1. Chapter 14: Organometallics, structure and nomenclature

2. Cyclopropyl lithium Vinyl sodiumDiethyl magnesium Methyl magnesium iodide Diethylaluminum chloride 14.1 – Organometallic nomenclature

3. 14.2 – Carbon-Metal Bonds in Organometallics

4. Penny Miner, YSU MS (Ricerca Biosciences) Organometallics at YSU

5. 14.2 – Carbon-Metal Bonds in Organometallics Penny Miner, YSU MS (Ricerca Biosciences) Organometallics at YSU Dipolar interactions guide regioselectivity

6. 14.2 – Carbon-Metal Bonds in Organometallics Miner, Wagner, Norris, Heterocycles 2005, 65, 1035-1049 Organometallics at YSU

7. 50-75% decrease in capsule production Preliminary Activity Against S. aureus Prof. Diana Fagan (YSU Biological Sciences)

8. 14.3 – Preparation of Organolithium Compounds Organolithiums

9. Organomagnesium compounds – Grignard reagents 14.4 – Preparation of Organomagnesium Compounds

10. CH 3 Li, (CH 3 ) 3 CLi, n-BuLi are extremely powerful bases Convenient preparation of LDA 14.5 – Organolithium Compounds as Bases

11. Lab Experiment Grignard Reagent Preparation Glassware must be clean and dry Dry with the “heat gun” Cool then begin experiment Be careful to use the right ether!

12. 14.5 – Organolithium Compounds as Bases

13. Carbonyl Polarization: Grignard Polarization: 14.6 – Synthesis of Alcohols Using Grignard Reagents

14. 14.6-7 – Synthesis of Alcohols Using Organometallic Reagents New Mechanism: Nucleophilic Addition Most often followed by a quench with acid:

15. Overall Sequence: Nucleophilic Addition then quench 14.6-7 – Synthesis of Alcohols Using Organometallic Reagents Very versatile alcohol synthesis

16. Example: Starting material product 14.6-7 – Synthesis of Alcohols Using Organometallic Reagents

17. Starting materialproduct Product IR: 3200 cm -1 Example:

18. Starting materialproduct Product MS: M + = 254 14.6-7 – Synthesis of Alcohols Using Organometallic Reagents

19. 14.8 – Synthesis of Acetylenic Alcohols

20. 14.9 – Organic Synthesis – Molecular Engineering DDT, 2003, 1128

21. 14.9 – Organic Synthesis – Molecular Engineering

22. 14.9 – Molecular Engineering – Designing and Building ACS Petroleum Research Fund Award 2006-2009

23. 14.9 – Retrosynthetic Analysis – Planning the Synthesis

24. PlanSynthesis

25. 14.9 – Retrosynthetic Analysis (synthetic equivalent)

26. 14.9 – Retrosynthetic Analysis (synthetic equivalent)

27. 14.9 – Retrosynthetic Analysis Example:

28. 14.9 – Retrosynthetic Analysis Example:

29. 14.9 – Retrosynthetic Analysis and Synthesis

30. 14.10 – Tertiary Alcohols from Esters and Grignard Reagents

31. Retrosynthesis: Synthesis: Also possible: 14.10 – Tertiary Alcohols from Esters and Grignard Reagents

32. Proposed structure: 14.11 – Alkane Synthesis Using Organocopper Reagents

33. Useful for coupling with primary alkyl halides Use of secondary and tertiary alkyl halides complicated by competing E2 reactions Works for simple alkyl halides, vinyl halides and aryl halides Mechanism not completely understood 14.11 – Alkane Synthesis Using Organocopper Reagents

34. Iodomethyl zinc iodide Simmons-Smith reaction 14.12 – An Organozinc Reagent for Cyclopropane Synthesis

35. Not covering 14.13 – 14.17