Model compound synthesis

E. A., and Chen, C. L. (1992) Biphenyl-type lignin model compounds Synthesis and car-bon-13 NMR substiment chemical shift additivity rule. Holzforschung 46(2), 127-134. 

The intramolecular version for synthesizing cyclic and polycyclic compounds offers a powerful synthetic method for naturally occurring macrocyclic and polycyclic compounds, and novel total syntheses of many naturally occurring complex molecules have been achieved by synthetic designs based on this methodology. Cyclization by the coupling of an enone and alkenyl iodide has been applied to the synthesis of a model compound of l6-membered car-bomycin B 162 in 55% yield. A stoichiometric amount of the catalyst was used because the reaction was carried out under high dilution conditions[132]. 

Polyanilines. Initial preparations of polyaniline (PANI) led to insoluble materials that were difficult to characterize. Use of model compounds and polymers (124,125) allowed for definitive stmctural analysis. Poly( phenylene amineimine) (PPAI) was synthesized directiy to demonstrate that PANI is purely para-linked (126). The synthesis was designed so as to allow linkage through the nitrogen atoms only (eq. 9). Comparison of the properties of PPAI and PANI showed PPAI to be an excellent model both stmcturaHy and electronically. 

Synthesis and reactions of NADH and NADPH model compounds with interconversion of central and axial chirality 97YGK132. 

Dihydropyridines not only are intermediates for the synthesis of pyridines, but also are themselves an important class of N-heterocycles an example is the coenzyme NADH. Studies on the function of NADH led to increased interest in the synthesis of dihydropyridines as model compounds. Aryl-substituted dihy-dropyridines have been shown to be physiologically active as calcium antagonists. Some derivatives have found application in the therapy of high blood pressure and angina pectoris. For that reason the synthesis of 1,4-dihydropyridines has been the subject of intensive research and industrial use. The Hantzsch synthesis has thus become an important reaction. 

The deoxyinositols (quercitols, cyclohexanepentols) are useful model compounds which display many of the physical and chemical properties of true deoxy sugars. Although (-b)-proto-quercitol, the best known isomer, was isolated from nature 118 years ago, no synthesis has been reported up until now. The synthesis here described is actually that of the (-)-enantiomer, starting with (-)-inositol however, identical procedures applied to the readily available ( + ) or dl-inositol would give (- -) or DL-proto-quercitol, respectively. The natural occurence of, )-proto-quercitol has... 

Synthesis of Model Compounds 16.2.1.3.1 Three-ring OVPs... 

Scheme 22. Synthesis of model compound 101 via a thermodynamically driven rearrangement of 95.

Chiral sulphoxides are the most important group of compounds among a vast number of various types of chiral organosulphur compounds. In the first period of the development of sulphur stereochemistry, optically active sulphoxides were mainly used as model compounds in stereochemical studies2 5 6. At present, chiral sulphoxides play an important role in asymmetric synthesis, especially in an asymmetric C—C bond formation257. Therefore, much effort has been devoted to elaboration of convenient methods for their synthesis. Until now, optically active sulphoxides have been obtained in the following ways optical resolution, asymmetric synthesis, kinetic resolution and stereospecific synthesis. These methods are briefly discussed below. 

The synthesis and characterization of the monomeric amidinato-indium(I) and thallium(I) complexes [Bu C(NAr)2]M[But(NAr(NHAr)] (M = In, Tl Ar = 2,6-Pr2CgH3) have been reported. Both compounds were isolated as pale yellow crystals in 72-74% yield. These complexes, in which the metal center is chelated by the amidinate ligand in an N, j -arene-fashion (Scheme 33), can be considered as isomers of four-membered Group 13 metal(I) carbene analogs. Theoretical studies have compared the relative energies of both isomeric forms of a model compound, In[HC(NPh)2]. ... 

The synthesis of three silaketenimines 105a-c prompted Tokitoh and Okazaki to calculate the optimized geometry of a model compound, PhiSiCNPh. This model reinforced that 105a-c are truly Lewis acid-base pairs, with the isocyanide donating its carbon lone pair to an empty p-orbital perpendicular to the lone pair... 

Suggest syntheses for TMs (9) and (10) needed as intermediates TM (9) in the synthesis of brominated hydroxy benzoic acids and TM (10) in the synthesis of model compounds for studying biological mechanisms of ester hydrolysis,... 

Exanrple Ester ( 2) was needed as a model compound to study mechanisms of biological ester hydrolysis. It is clearly made from acid (33) which could be made from aldehyde (34) by a Wittig reaction. We discussed the synthesis of (3b) on page 21. 

We shall return to the discussion of the orientation and electronic structure of the dioxygen ligand during the next section which is primarily concerned with recent advances in the synthesis and physical characterization (particularly X-ray analysis) of oxygencarrying metal porphyrin model compounds. 

Quideau, S. Ralph, J. A biomimetic route to lignin model compounds via silver(I) oxide oxidation. 1. Synthesis of dilignols and non-cyclic benzyl aryl ethers. Holzforschung 1994, 48, 12-22. 

Karhunen, P Rummakko, P. Pajunen, A. Brunow, G. Synthesis and crystal structure determination of model compounds for the dibenzodioxocine structure occurring in wood lignins. J. Chem. Soc., Perkin Trans. 1996, 1, 2303-2308. 

It should be noted that most of the substitution-based synthesis work with poly(organophosphazenes) has been preceded by exploratory studies at the small molecule, model compound level, often with the use of cyclic trimer I as a model for polymer II (6). 

The development of magnetic resonance techniques coupled with computer time averaging has made the study of enzyme structure and function by these techniques more fruitful. H NMR, 13C NMR and 19F NMR have been used successfully to determine the structure of B 12-compounds in solution. We are rapidly approaching the point where the structure and function of the B 12-coenzymes will be completely understood, and the need for the synthesis and study of simple Bi2-model compounds such as the cobaloximes (3) will be no longer necessary. However, even though studies on the chemistry of B 12-coenzymes is a necessary prerequisite to our understanding of their biochemical role, it is a wrong assumption to expect that the chemical properties of free coenzymes in aqueous solution should be duplicated in the enzymes. 

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