Synthesis chain substituents

The first asymmetric synthesis of (-l-)-abresoline was achieved from the chiral piperidine derivative 153, which upon treatment of its hydroxy side-chain substituent with carbon tetrabromide, triphenylphosphine, and triethyl-amine cyclized to the frarcr-quinazolidine 154. Deketalization and silyl protection of the phenolic group, followed by stereoselective reduction with lithium tri-t -butylborohydride (L-Selectride ), gave an alcohol, which after acylation and deprotection furnished (-l-)-abresoline 155 (Scheme 25) <2005TL2669>. 

In addition to its use in structural establishment of indoles, NMR has been widely applied to the study of (a) the protonation of indoles, (b) the stereochemistry of the side-chain substituents, and (c) the mechanism of the Fischer indole synthesis. 

To be successful in these applications, it is important that materials can self-assemble into precisely defined structures. Peptide polymers have many advantages over conventional synthetic polymers since they are able to hierarchically assemble into stable ordered conformations [4]. Depending on the amino acid side chain substituents, polypeptides are able to adopt a multitude of conformationally stable regular secondary structures (helices, sheets, turns), tertiary structures (e.g. the /J-slrand-helix-/J-strand unit found in /1-barrels), and quaternary assembhes (e.g. collagen microfibrils) [4], The synthesis of polypeptides that can assemble into non-natural structures is an attractive challenge for polymer chemists. 

One of the limitations of the Warren s adaptation of Homer-Wittig olefina-tion, the failure of the (Z)-selective route when the alkene has a branched chain substituent, has now been overcome. Reduction of the p-ketophosphonates carrying a-branches, e.g. (112) and (113), with sodium borohydride and cerium chloride gives excellent a / -stereoselectivity and hence (Z)-alkene on base-induced elimination. Enantioselective synthesis of both jy -(115) and anti- ll) P-hydroxy-phosphine oxides has been achieved with up to 90% e.e. through two separate approaches. The jyn-isomer was obtained by reduction of the corresponding ketone (114), while the anti-isomer is the product of the reaction of the oxazolidine substituted aldehyde (116) with lithiated diphenylmethyl-phosphine oxide (Scheme 10). A new, highly stereoselective approach to trisubstituted alkenes has been reported. Cerium(III) chloride-promoted... 

The third pathway for the synthesis of PAF is the oxidative fragmentation of phosphatidylcholines. When exposed to oxidative conditions, l-O-alkyl-2-arachidonyl-jn-glycero-3-phosphocholine breaks down into a variety of species of l-O-alkyl phospholipids containing different short-chain substituents at the sn-2 position. These 1-0-alkyl phospholipids interact with PAF receptors and induce a variety of biological effects (Stafforini et al, 1996). Analogs of PAF... 

POLY (N-ACYL ETHYLENEIMINES) WITH POLARIZABLE AROMATIC SIDE CHAIN SUBSTITUENTS AND THEIR COMPLEXES SYNTHESIS, STRUCTURE AND ELECTRONIC PROPERTIES... 

Kim O, Gross RA, Hammar WJ and Newmark RA, Microbial synthesis of poly(/3-hydroxyalkanoates) containing fluorinated side-chain substituents. Macromolecules 1996, 29 4572-4581. 

In the previous chapter, we learned how to substitute aromatic rings with a range of electrophiles. The first part of this chapter will show how one substituent may be exchanged for another, by various mechanisms. This will be followed by a brief section on reactions of side chains/substitu-ents on aromatic rings, and then we will be ready to tackle problems in the synthesis of aromatic... 

Furthermore, while some of the carboxylate-alumoxanes formed gels in THF only those with long chain substituents (e.g., dodecanoic acid) and hence low ceramic yield were melt-processable. It would thus be desirable not only to prepare alumoxane preceramics in a one-pot bench-top synthesis from readily available starting materials, but also to determine if lower hydrocarbon substituents could yield better processability. 

Chapters 9, 10 and 11 describe methods for substitution directly on the ring with successive attention to Nl, C2 and C3. Chapters 12 and 13 are devoted to substituent modification as C3. Chapter 12 is a general discussion of these methods, while Chapter 13 covers the important special cases of the synthesis of 2-aminoethyl (tryptaminc) and 2-aminopropanoic acid (tryptophan) side-chains. Chapter 14 deals with methods for effecting carbo cyclic substitution. Chapter 15 describes synthetically important oxidation and reduction reactions which are characteristic of indoles. Chapter 16 illustrates methods for elaboration of indoles via cycloaddition reactions. 

One of the virtues of the Fischer indole synthesis is that it can frequently be used to prepare indoles having functionalized substituents. This versatility extends beyond the range of very stable substituents such as alkoxy and halogens and includes esters, amides and hydroxy substituents. Table 7.3 gives some examples. These include cases of introduction of 3-acetic acid, 3-acetamide, 3-(2-aminoethyl)- and 3-(2-hydroxyethyl)- side-chains, all of which are of special importance in the preparation of biologically active indole derivatives. Entry 11 is an efficient synthesis of the non-steroidal anti-inflammatory drug indomethacin. A noteworthy feature of the reaction is the... 

The most widely used method for the laboratory synthesis of a ammo acids is a modification of the malonic ester synthesis (Section 21 7) The key reagent is diethyl acetamidomalonate a derivative of malonic ester that already has the critical nitrogen substituent m place at the a carbon atom The side chain is introduced by alkylating diethyl acetamidomalonate m the same way as diethyl malonate itself is alkylated... 

Properties. One of the characteristic properties of the polyphosphazene backbone is high chain dexibility which allows mobility of the chains even at quite low temperatures. Glass-transition temperatures down to —105° C are known with some alkoxy substituents. Symmetrically substituted alkoxy and aryloxy polymers often exhibit melting transitions if the substituents allow packing of the chains, but mixed-substituent polymers are amorphous. Thus the mixed substitution pattern is deUberately used for the synthesis of various phosphazene elastomers. On the other hand, as with many other flexible-chain polymers, glass-transition temperatures above 100°C can be obtained with bulky substituents on the phosphazene backbone. 

By varying the molecular stmcture, it is possible to synthesize dye initiators with the requited characteristics. The synthesis of polymethine dyes with different chain length, end groups, and substituents, or with other variations of the chromophore, has been summarized (3,4,9,21,73,74) (see also Cyanine dyes). 

The steric bulk of the three iodine atoms in the 2,4,6-triiodoben2ene system and the amide nature of the 1,3,5-substituents yield rotational isomers of the 5-A/-acyl-substituted 2,4,6-triiodoisophthalamides. Rotational motion in the bonds connecting the side chains and the aromatic ring is restricted. These compounds also exhibit stereoisomerism when chiral carbon atoms are present on side chains. (R,5)-3-Amino-l,2-propanediol is incorporated in the synthesis of iohexol (11) and ioversol (12) and an (3)-2-hydroxypropanoyl group is used in the synthesis of iopamidol (10). Consequendy, the resulting products contain a mixture of stereoisomers, ie, meso-isomers, or an optical isomer. 

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