The book concentrates in illustrating the applications of C-13 chemical shifts to structural and stereochemical analysis of a variety of organic, oranometallic and bio-organic compounds including dynamic NMR, the experimental conditions to determine and various multidimensional methods to assign the C-13 chemical shifts. First time a chemist who wants to employ C-NMR for solving a structural problem will find practically all necessary fundamental advice within the same covers. The book is a new volume in the successful series Methods in Stereochemical Analysis and is geared towards scientists and students. It is limited mainly to alicyclic chemistry in order to make the explanations transparent and understandable to readers.
1. Introduction. 1.1 Practical Considerations. 1.2 Assignment of 13 C NMR Spectra. References. 2. Substituent Effect Correlations. 2.1 General Remarks. 2.2 Parametrization and Selected Rules of Additivity. 2.3 Straightforward Application of (Single) Substituent Effects to Structure Elucidation. 2.4 Miscellaneous Applications to Stereochemical Analysis and Structure Determination. References. 3. On the Origin and Stereochemical Connections of the Substituent Effects. 3.1 alpha--Effects. 3.2 Steric Influence on alpha--Effects. 3.3 beta--Effects. 3.4 beta--Effects at Methyl Carbons. 3.5 gamma--Effects. 3.6 delta--Effects. 3.7 Vicinal and Poly Substitution Effects. 3.8 "Buttressing" Effects. 3.9 Influence of the Ring Heteroatoms on the Substituent Effect. References. 4A. Conformational and Configurational Analysis and Substituent Effects on the 13 C NMR Chemical Shifts of Alicyclic Compounds. 4A.1 A Complete Conformational Analysis with the Aid of 13 C NMR Chemical Shift Correlations: Methyl--Substituted Tetrahydro--1,3--oxazines. 4A.2 Conformational Analysis of Methyl--Substituted 1,3--Dioxanes and Related Compounds. 4A.3 Methyl--Substituted 2--Oxo--l,3,2--dioxathianes. 4A.4 Oxanes (Tetrahydropyranes). 4A.5 1,3--Dithianes. 4A.6 1,3--Oxathianes. 4A.7 Methyl--Substituted Isochromanes and Related Compounds. 4A.8 Thianes and Thianium Salts. 4A.9 Cyclohexanes. 4A. 10 Piperidines and N--Methylpiperidines. 4A.11 trans-- and cis--Decahydroquinolines and Some Related Systems. 4A.12 Some Miscellaneous Examples. References. 4B. Structural and Stereochemical Analysis of Four--, and Five--, and Seven--Membered Cyclanes and Some Other Systems. 4B.1 Four--Membered Cyclanes. 4B.2 Influence of Ring Heteroatoms on the 13 C Chemical Shifts of Ring Carbons in Five-- and Six--Membered Cyclanes. 4B.3 Five--Membered Cyclanes. 4B.4 Seven--Membered Heterocyclanes. 4B.5 Tautomerism and 13 C NMR Chemical Shifts. 4B.6 Alkaloids, Terpene Derivatives, Sugars, and Nucleosides. References. 4C. On the Origin of Stereoelectronic Substituent Effects. 4C.1 Interplay of Steric and Stereoelectronic Effects. 4C.2 The Anomeric Effect. 4C.3 The Gauche Effect. 4C.4 The Gauche/Gauche Effect. 4C.5 Intra-- and Intermolecular Hydrogen Bonding. References. 5. 13 C Chemical Shifts as Probes in Configurational and Conformational Analysis. 5.1 General Applications. 5.2 Stereochemistry of Rigid or Anancomeric Stereoisomers. 5.3 The Stereochemistry of Flexible Rings and Substituents in Unsaturated Compounds. 5.4 Factor Analysis of 13 C Chemical Shifts. 5.5 Conformational Analysis of Conjugated Compounds: Dihedral Angle Subject to Steric Hindrance. 5.6 Stereochemical Analysis of Acyclic Compounds. 5.7 13 C Chemical Shift Subject to Structural Variations to Indicate the Stereochemistry. 5.8 Stereochemically Relevant Deuterium Isotope Effects on 13 C Chemical Shifts. 5.9 Conformation--Dependent 13 C Chemical Shifts in the Solid State. 5.10 Miscellaneous Applications. References. 6. Dynamic NMR Spectroscopy and Frozen Spectra. 6.1 The Effect of Dynamic Processes on NMR Line Shape. 6.2 The Determination of Thermodynamic (DELTAG-) and Kinetic Parameters (DELTAG!=, DELTAH!=, DELTAS!=) Parameters from Line Shape Variations. 6.3 Experimental Preconditions. 6.4 Peculiarities of 13 C NMR Spectroscopy. 6.5 Applications of Dynamic 13 C NMR Spectroscopy. 6.6 Dynamic 13 C NMR Spectroscopy in the Solid State. References. 7. Application of 13 C NMR Spectroscopy to the Configurational and Conformational Analysis of Natural Products, Organometallic Compounds, and Synthetic Polymers. 7.1 Natural Products. 7.2 Organometallic Compounds. 7.3 Synthetic Polymers. References. 8. Application of Other NMR Parameters in Combination with the 13 C Chemical Shift in Conformational and Configurational Analysis. 8.1 1 H Chemical Shift. 8.2 Homonuclear Coupling Constants: 2 J H,H , 3 J H,H , and J long--range . 8.3 Heteronuclear Copling Constants 1 J C,H and 3 J C,H . 8.4 Nuclear Overhauser Effects and Spin--Lattice Relaxation Times. 8.5 Strategies for the Assignment of Medium--Sized and Larger Ring Natural Products by Multidimensional NMR Spectroscopy. References. Index.