Carbon quaternary

For hydrocarbon studies, analyses can be made without prior assumptions, since the carbons not carrying protons can be excited directly, this of course not being the case for hydrogen (e.g., quaternary carbons in alkanes, substituted carbons in aromatic rings). 

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. 

The cyclization to form very congested quaternary carbon centers involving the intramolecular insertion of di-, tri-, and tetrasubstituted alkenes is particularly useful for natural products synthesis[l36-138], In the total synthesis of gelsemine, the cyclization of 166 has been carried out, in which very severe steric hindrance is e.xpected. Interestingly, one stereoisomer 167... 

Section 13 18 One of the special techniques for distinguishing carbons according to the number of their attached hydrogens is called DEPT A series of NMR measurements using different pulse sequences gives normal nulled and inverted peaks that allow assignment of primary secondary tertiary and quaternary carbons... 

Quaternary carbon (Section 2 13) A carbon that is directly at tached to four other carbons... 

Two adjacent tertiary carbon atoms 730-920 770-725 Often a band at 530-524 cm indicates presence of adjacent tertiary and quaternary carbon atoms. 

Substituent group Primary carbon Secondary carbon Tertiary carbon Quaternary carbon... 

Akylsilanes undergo highly regioselective acylation to give P,y-unsaturated ketones (177). Acylation of y,y-dialkylallyltrialkylsilane provides a route to the constmction of difficulty accessible quaternary carbon centers. 

Carbon atoms are classified according to their degree of substitution by other carbons. A primary carbon is directly attached to one other carbon. Similarly, a secondary carbon is directly attached to two other carbons, a tertiary carbon to three, and a quaternary carbon to four. Alkyl groups are designated as primary, secondary, or tertiary according to the degree of substitution of the carbon at the potential point of attachment. 

Conjugate addition [2] to Midiael acceptors is die most important and usefid reaction in orgatiocopper diemistiy, and die reaction is ofien used as die key step in die syndiesis of numerous natural and unnatural products. Perhaps one of die most efficient methods for die syndiesis of quaternary carbon centers is organo-copper-mediated conjugate addidon to /, / -disubstituted enones. 

As we have seen previously, succinimides containing a quaternary carbon form the basis for a series of anticonvulsant drugs. In the course of research in this series, it was found that the inclusion of additional hetero atoms in the ring was quite compatible with anticonvulsive activity. We consider here the oxa-zolidinediones a discussion of the hydantoins is found later in this section. 

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). 

Primary carbon (1°) Secondary carbon (2°) Tertiary carbon (3°) Quaternary carbon (4C]... 

Putting together the information from all three spectra makes it possible to tell the number of hydrogens attached to each carbon. The CH carbons are identified in the DEPT-90 spectrum, the CH2 carbons are identified as the negative peaks in the DEPT-135 spectrum, the CH3 carbons are identified by subtracting the CH peaks from the positive peaks in the DEPT-135 spectrum, and quaternary carbons are identified by subtracting all peaks in the DEPT-135 spectrum from the peaks in the broadband-decoupled spectrum. 

DEPT-NMR (Section 13.6) An NMR method for distinguishing among signals due to CH3, CH2, CH, and quaternary carbons. That is, the number of hydrogens attached to each carbon can be determined. 

Quaternary carbon. 84 Quaternary structure (protein). 1038 Quinine, structure of, 533, 950 Quinoline, aromaticity of, 533... 

Recently, Uneyama reported that treatment of (R)-l-tosyl-2-trifTuoromethylazir-idine 76 (Scheme 3.24) with w-BuLi at -100 °C and subsequent trapping of the anion with electrophiles such as chloroformates produced aziridine-2-carboxylates 77 in good to excellent yields [71]. The retention of the configuration of the tri-fluoromethylated quaternary carbon center in the course of the reaction was confirmed by derivatization of the product and by X-ray studies. 

Scheme 8.46 Construction of the quaternary carbon center of fasicularin.

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