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Chapter 4. Equilibrium of the compositions of Grignard reagents.

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Presentation on theme: "Chapter 4. Equilibrium of the compositions of Grignard reagents."— Presentation transcript:

1 Chapter 4

2 Equilibrium of the compositions of Grignard reagents

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5 n-butyllithium and potassium t-butoxide(super base) greater stability of sp2 carbanions Retention of configuration

6 Metal-halogen exchange

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9 Reduction of sulfides dimethylaminonaphthalene(LDMAN)

10 Shapiro reaction vinyllithium compounds Nicolaou et al. J.Am.Chem.Soc.Vol.117,No.2,1995,634.

11 Reactions with Alkylating Agents Limited in scope Radicals involved Hydrogen abstraction

12 Allyllithium and benzyllithium reagents

13 Ring closure Grignard reagents Reaction with Carbonyl Compoundds addition of Grignard reagents

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17 good leaving group +

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19 Competing reactions Meerwein- Pondorff-Verley reduction Enolization of the ketone

20 1234 123412 3 4 homoallylic system

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22 Lewis acid

23 directed ortho lithiation

24 stable at low temperature

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26 (DMF)

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41 fast electron transfer step no free radicals are generated

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59 Heck reactions:

60 Kumada coupling

61 Organozinc compounds (Negishi coupling)

62 SYNTHESIS September 1992 Palladium-Catalysed Reactions of Organotin Compounds Tetence N.Mitchell Fachbereich Chemli,Universitāt Dortmund,Posifach 500 500,D-4600 Dortmund 50. Germany Received 16 August 1991;revised 12 December 1991

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64 Sonogashira Coupling

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72 Skeleton Reanangement

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