OrganoLithium Compounds

Peter H.M. Budzelaar

 Organo-lithium compounds

• Ionic character, electron-deficient

– oligomeric or polymeric structures

• Strongly basic and nucleophilic

– applications in organic synthesis

• Reducing
– unwanted side reactions

2 OrganoLithium Compounds
 Organo Na, K compounds

• "Purely" ionic
– polymeric structures
– pyrophoric solids
– mostly insoluble in any solvent they don't react with

• Very strong bases, not that good as nucleophiles

– few applications
– organoLi compounds are much easier to handle

3 OrganoLithium Compounds
 Driving force for oligomerization

• ionic interpretation:
-
+ - +
+
- + - - - + -
+ +

Ionic interactions are "soft"

but not weak!

4 OrganoLithium Compounds
 Driving force for oligomerization

• covalent interpretation

Li
Li Li

2e-3c and 2e-4c bonds are

not just bonding between Li and C,
but also bonding between the Li atoms

5 OrganoLithium Compounds
 Structure of [EtLi]4

6 OrganoLithium Compounds
 Structure of [CyLi]6

7 OrganoLithium Compounds
 Structure of [BuLi(THF)]4

8 OrganoLithium Compounds
 Structure of [o-Me2NCH2C6H4Li]4

9 OrganoLithium Compounds
 Structure of [2,6-(MeO)2C6H3Li]4

10 OrganoLithium Compounds
 Structure of [MeLi(sparteine)]2

not all hydrogen positions

well-determined

used for
enantioselective
deprotonation

11 OrganoLithium Compounds
 Structure of PhLi(pmdta)

pmdta =
Me2N N NMe2
Me

12 OrganoLithium Compounds
 Structure of (Allyl)Li(pmdta)

2.33
2.25
2.72

13 OrganoLithium Compounds
 Structure of [BzNa(pmdta)]∞

14 OrganoLithium Compounds
 Structure of [(Me3Si)3CRb]∞

15 OrganoLithium Compounds
Structure of (naphthalene)[Li(tmeda)]2
tmeda =
Me2N NMe2

16 OrganoLithium Compounds
 Synthesis of OrganoLi Compounds
Direct synthesis

RX + Li RLi + LiX
– Reactivity: alkyl > aryl, Cl < Br < I etc
– Commercial synthesis: mostly from chlorides
– In laboratory: usually from alkyl bromides/iodides (easier to start)
– Complication: Li reacts with N2, do reaction under Ar !
– Side reaction: Wurtz coupling, especially for X = I
– In apolar or weakly polar solvents
– Radical mechanism

Transmetallation

RM + Li RLi + M
– M less electropositive than Li
– Infrequently used

17 OrganoLithium Compounds
 Reactions of OrganoLi Compounds
Metallation

RLi + R'H R'Li + RH

– Faster for more basic R-
– Faster in polar and/or coordinating solvents
– Works well if product capable of
intramolecular coordination

Metal-halogen exchange
RLi + R'Br R'Li + RBr

– Facile for I and Br, usually (too) slow for Cl, F

– Regioselective synthesis of R'Li
– Side reaction: Wurtz coupling
– Usually done at low temperature (-80 to -20°C)

18 OrganoLithium Compounds
 Reactions of OrganoLi Compounds

Metathesis
n RLi + MXn n LiCl + R nM

– Driving force: stability of LiCl (lattice energy!)

– Selective synthesis of RlMXm often hard

PhLi + PhPCl2 (1:1) PhPCl2 + Ph2PCl + Ph 3P

– With excess RLi often "ate" complexes (Rn+1M-)

19 OrganoLithium Compounds
 Structure of [(tmeda)LiMe2]2Mg

20 OrganoLithium Compounds