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Journal ArticleDOI

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

17 Jun 2003-ChemInform (WILEY‐VCH Verlag)-Vol. 34, Iss: 24

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.
Topics: Diazo (69%), Tosyl (53%), Nucleophile (51%)

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S1
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

S3
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

S4

S5

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Abstract: For many years diazocarbonyl compounds have been studied due to their versatility and usability in many chemical transformations. In this review, we summarize the traditional methods to prepare these compounds as well as the new methods and recent improvements in experimental procedures. Moreover, emergence of continuous flow techniques has allowed safer and environmentally friendly procedures for the handling of diazomethane and diazo compounds and will also be a topic in this review

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  • ...The base-mediate addition of diazocarbonyls to electron-deficient imines such as N-acyl, N-tosyl and N-sulfonyl imines has also been reported to provide the corresponding β-amino α-diazo carbonyl derivatives (Jiang et al. 2003, Zhao et al. 2004, 2005, Zhao and Wang 2005) (Figure 48)....

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Abstract: 1,2-Shift or 1,2-migration reaction is one of the most common reactions of the organic intermediates-carbocation, free radical, carbanion, free carbene and metal carbene. Although the 1,2-migration reactions for the former four intermediates have been comprehensively studied, there has been no systematic investigation for the corresponding reaction of metal carbene. We have studied the 1,2-migration of Rh(II) carbene and observed remarkable substituent effect. This paper will present a general review of the 1,2-shift reactions.

References
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Journal ArticleDOI
Nan Jiang1, Zhihua Ma1, Zhaohui Qu1, Xiaoyu Xing1  +2 moreInstitutions (1)
TL;DR: It was found that, in most cases, the diazo decomposition gave preferentially 1, 2-aryl migration product, but 1,2-hydride migration predominated when PhCO(2)Ag/Et(3)N was the catalytic system.
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.

59 citations