Alkyl Halides Organometallic Reagents 1) Grignard R X + Mg0

ether or THF

R MgII X now nucleophilic

reacts with: H+, D+ electrophile (H2O, D2O) O R R or R O H

HO
1 2 3

6 5 4 1 2

HO
3

6 5 4

disconnect between carbons 2 and 3

MgBr

O +
6 3 4 5

MgBr O
1 2 3 6 5 4

H2O

HO
1 2 3

6 5 4

2) Organolithium a) Li n-butyl lithium H3C H3C

b)

2 H3C

Li + CuI

ether

CuLi +

LiI

Formation

H3C H3C

CuLi

2 1

ether
1

LiI

CH3Cu Reaction

any alkyl group

Remember pKa of alkyl group is ~50 (very high) so deprotonated alkyl group is VERY basic

H3C CH2 H2 H3C C Li

NaBr

very basic carbons

will react w/ acidic proton like H2O (pKa 15.7) HC CH (pKa 25)

Not mentioned in class: Chapter 10.10 Be familiar with terminology, oxidation, and reduction. In inorganic/general chemistry: (M=metal) M0 M2+ Organic chemistry: reduction: gain in electron density by carbon oxidation: loss of electron density by carbon In practice: oxidation reduction C O C N C X bonds will form M2+ oxidation M0 reduction

C H break C H will form C O A very common example: H2C CH2 Pd/C N2 H3C CH3 Reduction C N C X bonds will break