Primary natural products

The carbohydrates, amino acids, proteins, and nucleic acids discussed in Chapters 25, 26, and 27 are sometimes called primary natural products because they are found in all types of organisms and are the products of primary metabolism. Secondary natural products are usually produced from primary natural product precursors, such as amino acids or acetate ion, and, in general, are less widespread in occurrence. Today, natural product chemistry usually refers to the structure, reactions, and synthesis of these secondary natural products. 

This chapter discusses some of the more important natural products terpenes, steroids, alkaloids, fats, and prostaglandins. (Fats are primary natural products, but it is convenient to include them in this chapter.) The structures and various aspects of their biosynthesis and chemical reactions are presented in subsequent sections. Because entire books have been written on each of these groups of compounds, the coverage here is necessarily incomplete. However, the intent is to present some of the flavor of their chemistry. Many other classes of naturally occurring organic compounds are not included for reasons of space. 

Primary natural products (Chapter 28) Naturally occurring compounds that are found in all types of organisms and are the products of primary metabolism includes carbohydrates, amino acids, proteins, and nucleic acids. 

Secondary natural products (Chapter 28) Natural products that are usually produced from primary natural product precursors, such as amino acids or acetate ion, and, in general, are less widespread in occurrence than primary natural products. 

In keeping with its biogenetic origin m three molecules of acetic acid mevalonic acid has six carbon atoms The conversion of mevalonate to isopentenyl pyrophosphate involves loss of the extra carbon as carbon dioxide First the alcohol hydroxyl groups of mevalonate are converted to phosphate ester functions—they are enzymatically phosphorylated with introduction of a simple phosphate at the tertiary site and a pyrophosphate at the primary site Decarboxylation m concert with loss of the terti ary phosphate introduces a carbon-carbon double bond and gives isopentenyl pyrophos phate the fundamental building block for formation of isoprenoid natural products... 

There is a wide range of conversion levels. The term maximum conversion type has no precise definition but is often used to describe a level of conversion, where there is no net fuel oil manufactured. A fuel products refinery with specialities may manufacture lubricating oils, asphalts, greases, solvents, waxes and chemical feed stocks in addition to the primary fuel products. The number and diversity of products will naturally vary from one refinery to another. Refineries produce chemical feed stocks for sale to the chemical affiliates and do not have responsibility for the manufacture of chemical products directly. Both operations may be carried out at the same physical location but the corporate product responsibilities are usually separate. 

When cyanogen bromide was used instead of CS2, the corresponding guanidines 169 were obtained under analogous conditions [108]. Moreover, differently substituted guanidines 171 could be obtained in very good yields when the isothiourea 168 was alkylated with Mel under microwave irradiation and the product treated with a primary amine. An intramolecular version of this reaction was also described for the preparation of structure 172 present in several important natural products (Scheme 61). 

Allylic alcohols can be converted to epoxy-alcohols with tert-butylhydroperoxide on molecular sieves, or with peroxy acids. Epoxidation of allylic alcohols can also be done with high enantioselectivity. In the Sharpless asymmetric epoxidation,allylic alcohols are converted to optically active epoxides in better than 90% ee, by treatment with r-BuOOH, titanium tetraisopropoxide and optically active diethyl tartrate. The Ti(OCHMe2)4 and diethyl tartrate can be present in catalytic amounts (15-lOmol %) if molecular sieves are present. Polymer-supported catalysts have also been reported. Since both (-t-) and ( —) diethyl tartrate are readily available, and the reaction is stereospecific, either enantiomer of the product can be prepared. The method has been successful for a wide range of primary allylic alcohols, where the double bond is mono-, di-, tri-, and tetrasubstituted. This procedure, in which an optically active catalyst is used to induce asymmetry, has proved to be one of the most important methods of asymmetric synthesis, and has been used to prepare a large number of optically active natural products and other compounds. The mechanism of the Sharpless epoxidation is believed to involve attack on the substrate by a compound formed from the titanium alkoxide and the diethyl tartrate to produce a complex that also contains the substrate and the r-BuOOH. ... 

Most often, the application of cyanohydrin acetonide couplings to a natural product synthesis calls for coupling with a primary alkyl halide. This has proven successful in every instance. However, on occasion, alkylations of more hindered epoxides or hindered alkyl halides are desirable. These reactions are less dependable. 

The biochemical industry derives its products from two primary sources. Natural products are yielded by plants, animal tissue, and fluids, and they are obtained via fermentation from bacteria, molds, and fungi and from mammalian cells. Products can also be obtained by... 

Mode of action research has caused similar challenges for investigators working with either natural products or synthetic pesticides. The major difficulty is to separate secondary effects from primary causes. Although effects can be measured in... 

---