Summary of CH14 Delocalized Systems VI.

Allylic Grignard and allylithium reagents

I. Definition • Preparations
X
Delocalized systems: extended overlap of three or more contiguous p orbitals Mg/Et2O
R2R1C C CH2 R2R1C C CH2MgX
bond bond H H
allylic halide allylic Grignard
p orbital
R2R1C CH CH3 n-BuLi/TMEDA R2R1C C CH2Li
H
allyllithium

• Allylic Grignard and allyllithium reagents react with electrophiles

Allylic systems (C+, C•, C–) Conjugated dienes like other organometallic compounds.
II. Stability of delocalized -systems
• -electron delocalization stabilizes the entire -system VII. Conjugated Dienes
Synthesis The Heck Rection
C+: substituted allylic > 3° > allyl > 2° > 1°
Pd, or Ni
C•: substituted allylic or allyl > 3° > 2° > 1° CH2 CHCl + CH2 CH2
C–: CH2=CH-CH2– > CH3-CH2-CH2–
• Review resonance theory
VIII. Electrophilic 1,2 vs 1,4-additions of H-X or X2 to conjugated
-know how to draw resonance structures and determine their relative
dienes
stabilities.
H
-explain the formal charge (C+, C•, C–) distribution in a delocalized H2C C C CH2
-system H
H–X X H
H2C C C CH2 H2C C C CH2 X– (or
-know how resonance structures contribute to the stability of the actual R R or X–X 1,2-addition
X)
H H
molecule H
(X: Cl, Br) (or X)
• MO theory H2C C C CH2
-numbers of AOs is equal to numbers of MOs H
X H H
-node and its relationship to stability of MO (or
1,4-addition
X)
-explain the formal charge (C+, C•, C–) distribution
according to individual MO • Ionic mechanism via a delocalized C+ intermediate
-Fill up the bonding MOs with electrons lowers the • 1,2-addition is the kinetic product while 1,4-addition is the
energy of the system (stabilization) thermodynamic product
IX. Diels-Alder cycloadditions
III. Kinetic vs. Thermodynamic control • Diels-Alder reaction is a concerted reaction with a high
• Kinetic control: the ratio of products of a reaction is determined by the stereospecificity
relative rate.
• Conditions favor kinetic control: short reaction time, lower reaction
temp, irreversible reactions
• Thermodynamic control: the ratio of products of a reaction that reaches
equilibrium is determined by the relative stabilities of the products
• Conditions favor thermodynamic control: longer reaction time, higher
reaction temperature, reversible reactions
IV. Allylic halogenation
Br2 (low conc. high temp.) • Kinetically controlled addition favors endo products while
H2C CH CH2 H2C CH CH2
or NBS/hv or ROOR thermodynamically controlled addition favors exo products.
H allylic halide Br • Most Diels-Alder reactions are reversible.

• Radical substitution (favored by the formation of an allylic radical) vs.

X. Intra molecular Electrocyclic reactions
ionic addition
• NBS in the presence of ROOR or hv (radical mechanism) gives exclusive
allylic bromination or hu
V. Nucleophilic substitutions
Nu
good Nu–
H2C C C
SN2 H R1 inversion
R1
R2 R2
H2C C C R1
H Nu
X poor Nu– R2
H2C C C H2C C C
SN1 H R1 H
R2 Nu

racemic mixture

1° or 2° allylic halides undergo SN1 reactions with poor nucleophiles

and SN2 reactions with good nucleophiles and 3° allylic halides
always undergo SN1 reactions.