anomeric proton of the /3-anomer of glucose at 4.67 ppm also shows six correlations to the carbons of its respective glucose residue. 

Compared to caryophyllene oxide and lactose, the HMQC spectrum for the tetra-peptide appears relatively simple (Figure 5.33). Indeed, VGSE has only 10 carbon atoms with attached protons and the spectrum shows correlations to nine carbons. Actually, there are 10 correlations as can be seen in the inset of the shielded methyl portion of the spectrum. Let us summarize the complementary information up to and including the HMQC spectrum. 

Chapter 5 still covers 2-D correlation but has been reorganized, expanded, and updated, which reflects the ever increasing importance of 2-D NMR. The reorganization places all of the spectra together for a given compound and treats each example separately ipsenol, caryophyllene oxide, lactose, and a tetrapeptide. Pulse sequences for most of the experiments are given. The expanded treatment also includes many new 2-D experiments such as ROESY and hybrid experiments such as HMQC-TOCSY. There are many new Student Exercises. 

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