Chemistry Reference
In-Depth Information
Table 7 POAV pyramidalization angles and bowl depths of sumanene and its derivatives
Compound
POAV (deg)
a
)
b
G
{
inv
(kcal/mol)
Bowl depth (
ʔ
References
Å
19.6, 20.4
c
2
8.8
1.11
[
134
,
136
,
137
]
118 (R
¼
C
3
H
5
)
-
-
19.2
[
137
]
118 (R
¼
MB
d
)
-
-
18.2
[
137
]
123
9.6
1.24
-
[
140
]
129
9.1, 8.6
1.11
21.6
[
145
,
152
]
131
-
-
23.3, 21.5 (calcd.)
[
149
]
132
6.3
0.79
-
[
150
]
133
0.23
-
[
151
]
139
10.8, 9.8
1.30
42.2, 39.9 (calcd.)
[
153
]
a
POAV angles at the hub six carbons of the sumanenes, and the values obtained by averaging the
POAV angles of symmetry-related carbon atoms of sumanenes
b
The bowl depth is gauged from the distance between hub and rim planes
c
Determined by 117 (E
¼
D)
d
MB
4-methoxybenzyl
O
R
R
O
N
N
R
Pd(OAc)
2
Bu
4
NOAc
PPh
3
,Na
2
CO
3
dioxane, 100 ºC
57%
R
I
N
O
N
1) HCl, HOAc, 60 ºC
2) C
6
F
5
OP(=O)Ph
2
HN(
i
-Pr)
2
,DMF
0to60ºC
59%
O
N
O
R
134
N
O
N
135
R
136
R
R=
p
-MeOC
6
H
4
CH
2
O
SMe
SMe
N
N
1) Lawesson's reagent
C
2
H
4
Cl
2
,
m
w, 160 ºC
Ph
3
CBF
4
DTBMP
N
N
2) CF
3
CO
2
H,
m
w, 100 ºC
3) MeI, K
2
CO
3
,DMF,30ºC
CH
2
Cl
2
,25ºC
MeS
MeS
73%
64%
N
SMe
N
SMe
137
138
SO
2
Me
N
S
MeO
P
SP
S
m
-CPBA
N
OMe
CH
2
Cl
2
0to15ºC
MeO
2
S
S
t
-Bu
N
t
-Bu
90%
Lawesson's reagent
DTBMP
N
SO
2
Me
139
Scheme 43 Synthesis of triazasumanenes [
153
]
