Groups from synthesis

Alcohols are key functional groups in synthesis because their synthesis can be plaimed by an important disconnection and because they can be converted into a whole family of other functional groups. List three types of molecule you might make from an alcohol by FGI. 

Regioselectivity of C—C double bond formation can also be achieved in the reductiv or oxidative elimination of two functional groups from adjacent carbon atoms. Well estab llshed methods in synthesis include the reductive cleavage of cyclic thionocarbonates derivec from glycols (E.J. Corey, 1968 C W. Hartmann, 1972), the reduction of epoxides with Zn/Nal or of dihalides with metals, organometallic compounds, or Nal/acetone (seep.lS6f), and the oxidative decarboxylation of 1,2-dicarboxylic acids (C.A. Grob, 1958 S. Masamune, 1966 R.A. Sheldon, 1972) or their r-butyl peresters (E.N. Cain, 1969). 

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. 

Cyclopentadiene itself has been used as a feedstock for carbon fiber manufacture (76). Cyclopentadiene is also a component of supported metallocene—alumoxane polymerization catalysts in the preparation of syndiotactic polyolefins (77), as a nickel or iron complex in the production of methanol and ethanol from synthesis gas (78), and as Group VIII metal complexes for the production of acetaldehyde from methanol and synthesis gas (79). 

Pyruvate kinase possesses allosteric sites for numerous effectors. It is activated by AMP and fructose-1,6-bisphosphate and inhibited by ATP, acetyl-CoA, and alanine. (Note that alanine is the a-amino acid counterpart of the a-keto acid, pyruvate.) Furthermore, liver pyruvate kinase is regulated by covalent modification. Flormones such as glucagon activate a cAMP-dependent protein kinase, which transfers a phosphoryl group from ATP to the enzyme. The phos-phorylated form of pyruvate kinase is more strongly inhibited by ATP and alanine and has a higher for PEP, so that, in the presence of physiological levels of PEP, the enzyme is inactive. Then PEP is used as a substrate for glucose synthesis in the pathway (to be described in Chapter 23), instead... 

The net result of this biosynthetic cycle is the synthesis of a four-carbon unit, a butyryl group, from two smaller building blocks. In the next cycle of the process, this butyryl-ACP condenses with another malonyl-ACP to make a... 

Phosphatidylethanolamine synthesis begins with phosphorylation of ethanol-amine to form phosphoethanolamine (Figure 25.19). The next reaction involves transfer of a cytidylyl group from CTP to form CDP-ethanolamine and pyrophosphate. As always, PP, hydrolysis drives this reaction forward. A specific phosphoethanolamine transferase then links phosphoethanolamine to the diacylglycerol backbone. Biosynthesis of phosphatidylcholine is entirely analogous because animals synthesize it directly. All of the choline utilized in this pathway must be acquired from the diet. Yeast, certain bacteria, and animal livers, however, can convert phosphatidylethanolamine to phosphatidylcholine by methylation reactions involving S-adenosylmethionine (see Chapter 26). 

There are many possibilities and I shall simply analyse the published synthesis. Removal of the methyl group from (50) gives ketone (51) which can be made from enone (52) by Michael addition of an ethyl group. Unambiguous cross-condensation between enolisable (54) and reactive (53) gives (52). 

The rest are more difficult to classify, but (39) looks like the Robinson annelation product as the two phenyl groups prevent synthesis from an aromatic compound. 

As an example we quote the formation of hydrocarbons from synthesis gas with Group 8 metal catalysts. 

Lipase-catalyzed synthesis of polyesters from cyclic anhydrides and oxi-ranes was reported. The polymerization took place by PPL catalyst and the molecular weight reached 1 x 10" under the selected reaction conditions. During the polymerizahon, the enzymatically formed acid group from the anhydride may open the oxirane ring to give a glycol, which is then reacted with the anhydride or acid by lipase catalysis, yielding the polyesters. 

---