1. Chapter 15: Alcohols, Diols, and Ethers
Alcohols by reduction of aldehydes and ketones
Metal hydride reagents
Reduction of carboxylic acid derivatives with LiAlH4
Alcohols by opening of epoxides
Preparation of diols
Reactions of alcohols

2. Chapter 15: Alcohols, Diols, and Ethers
Alcohol synthesis using organometallic reagents

3. Chapter 15: Alcohols, Diols, and Ethers
aldehydes
ketones
Chapter 15
Use of alcohols to make other functional groups

4. 15.1 – Sources of Alcohols

5. 15.1 – Sources of Alcohols

6. 15.1 – Sources of Alcohols
Progesterone
Testosterone

7. Organic Synthesis – Molecular Engineering
Two main components :
Carbon-Carbon bond formation – organometallics
Functional group manipulation – e.g. R2CHOH to R2C=O

8. 15.2 – Preparation of Alcohols by Reduction of RR’C=O

9. 15.3 – Preparation of Alcohols by Reduction of RCO2R’
Mechanism analogous to Grignard-Ester Reaction

10. 15.4 – Preparation of Alcohols from Epoxides
Nucleophilic ring-opening is an SN2 process governed by steric hindrance
around the electrophilic carbon being attacked

11. Cis-dihydroxylation via an osmate ester intermediate
15.5 – Preparation of Diols
Cis-dihydroxylation via an osmate ester intermediate

12. 15.5 – Preparation of Diols
Zhou, M.; O’Doherty, G. A. Org. Lett. 2006, 8,

13. 15.6 – Reactions of Alcohols – Review

14. 15.7 – Conversion of Alcohols to Ethers
Acid-base reaction followed by SN2 reaction on alkyl halide
Limited to primary alkyl halides (secondary give E2 in competition)

15. 15.7 – Conversion of Primary Alcohols to Ethers
Acid-base reaction followed by SN2 reaction on alcohol
Limited to primary alcohols (2o/3o give elimination products)

16. 15.7 – Conversion of Primary Alcohols to Ethers

17. 15.8 – Esterification of Alcohols
Examples

18. 15.8 – Other Methods of Esterification
Acyl chlorides
Acetic anhydride
Skip Section 15.9

19. 15.10 – Oxidation of Alcohols

20. 15.10 – Oxidation of Alcohols – Mechanism 15.3

21. 15.10 – Oxidation of Alcohols – Stopping at the Aldehyde
Also works for secondary alcohols to ketones

22. 15.11 – Oxidation of Alcohols – Biological Oxidation
Structure of NAD+
Figure 15.2

23. 15.11 – Oxidation of Alcohols – Biological Oxidation

24. 15.11 – Oxidation of Alcohols – Biological Oxidation

25. 15.12 – Oxidative Cleavage of Vicinal Diols
Use:
Compare to ozonolysis:

26. Important – more acidic than alcohols: pKa ~ 10
15.13 – Thiols
Important – more acidic than alcohols: pKa ~ 10

28. Synthesis

29. Synthesis