Biochemistry - The Chemical Reactions of Living Cells, Volume 2 - D. Metzler 1980

Organization of Metabolism: Catabolic Pathways
Fatty Acid Oxidation

METABOLISM involves an immense variety of Chemical Reactions. Many of these are organized into complex cycles that can sometimes be difficult to follow. Yet, underlying this complexity are logic and order. With few exceptions, metabolic pathways consist of sequential reactions such as those described in chapters 7, 8, and 10 (and summarized in Table 9-1), with each chain of reactions organized to accomplish a specific chemical task.

In this chapter, we will examine some of the primary pathways involved in the Catabolism of Cell/8.html">Nutrients and Cellular components. Anabolic (biosynthetic) reactions will be discussed in subsequent chapters.

The combustion of Hydrocarbons yields substantially more energy than the combustion of most other Organic compounds, so it is hardly surprising that fats—the primary form of nutrient storage in the body—are predominantly hydrocarbon in nature. From an energetic standpoint, the fatty acid components are of the greatest significance. Most aerobic Cells are capable of completely oxidizing Fatty acids to СО2 and Water through processes that take place within the mitochondrial matrix of Eukaryotic cells.

The site of chemical attack is the oxidized end of the fatty acid. The initial stage is a "priming reaction" in which the fatty acid undergoes a sequence of chemical transformations S1A(a) [see Table 7-2 — Ed.] to form a water-soluble acyl-CoA derivative, a compound in which the α-hydrogens of the fatty acid radicals are "activated" [Equation (9-1)]:

Class="center">

This reaction is catalyzed by acetate thiokinase [Equation (7-30)] and other acyl-CoA synthetases—Enzymes that activate fatty acids. There are at least Two Types of such enzymes: some are specific for medium-length carbon chains (ranging from 4 to 12 carbon atoms), while others target longer chains. Mitochondria also contain acyl-CoA synthetases [1] capable of cleaving GTP to GDP and Pi, in which case The sequence of reactions is SlA(y).

Major Types of Metabolic Reactions

Reaction

Table (page)

Figure

Text (page)

1. Nucleophilic substitution

88


91

A. At —CH2Y



93

B. At — СО—Y

192


103

C. At a phosphorus atom



115

D. At a sulfur atom



139

S1. Sequential substitution at P and C, frequently coupled with ATP Cleavage. Utilized in the synthesis of esters, amides, thioesters, as well as in substrate-level phosphorylation

136


132

2. Addition




A. To C = О or C = N

88


140

B. To C = С



145

3. Elimination




A. With formation of C = О or C = N



140

B. With formation of C = С



145

C. With decarboxylation

4. Formation of enolate anions and enamines and their participation in isomerization reactions

89

7-9

153

154

5. Enolate anions as nucleophiles

89


160

A. Substitution at C = О



162

S 5A. Biotin-dependent carboxylation

195


194

B. Addition to C = О (aldol Condensation)


7-10

7-11

162

C. Addition to СО2 (ß-carboxylation)



170

6. Selected structural rearrangements 7. Thiamine-dependent α-cleavage

S7A. Synthesis

90

8-3

176

201

ATP involving phosphoketolase


8-4

206

S7B. Oxidative Decarboxylation of α-keto acids


8-19

268

S7C. Reaction involving Pyruvate formate-lyase


8-19

274

8. Pyridoxal phosphate Schiff base reactions


8-6, 8-7

209

9. Hydrogen and Electron transfer reactions

239, 257


237

A. NAD+- and NADP+-dependent

239

8-10

240

B. Flavin-dependent

257

8-14

253

C. Lipoate-dependent


8-18

268

D. Iron-sulfur protein reactions


(10-4)—(10-6)

379

E. Quinone reactions


10-8

383

F. Cytochrome reactions


10-3

373

G. Selenium-dependent dehydrogenation



331

S9C. ATP formation coupled with aldehyde oxidation


8-13

246

10. Vitamin B12-dependent reactions

290


283

Isomerization reactions



292

Reactions Catalyzed by Ribonucleotide reductase



294

Methyl group transfer reactions



296

11. Hydroxylation

Reactions involving Dioxygenases



435

Reactions involving monoxygenases (hydroxylases)



436

Flavin-containing

Pteridine-dependent



437

438

α-Ketoglutarate-dependent



440

Ascorbate-dependent



441

Cytochrome P-450-dependent



443

12. Peroxide reactions




Oxidative decarboxylation



273

Involving Glutathione peroxidase



370

13. Folic acid-dependent reactions

281

8-20, 8-21

275



Last update: 06/08/2026

Editorial and Educational Adaptation: This material has been compiled based on the primary/original source text. The project team performed an editorial review, corrected technical inaccuracies, structured sections, and adapted the content for an educational format.

What was processed:

  • elimination of formatting defects (OCR errors, structural breaks, corrupted characters);
  • editorial organization of content;
  • standardization of terminology in accordance with academic sources;
  • verification of factual statements against the original source text.

All mentions of the author, publication year, and origin of the primary text have been preserved in accordance with the source.