Simultaneous determination of the magnitude and the sign of multiple heteronuclear coupling constants in 19 F or 31 P‐containing compounds

The presence of a highly abundant passive nucleus (Z =  19  F or 31 P) allows the simultaneous determination of the magnitude and the sign of up to three different heteronuclear coupling constants from each individual cross‐peak observed in a 2D 1 H‐X selHSQMBC spectrum. Whereas J (HZ) and J (XZ) coupling constants are measured from E.COSY multiplet patterns, J (XH) is independently extracted from the complementary IPAP pattern generated along the detected F2 dimension. The incorporation of an extended TOCSY transfer allows the extraction of a complete set of all these heteronuclear coupling constants and their signs for an entire 1 H subspin system. 1 H‐X/ 1 H‐Y time‐shared versions are also proposed for the simultaneous measurement of five different couplings ( J (XH), J (YH), J (XZ), J (YZ), and J (ZH)) for multiple signals in a single NMR experiment. Copyright © 2015 John Wiley & Sons, Ltd.