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33 Carbocations 1
33 Carbocations 1
33 Carbocations 1
Evans
Chem 206
http://www.courses.fas.harvard.edu/colgsas/1063
Chemistry 206
Advanced Organic Chemistry
Carbocation Stabilization
Lecture Number 33
Other Relevant
Background
Reading
Monday
D. A. Evans
11, 2006
December
Saunders, M. and H. A.
Jimenez-Vazquez (1991).
Recent studies of
carbocations. Chem. Rev.
91: 375.
Problem 17: The reaction illustrated below was recently reported by Snider and co-workers (Org.
Lett. 2001, 123, 569-572). Provide a mechanism for this transformation. Where stereochemical
issues are present, provide clear three dimensional drawings to support your answer.
O
Me
EtAlCl2
CH2Cl2, 0 C
Me
OH
CHO
NH2
O
R
Me
NaNO2
HOAc/H O
2
M. Shair, D. Evans
R + H2O
Definition:
ROH + H
R+
ROH
aR+
aH+
a
a = activity
H2O
PCl5
(4-MeO-C6H4)3C
0.82
Ph3C
6.63
Fe
(3-Cl-C6H4)3C
11.0
CHPh
CH2
Fe
0.40
Ph
0.75
13.3
CHPh R
Cr(CO)
10.4
Co2
3
7.4
H7 C3
+
HC
7
3 7.2
C3H7
most stable
4.77
Carbocation Generation
Hydride abstraction from neutral precursors
R3C H +
Lewis-Acid
H
R3C H =
H
H
RS
RS
RC
LAX
salts
LA
RCX +
R
:
A
r
yl
+
o
t
h
e
r
c
h
a
r
g
e
s
t
a
b
ili
zi
n
g
su
bst
itu
ent
s
X:
SO
4
2-
,
Cl
O4
-
,
FS
O3
-
,
CF
3S
O3
-
From neutral
precursors via
heterolytic
dissociation
solvent
R3C X
+ X
H
H
R
R
R
H
C CH2OH
Br
Carbocations: Structure
D. A. Evans, B. Breit
H
C
H C
H
C
FMO Description
Take linear combination of CR (filled) and C pz-orbital (empty):
E
CR
CR
CR
C
H
CR
Chem 206
D. A. Evans, K. Scheidt
Me
Me
F
Me
H
Me
Me
+
2 SbF5
[F SbFSbF ]
5
Me
H
Me
Me
Chem 206
Ph
Ph
Cl
Me
Me
AgSbF6
Me
Me
F Sb
5
SbF
1.495
2.092
1.739 **
1.467
+
1.467
1.855
1.442
C
C
hyperconjugation
no bridging
1.50
3
D. A. Evans, K. Scheidt
1.442
1.446
+
1.43
9
1.508
1.
34
2
1.421
1
.
4
Chem 206
2.092
+
1.432
1.371
1.491
1.467
1.739
+
1.442
1.668
Cl
1.432
1.422
Cl
1.725
1.467 1.495
+
1
.
8
5
5
1.621
98.2
1.622
1.608
Nomenclat
ure:
classical
vs
nonclassic
1.503
al
1.551
CC
C
C
s
y
m
m
e
t
r
i
c
hyperconju
a
opengation
unsymmetrical l
b
r
i
d
g
i
no
n
trivalentbridging
bridging
g
increasin
g
nonclass
ical
characte
r
cla
ssi
cal
C
C
n
o
n
c
l
a
s
s
i
c
a
l
Chem 30
Substitution Reactions
Substitution (SN1)
R
Favorable
R
Me
H C
Unfavorable
Me
H
X
H2C
H
Sp hybridized Carbon
is more electronegative
Si
1.221
1.946
Si
Me
Si
Si
Me
Me
Me
CMe3
D. A. Evans, B. Breit
Chem 206
Vinyl &
Phenyl
Cations:
Highly
Unstable
Eviden
ce
sugge
sts
that
vinyl
cation
s are
linear.
orbital retains
sp character.
Additionally, the empty orbital lies
in the nodal plane of the ring,
effectively prohibiting conjugative
stabilization.
Hydride ion
OS
allyl cation
Stabilization by Phenylgroups
The Benzyl cation is
approximately as stable as a tButylcation.
affinities (HI)
+21
H3 C
CH2
276
+11
H2 C
r
i
n
R
R
HOSolv
A
s
Carbocation
Stabilization via delocalization
OTf
olv
CH
287
(CH3)3C + PhCH3
(CH3)
(CH3)3C + PhCH2Cl
(CH3
Ph
298
The
ring
geometry
opposes
rehybridization (top) so the vacant
Hydri
de
ion
affinit
ies
versu
s
Rates
of
Solvo
lysis
HI
-HI
Relative
Solvolysis
rates in 80%
EtOH, 80 C
Chem 206
Ho, Nouri, Tantillo,
JOC 2005, 70, 51395143
Me Me
HO
Me
Me
Me
Me
Me
75%
CH2
TFA, K2CO3
longfifolene
Me Me
HO
ZnBr2
NaBH3CN
94%
HO
Me
H
CH2
Me
steps
ZnBr2
longfifolene
Me
Me Me
Me
Me Me
Me
Me
Me Me
Me Me
Me
Me
FIGURE 1. Relative
energies (kcal/mol) of
stationary points for the
mechanism shown in
Scheme 2 (B3LYP/631G(d) zero-point corrected
energies in italics,
B3LYP/6-31G(d) free
energies at 0 C in bold,
and CPCM-B3LYP/631G(d) energies in water
underlined).
D. A. Evans, B. Breit
Chem 206
24
Me OTs
Me
Cl
Mek
rel
=1
OTs
O
1.517
1.478
1.222
krel = 10
1.474
CareyA, p 286
Bridgehead
Carbocation
s
1.464
1.541
Me
1.409
Me
OTs
Me
1.444
1
1.534
TsO
10-7
TsO
why so reactive?
TsO
Chem 206
"The Synthesis and Isolation of Stable Hypervalent Carbon Compound (10-C-5) Bearing a 1,8-Dimethoxyanthrecene Ligand"
Akibe, et al. JACS 1999, 121, 10644-10645
Me MeO
CO Me
OMe
OMe
Me
OMe
Me3O BF4
O C
B F
2
"The relevant CO distances are longer than a covalent CO bond (1.43 ) but shorter than
the sum of the van der Waals radii (3.25 )."
2.428
1.483
2.428
2.452
2.45
2
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