Investigation of the Transition‐Metal‐ and Acid‐Catalyzed Reactions of β‐(N‐Tosyl)amino Diazo Carbonyl Compounds.

TLDR: In this article, a series of β-(N-tosyl)amino diazo carbonyl compounds have been prepared by nucleophilic condensation of N -tosylimines with acyldiazomethanes.

Abstract: A series of β-(N-tosyl)amino diazo carbonyl compounds have been prepared by nucleophilic condensation of N-tosylimines with acyldiazomethanes. The diazo decomposition of these diazo carbonyl compounds under various catalytic conditions, including Rh(II) carboxylates, Cu(I) and Cu(II) complexes, PhCO2Ag/Et3N, TsOH, and SnCl2·2H2O, has been investigated. It was found that, in most cases, the diazo decomposition gave preferentially 1,2-aryl migration product, but 1,2-hydride migration predominated when PhCO2Ag/Et3N was the catalytic system. Hammett correlation has been applied in the analysis of the electronic effects of 1,2-aryl migration. The factors that govern the migratory preference and the mechanistic aspects of the reaction are discussed.

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Supporting Information
Investigation on the Transition Metal and Acid Catalyzed Reaction
of β–(N-Tosyl)amine Diazo Carbonyl Compounds
Nan Jiang, Zhihua Ma, Zhaohui Qu, Xiaoyu Xing, Linfeng Xie and Jianbo Wang*
Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education,
Department of Chemical Biology, College of Chemistry, Peking University, Beijing 100871, P. R. China,
Ar OEt
ONTs
H
N
2
H
TsN
OEt
OH
Ar
H
AgO
2
CPh
Et
3
N
Ar
OEt
O
H
H
major
major
Rh
2
(OAc)
4
or TsOH
NTs

S2
Table S1.
Relative Migratory Aptitude in the Reaction Catalyzed by Rh
2
(OAc)
4
Entry
N
-Tosyl
α−
diazo- Product ratio
k
H
/
k
X
log
k
H
/
k
X
ketamines
10 : 11 : 12
1
5a
(C
6
H
5
-) 85 : 3 : 12 1 0
2
5b
(
p
-MeOC
6
H
4
-) 84 : 9 : 7 1.83 0.26
3
5c
(
m
-BrC
6
H
4
-) 73 : 5 : 22 0.046 -0.33
4
5d
(
m
-CF
3
C
6
H
4
-) 62 : 5 : 33 0.27
-0.57
5
5e
(
m
-CNC
6
H
4
-) 51 : 6 : 47 0.18
-0.75
6
5f
(
p
-PhC
6
H
4
-) 92 : 4 : 4 2.92
0.47
7
5g
(
p
-FC
6
H
4
-) 93 : 3 : 4 3.21
0.51
8
5h
(
p
-ClC
6
H
4
-) 75 : 12 : 13 0.92
-0.038
Figure S1. Hammett correlation of relative migratory Figure S2. Hammett correlation of relative migratory
aptitude of Rh
2
(OAc)
4
-catalyzed reaction with σ+ aptitude of Rh
2
(OAc)
4
-catalyzed reaction with σ-
k
X
{[
10
+
11
]/[
12
]}
X
=
k
H
{[
10
+
11
]/[
12
]}
H
-1.0 -0.8 -0.6 -0.4 -0.2 0.0 0.2 0.4 0.6 0.8 1.0
-1.0
-0.8
-0.6
-0.4
-0.2
0.0
0.2
0.4
0.6
0.8
1.0
Rh
2
(OAc)
4
ρ
= -0.85
r = -0.78
lg k
X
/k
H
σ
+
-0.4 -0.2 0.0 0.2 0.4 0.6
-1.0
-0.8
-0.6
-0.4
-0.2
0.0
0.2
0.4
0.6
0.8
1.0
Rh
2
(OAc)
4
ρ = -1.47
r = -0.88
lg k
X
/k
H
σ
−

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Table S2.
Relative Migratory Aptitude in the Reaction Catalyzed by AgO
2
CPh/Et
3
N
Entry
N
-Tosyl
α−
diazo- Product ratio
k
H
/
k
X
log
k
H
/
k
X
ketamines
10 : 11 : 12
1
5a
(C
6
H
5
-) 27 : 16 : 57 1 0
2
5b
(
p
-MeOC
6
H
4
-) 16 : 25 : 59 0.92 -0.036
3
5c
(
m
-BrC
6
H
4
-) 14 : 25 : 61 0.96 -0.018
4
5d
(
m
-CF
3
C
6
H
4
-) 10 : 27 : 63 0.96
-0.018
5
5e
(
m
-CNC
6
H
4
-) 10 : 22 : 68 0.85
-0.072
6
5f
(
p
-PhC
6
H
4
-) 21 : 21 : 58 0.77 -0.11
7
5g
(
p
-FC
6
H
4
-) 17 : 25 : 58 0.62 -0.20
Figure S3. Hammett correlation of relative migratory Figure S4. Hammett correlation of relative migratory
aptitude of
AgO
2
CPh/Et
3
N
-catalyzed reaction with σ+ aptitude of
AgO
2
CPh/Et
3
N
-catalyzed reaction with σ-
-0.8 -0.6 -0.4 -0.2 0.0 0.2 0.4 0.6 0.8
-0.3
-0.2
-0.1
0.0
0.1
0.2
0.3
PhCO
2
Ag / Et
3
N
ρ
= -0.11
r = -0.67
lg k
X
/k
H
σ
+
-0.4 -0.2 0.0 0.2 0.4 0.6 0.8 1.0 1.2
-0.3
-0.2
-0.1
0.0
0.1
0.2
0.3
PhCO
2
Ag / Et
3
N
ρ
= -0.20
r = -0.83
lg k
X
/k
H
σ
−
k
X
{[10+11]/[12]}
X
=
k
H
{[10+11]/[12]}
H

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