Acceptor double

The rearside attack model became equally important in the discussion of stereoselectivity in the aldol condensation. In 1981, Seebach and Golinski proposed a topological rule for aldol-like reactions which says that the H atom, the smaller substituent on the donor component, adopts an anti position with respect to the acceptor double bond C=A in the preferred transition state, cf. A and B in Scheme 6.28 [35]. This preference of A over B comes about as a result of the increases in steric hindrance when the donor substituent R2 is jammed against Rj and H of the acceptor in the non-perpendicular approach B. 

Cravino, A., G. Zerza, M. Maggini, S. Bucella, M. Svensson, M.R. Andersson, H. Neugebauer, and N.S. Sariciftci. 2000. A novel polythiophene with pendant fullerenes Toward donor/acceptor double-cable polymers. Chem Commun 2487-2488. 

Giacalone, R, J.L. Segura, N. Martin, M. GateDani, S. Luzzati, and N.-O. Lupsac. 2003. Synthesis of soluble donor-acceptor double-cable polymers based on polythiophene and tetracyanoanthraqui-nodimethane (TCAQ). Org Lett 5 1669-1672. 

Maleic anhydride (MA) occupies a unique position in a large family of monomers used to prepare polymeric materials. The simultaneous presence in the molecule of both an electron-acceptor double bond and an anhydride moiety confers unique properties to MA and enables the monomer to be used in both addition and condensation polymerization systems. In fact, one of the largest uses of the monomer, unsaturated polyester resins, employs both moieties for producing the final products (see Chapter 12). 

Ouhib, R, Khoukh, A., Ledeuil, J.-B. et al. (2008a) Diblock and random donor/acceptor double cable polythiophene... 

A gap level is called an acceptor level if tlie defect is neutral when tlie state is empty (no electron). It is called a donor level if tlie defect is neutral when tlie state is occupied (one electron). The foniier is often labelled (0 / -) and tlie latter (-t / 0), where tlie first (second) sign refers to tlie charge of tlie defect when no electron (one electron) is present. Double or triple acceptor and donor levels are similarly labelled. 

Shallow donors (or acceptors) add new electrons to tire CB (or new holes to tire VB), resulting in a net increase in tire number of a particular type of charge carrier. The implantation of shallow donors or acceptors is perfonned for tliis purjDose. But tliis process can also occur unintentionally. For example, tire precipitation around 450°C of interstitial oxygen in Si generates a series of shallow double donors called tliennal donors. As-grown GaN crystal are always heavily n type, because of some intrinsic shallow-level defect. The presence and type of new charge carriers can be detected by Flail effect measurements. 

These oxazolines have cationic surface-active properties and are emulsifying agents of the water-in-oil type. They ate acid acceptors and, in some cases, corrosion inhibitors (see Corrosion). Reaction to oxazoline also is useful as a tool for determination of double-bond location in fatty acids (2), or for use as a protective group in synthesis (3). The oxazolines from AEPD and TRIS AMINO contain hydroxyl groups that can be esterified easily, giving waxes (qv) with saturated acids and drying oils (qv) with unsaturated acids. 

When heated in the presence of a carboxyHc acid, cinnamyl alcohol is converted to the corresponding ester. Oxidation to cinnamaldehyde is readily accompHshed under Oppenauer conditions with furfural as a hydrogen acceptor in the presence of aluminum isopropoxide (44). Cinnamic acid is produced directly with strong oxidants such as chromic acid and nickel peroxide. The use of t-butyl hydroperoxide with vanadium pentoxide catalysis offers a selective method for epoxidation of the olefinic double bond of cinnamyl alcohol (45). 

Note. Both the rearrangement In t-ButanoI) and the double bond isomerization of (114) (In Benzene) are quenched in a diffusion-controlled process by suitable triplet acceptors e.g., naphthalene or 2,5-dimethylhexa-2,4-diene). The rearrangement (114) (118) -I- (120) is also observed on irradiation in... 

Dehydrofluorination by primary and secondary aliphatic amines occurs at room temperature and is the basis of diamine cross linkmg, which occurs by dehydrofluonnation and subsequent nucleophihc substitution of the double bond The locus of dehydrofluonnation is a VDF unit flanked by two perfluoroolefin units This selectively base-sensitive methylene group also undergoes elimination as the first step in phase-transfer-catalyzed cross-hnking with quaternary ammo mum or phosphomum salts, bisphenols, and morganic oxides and hydroxides as HF acceptors [31, 32]... 

FIGURE 14.22 Glutamate aspartate aminotransferase, an enzyme conforming to a double-displacement bisnbstrate mechanism. Glutamate aspartate aminotransferase is a pyridoxal phosphate-dependent enzyme. The pyridoxal serves as the —NH, acceptor from glntamate to form pyridoxamine. Pyridoxamine is then the amino donor to oxaloacetate to form asparate and regenerate the pyridoxal coenzyme form. (The pyridoxamine enzyme is the E form.)... 

This impressive reaction is catalyzed by stearoyl-CoA desaturase, a 53-kD enzyme containing a nonheme iron center. NADH and oxygen (Og) are required, as are two other proteins cytochrome 65 reductase (a 43-kD flavo-protein) and cytochrome 65 (16.7 kD). All three proteins are associated with the endoplasmic reticulum membrane. Cytochrome reductase transfers a pair of electrons from NADH through FAD to cytochrome (Figure 25.14). Oxidation of reduced cytochrome be, is coupled to reduction of nonheme Fe to Fe in the desaturase. The Fe accepts a pair of electrons (one at a time in a cycle) from cytochrome b and creates a cis double bond at the 9,10-posi-tion of the stearoyl-CoA substrate. Og is the terminal electron acceptor in this fatty acyl desaturation cycle. Note that two water molecules are made, which means that four electrons are transferred overall. Two of these come through the reaction sequence from NADH, and two come from the fatty acyl substrate that is being dehydrogenated. 

Van Leusen and co-workers also demonstrated the utility of dilithio-tosylmethyl isocyanide (dilithio-TosMIC) to extend the scope of the application. Dilithio-TosMIC is readily formed from TosMIC and two equivalents of n-butyllithium (BuLi) in THF at -70"C. Dilithio-TosMIC converts ethyl benzoate to oxazole 14 in 70% yield whereas TosMIC monoanion does not react. In addition, unsaturated, conjugated esters (15) react with dilithio-TosMIC exclusively through the ester carbonyl to provide oxazoles (16). On the other hand, use of the softer TosMIC-monoanion provides pyrroles through reaction of the carbon-carbon double bond in the Michael acceptor. 

TT-acceptor function of the C2C3 double bond. Lithiated benzothiophene can be quenched by [Pt(dppe)Cl2] to give 279 [97JCS(D)2955]. 

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