This work evaluates the efficiency of economic levels of theory for the prediction of 3J HH spin-spin coupling constants, to be used when robust electronic structure methods are prohibitive. To that purpose, DFT methods like mPW1PW91, B3LYP and PBEPBE were used to obtain coupling constants for a test set whose coupling constants are well known. Satisfactory results were obtained in most of cases, with the mPW1PW91/6-31G(d,p)//B3LYP/6-31G(d,p) leading the set. In a second step, B3LYP was replaced by the semiempirical methods PM6 and RM1 in the geometry optimizations. Coupling constants calculated with these latter structures were at least as good as the ones obtained by pure DFT methods. This is a promising result, because some of the main objectives of computational chemistry - low computational cost and time, allied to high performance and precision - were attained together. © 2012 Elsevier B.V.1001 714Wiitala, K.W., Cramer, C.J., Hoye, T.R., Comparison of various density functional methods for distinguishing stereoisomers based on computed 1H or 13C NMR chemical shifts using diastereomeric penam β-lactams as a test set (2007) Magn. Reson. Chem., 45, pp. 819-829Bagno, A., Rastrelli, F., Saielli, G., Toward the complete prediction of the 1H and 13C NMR spectra of complex organic molecules by DFT methods: application to natural substances (2006) Chem. Eur. J., 12, pp. 5514-5525Barone, G., Gomez-Paloma, L., Duca, D., Silvestri, A., Riccio, R., Bifulco, G., Structure validation of natural products by quantum-mechanical GIAO calculations of 13C NMR chemical shifts (2002) Chem. Eur. J., 14, pp. 3233-3239Facelli, J.C., Calculations of chemical shieldings: theory and applications (2004) Concepts Magn. Reson. Part A, 20 A, pp. 42-69Subramaniam, G., Karimi, S., Phillips, D., Solution conformation of longifolene and its precursor by NMR and ab initio calculations (2006) Magn. Reson. Chem., 44, pp. 1118-1121Ragazzi, M., Carbone, P., Ferro, D.R., Ab initio molecular modeling of 13C NMR chemical shifts of polymers. 1. Ethylene-Norbornene Copolymers (2002) Int. J. Quant. Chem., 88, pp. 663-669Rychnovsky, S.D., Predicting NMR spectra by computational methods: structure revision of hexacyclinol (2006) Org. Lett., 8, pp. 2895-2898Gauze, G.F., Pontes, R.M., Basso, E.A., A factorial design analysis of wave functions to be used in calculations of NMR parameters of ketones (2004) J. Mol. Struct. (THEOCHEM), 712, pp. 91-100Basso, E.A., Fiorin, B.C., Rittner, R., Conformational behaviour in S-methyl halothioacetates through NMR, FT-IR, and theoretical calculations (2004) Can. J. Chem., 82, pp. 418-426Taha, H.A., Castillo, N., Sears, D.N., Wasylishen, R.E., Lowary, T.L., Roy, P., Conformational analysis of arabinofuranosides: prediction of 3J H,H using MD simulations with DFT-derived spin-spin coupling profiles (2010) J. Chem. Theory Comput., 6, pp. 212-222Vaara, J., Jokisaari, J., Wasylishen, R.E., Bryce, D.L., Spin-Spin coupling tensors as determined by experiments and computational chemistry (2002) Prog. Magn. Reson. Spec., 41, pp. 233-304Zampella, A., Auria, M.V.D., Paloma, L.G., Casapullo, A., Minale, L., Henin, Y., Callipeltin A, an Anti-HIV cyclic depsipeptide from the new caledonian lithistida sponge Callipelta sp. (1996) J. Am. Chem. Soc., 118, pp. 6202-6209Bassarello, C., Zampella, A., Monti, M.C., Gomez-Paloma, L., D'Auria, M.V., Riccio, R., Bifulco, G., Quantum mechanical calculation of coupling constants in the configurational analysis of flexible systems: determination of the configuration of Callipeltin A (2006) Eur. J. Org. Chem., pp. 604-609Jain, R., Bally, T., Rablen, P.R., Calculating accurate proton chemical shifts of organic molecules with density functional methods and modest basis sets (2009) J. Org. Chem., 74, pp. 4017-4023Palermo, G., Riccio, R., Bifulco, G., Effect of electronegative substituents and angular dependence on the heteronuclear spin-spin coupling constant 3J(C-H): an empirical prediction equation derived by density functional theory calculations (2010) J. Org. Chem., 75, pp. 1982-1991Barone, V., Cossi, M., Tomasi, J., A new definition of cavities for the computation of solvation free energies by the polarizable continuum model (1997) J. Chem. Phys., 107, pp. 3210-3221Bondi, A., Van der Waals volumes+radii (1964) J. Phys. Chem., 68, pp. 441-451Frisch, M.J., Trucks, G.W., Schlegel, H.B., Scuseria, G.E., Robb, M.A., Cheeseman, J.R., Montgomery, J.J.A., Gonzalez, C.J.A., (2004), Pople Gaussian. Wallingford CT: Gaussian, IncStewart, J.J.P., Optimization of parameters for semiempirical methods V: modification of NDDO approximations and application to 70 elements (2007) J. Mol. Mod., 13, pp. 1173-1213Rocha, G.B., Freire, R.O., Simas, A.M., Stewart, J.J.P., RM1: a reparameterization of AM1 for H, C, N, O, P, S, F, Cl, Br, and I (2006) J. Comput. Chem., 27, pp. 1101-1111Stewart, J.J.P., http://OpenMOPAC.net, Stewart Computational Chemistry, Version 11.017WDi Micco, S., Chini, M.G., Riccio, R., Bifulco, G., Quantum mechanical calculation of NMR parameters in the stereostructural determination of natural products (2010) Eur. J. Org. Chem., pp. 1411-1434Rosselli, S., Bruno, M., Maggio, A., Bellone, G., Formisano, C., Mattia, C.A., Di Micco, S., Bifulco, G., Two new flavonoids from bonannia graeca: a DFT-NMR combined approach in solving structures (2007) Eur. J. Org. Chem., pp. 2504-2510Aav, R., Pehk, T., Tamp, S., Tamm, T., Kudrjašova, M., Parve, O., Lopp, M., Theoretical prediction and assignment of vicinal 1H- 1H coupling constants of diastereomeric 3-alkoxy-6,7-epoxy-2-oxabicyclo[3.3.0]octanes (2011) Magn. Reson. Chem., 49, pp. 76-82Williamson, R.T., Marquez, B.L., Sosa, A.C.B., Koehn, F.E., Relative stereochemical determination of β-hydroxycarbonyl compounds (aldol products) utilizing the J-based configuration analysis method (2003) Magn. Reson. Chem., 41, pp. 379-385Tormena, C.F., Rittner, R., Abraham, R.J., Basso, E.A., Pontes, R.M., Conformational analysis. Part 33.1 An NMR, solvation and theoretical investigation of conformational isomerism in N,N-dimethylfluoroacetamide and N,N-dimethyl-α-fluoropropionamide (2000) J. Chem. Soc., Perkin Trans., 2, pp. 2054-2059