Determination of relative stereochemistry

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This review article discusses use of ^2,3J_CH, ³J_HH scalar couplings and ¹³C chemical shifts for assignment of relative stereochemistry of centers (marked in bold) in -CHX-CHY- and -CHX-CH₂-CHY- hydrocarbon fragments, where X and Y are polar substituents.

²J_CH couplings are useful in fragments CYH-CHX where substituent X is polar (and the coupling between atoms marked in bold is observed).

Bifulco, G., Dambruoso, P., Gomez-Paloma, L., Riccio, R.. Determination of Relative Configuration in Organic Compounds by NMR Spectroscopy and Computational Methods

Chem Rev 107(9):3744--79, 2007

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Riccio, R., Bifulco, G., Cimino, P., Bassarello, C., Gomez-Paloma, L.. {Stereochemical analysis of natural products. Approaches relying on the combination of NMR spectroscopy and computational methods}

Pure and Applied Chemistry 75(2-3):295--308, 2003

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Marquez, B.L., Gerwick, W.H., Williamson, R.T.. {Survey of NMR experiments for the determination of n J (C, H) heteronuclear coupling constants in small molecules}

Magn. Reson. Chem 39:499--530, 2001

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The article below is the pioneering work showing that ^2,3J_CH and ³J_HH coupling constants can be used to determine relative stereochemistry of two adjacent stereocenters in acyclic hydrocarbons. The analysis is based on the assumption (supported by molecular mechanics calculations) that most acyclic hydrocarbons substituted with -OH, -OCH₃, -CH₃ and other non-bulky substituents favor gauche or anti conformations within 10^o accuracy. Also authors state that this J-based method to determine relative stereochemistry works for the cases where one rotamer is at least 85% populated.

Matsumori, N., Kaneno, D., Murata, M., Nakamura, H., Tachibana, K.. Stereochemical determination of acyclic structures based on carbon-proton spin-coupling constants. A method of configuration analysis for natural products

J. Org. Chem 64(3):866--876, 1999

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Ciminiello, P., Dell'Aversano, C., Fattorusso, E., Forino, M., Magno, S., Di Rosa, M., Ianaro, A., Poletti, R.. {Structure and Stereochemistry of a New Cytotoxic Polychlorinated Sulfolipid from Adriatic Shellfish}

Journal of the American Chemical Society 124(44):13114--13120, 2002

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Murata, M., Matsuoka, S., Matsumori, N., Paul, GK, Tachibana, K.. {Absolute configuration of amphidinol 3, the first complete structure determination from amphidinol homologues: application of a new configuration analysis based on carbon-hydrogen spin-coupling constants}

J Am Chem Soc 121:870--871, 1999

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