Quaternary carbon compounds

Catelani D, A Colombi, C Sorlini, V Treccani (1977) Metabolism of quaternary carbon compounds 2,2-dimethylheptane and tcrt-butylbenzene. Appl Environ Microbiol 34 351-354. 

Because reductive cleavage of aliphatic nitro compounds with Bu3SnH proceeds via alkyl radicals, nitro compounds are also used as precursors to alkyl radicals. Reactions using nitro compounds may have some advantages over other ones, since aliphatic nitro compounds are available from various sources. For example, the sequence of the Michael additions of nitro compounds provides an excellent method for the construction of quaternary carbon compounds (Eq. 7.79).126 Newkome has used this strategy for the construction of dendritic polymers (Eq. 7.80).127... 

A major difficulty with the Diels-Alder reaction is its sensitivity to sterical hindrance. Tri- and tetrasubstituted olefins or dienes with bulky substituents at the terminal carbons react only very slowly. Therefore bicyclic compounds with polar reactions are more suitable for such target molecules, e.g. steroids. There exist, however, several exceptions, e. g. a reaction of a tetrasubstituted alkene with a 1,1-disubstituted diene to produce a cyclohexene intermediate containing three contiguous quaternary carbon atoms (S. Danishefsky, 1979). This reaction was assisted by large polarity differences between the electron rich diene and the electron deficient ene component. 

Cyclopropanes are now readily available and have become useful, through hydrogenolysis, for synthesis of compounds containing quaternary carbons, em-dialkyl, r-butyl, and angular-methyl substituents (779), compounds often available only with difficulty otherwise (.77,5i,55,750,756), Cyclopropanes can be formed in good yields by hydrogenation of cyclopropenes (26). 

P450 is able to hydroxylate the -CHj group of the quaternary methyl group of 5,5-difluorocamphor (Figure 7.45a) to the 9-hydroxymethyl compound (Fble and Dawson 1984), and both adamantane and adamantan-4-one at the -CH quaternary carbon atom (Figure 7.45b) (White et al. 1984). 

N-Aziridinylimines are valuable substrates for domino radical cydizations since they are able to serve simultaneously as radical acceptors and donors. They allow a versatile and general construction of quaternary carbon centers from carbonyl compounds [33]. By employing this methodology, an elegant and stereoselective synthesis of ( )-modhephene (3-70), one of the rare naturally occurring [3.3.3]propellanes,... 

Thus, the rule of Keulemans (49), that a-quaternary carbon formyl compounds are not formed, was followed. The olefin isomerized to allow formyl attachment to a primary carbon atom. Addition of phosphine, which decreases isomerization, resulted in no reaction. 

For an adamantane-type compound, it is possible to substitute the four tertiary hydrogen atoms and make four quaternary carbon atoms. These carbon atoms can be asymmetric if the four substituents are chosen properly. It is possible to specify these chiral centers separately, but their chiralities can also be so interlinked that they collectively produce one pair of enantiomers with only one chiral center. Usually it is more convenient to collectively specify the chirality with reference to a center of chirality taken as the unoccupied centroid of the adamantane frame. 

The previous section discussed chelation enforced intra-annular chirality transfer in the asymmetric synthesis of substituted carbonyl compounds. These compounds can be used as building blocks in the asymmetric synthesis of important chiral ligands or biologically active natural compounds. Asymmetric synthesis of chiral quaternary carbon centers has been of significant interest because several types of natural products with bioactivity possess a quaternary stereocenter, so the synthesis of such compounds raises the challenge of enantiomer construction. This applies especially to the asymmetric synthesis of amino group-substituted carboxylic acids with quaternary chiral centers. 

Table I gives the compositions of alkylates produced with various acidic catalysts. The product distribution is similar for a variety of acidic catalysts, both solid and liquid, and over a wide range of process conditions. Typically, alkylate is a mixture of methyl-branched alkanes with a high content of isooctanes. Almost all the compounds have tertiary carbon atoms only very few have quaternary carbon atoms or are non-branched. Alkylate contains not only the primary products, trimethylpentanes, but also dimethylhexanes, sometimes methylheptanes, and a considerable amount of isopentane, isohexanes, isoheptanes and hydrocarbons with nine or more carbon atoms. The complexity of the product illustrates that no simple and straightforward single-step mechanism is operative rather, the reaction involves a set of parallel and consecutive reaction steps, with the importance of the individual steps differing markedly from one catalyst to another. To arrive at this complex product distribution from two simple molecules such as isobutane and butene, reaction steps such as isomerization, oligomerization, (3-scission, and hydride transfer have to be involved.

Nitrite substitutes can be divided into seven chemical categories (1) amine benzoates (2) fatty acid amines (3) phosphate or carbonate silicates (4) organophosphates (5) amine borates (6) alkanolamines and (7) quaternary ammonium compounds ("quats"). Thus, the technology already exists for replacing nitrite with no loss in rust protection. However, most replacements for nitrite are more expensive, less effective, less likely to be compatible with other additives, and work by a different mechanism (12). It is therefore not surprising that fluids containing nitrite are still relatively com mon. 

The determination of alkyl and alkylbenzyl quaternary ammonium compounds may be complicated by the polarity of the compound, its tendency to form micelles when the alkyl groups have 12 or more carbon atoms and lack of chromophores. Addition of tetrahydrofuran as organic modifier to the solvent precluded micelle formation and allowed the separation of a mixture of alkylbenzyl and alkylbenzylethyl quaternary ammonium compounds by CZE. Indirect determination of these compounds is achieved on addition of cationic chromophores to the buffer, using a standard UVD421. The indirect methods of detection for CE have been reviewed422. 

The second new compound linearilin (13) was an amorphous powder with [a] = -f 18.35° The HRMS of the compound m z 469.2669 and NMR with one methyl, four methoxy, six methylene, nine methine and four quaternary carbon atoms indicated the molecular formula C Hj NOg. 

C-21 methyl protons. The C-3 and C-16 melhine protons appeared at 8 3.82 and 4.99, respectively. The downfield chemical shift values of C-3 and C-6 methine protons were indicative of the presence of geminal oxygen functionahties. The C-6 resonated at 8 5.36 while the sp hybridized C-28 methylene protons resonated as two singlets, integrating for one proton each, at 8 5.56 and 6.06. A combination of H and C-NMR spectral data indicated to us that compound 11 has a steroidal skeleton. A detailed interpretation of broad C-NMR and DEPT spectra revealed the presence of three metlyl, ten methylene, eight methine and five quaternary carbon atoms in 11. The stereochemistry at various chiral centers was estabhshed with the aid of NOESY spectrum. 

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