New NMR pulse schemes completely driven under homonuclear and heteronuclear cross-polarization conditions are proposed for the study and the measurement of coupling constants in symmetrical molecules in solution. The appropriate superimposition of independent magnetization components can afford several spin-selective multiplet patterns that are suitable for the determination of the magnitude and the sign of proton-proton and proton-carbon coupling constants with optimum sensitivity levels. A detailed product operator formalism analysis for the proposed doubly selective 1D and nonselective 2D HCP-TOCSY versions is provided and experimental verification for the configurational analysis of symmetric olefinic systems having chemical equivalence is demonstrated.
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