Silver-catalyzed three-component reaction of phenyldiazoacetate with arylamine and imine

Article abstract of DOI:10.1016/S1872-2067(18)63088-8

A new method was developed to diastereoselectively synthesize polysubstituted 1,2-diamine compounds from the reaction of diazoesters with arylamines and diaryl imines by using the dioxazoline ligand L₂-ligated silver catalyst. The Lewis acidity of the silver catalyst affected the different types of substrate diastereoselectivities; It also led to the formation of amine-exchange side products.

Full text of DOI:10.1016/S1872-2067(18)63088-8

Chinese Journal of Catalysis 39 (2018) 1594–1598
a v a i l a b l e a t w w w . s c i e n c e d i r e c t . c o m
j o u r n a l h o m e p a g e : w w w . e l s e v i e r . c o m / l o c a t e / c h n j c
Communication
Silver‐catalyzed three‐component reaction of phenyldiazoacetate
with arylamine and imine
Bai‐Ling Chena,b,Zhen Wanga, You‐Can Zhanga, Zhi‐Gang Zhaob,#, Zili Chena,*
a Department of Chemistry, Renmin University of China, Beijing 100872, China
b College of Chemistry & Environment Protection Engineering, Southwest University for Nationalities, Chengdu 610041, Sichuan, China
A R T I C L E I N F O
A B S T R A C T
Article history:
A new method was developed to diastereoselectively synthesize polysubstituted 1,2‐diamine com‐
pounds from the reaction of diazoesters with arylamines and diaryl imines by using the dioxazoline
ligand L2 ‐ligated silver catalyst. The Lewis acidity of the silver catalyst affected the different types of
substrate diastereoselectivities; It also led to the formation of amine‐exchange side products.
© 2018, Dalian Institute of Chemical Physics, Chinese Academy of Sciences.
Received 26 March 2018
Accepted 23 April 2018
Published 5 October 2018
Published by Elsevier B.V. All rights reserved.
Keywords:
Silver catalysis
Carbene transfer reaction
Three‐component reaction
Ammonium ylide
Diamine compouds
The metal‐catalyzed carbene‐transfer reaction of diazo
compounds has become an important synthetic tool in organic
synthesis [1,2]. In this field, the reactions of cyclopropanation,
X–H (X = C, N, O, Si, S) insertion, and carbonyl/imine ylide cy‐
cloaddition have been extensively investigated in the past dec‐
ades. In 2003, Hu and his colleagues described a new type of
reaction, in which the seemingly unstable ammonium ylides
could be trapped with imine, giving 1,2‐diamines with a high
diastereoselectivity (Eq. (3), Scheme 1) [3–7]. In their subse‐
quent research, ammonium ylides and oxonium ylides inter‐
mediates [8,9] were found to undergo nucleophilic addition
onto a series of suitable electrophiles, such as ketone [10], al‐
dehyde [11,12], β, γ‐unsaturated α‐ketoester [13,14], and
azodicarboxylate [15]. These diazo compound reactions were
usually mediated through rhodium (III) catalysis [16–19].
Our group have recently reported that silver salts could be
utilized as a catalyst to mediate the carbene transfer reaction of
diazo compounds for the synthesis of oxirane molecules
through the [2+1] cycloaddition of the diazo compounds with
aldehydes
(Eq.
(1),
Scheme
1)
[20],
and of
2,5‐dihydrofurans/tetrahydrofurans through the [2+2+1] cy‐
cloaddition of the diazo compounds with aldehydes and al‐
kyne/olefin dipolarophiles (Eq. (2), Scheme 1) [21]. As a con‐
tinuation of our previous research, we herein explore the silver
(I)‐catalyzed three‐component reactions of phenyl diazoacetate
with arylamine and imine, which provide a series of polysub‐
stituted 1,2‐diamine derivatives in moderate to good yields
[22–25].
The reaction of methyl phenyldiazoacetate 1a with phe‐
nylamine 2a and 4‐nitrophenyl‐N‐phenylmethanimine 3a was
chosen as the model system for our initial investigation. Fol‐
lowing our previous procedure, the combination
IPrAgCl/AgOTf was utilized as the catalyst. As shown in Table
1, a mixture of 1a (0.1 mmol), 1.2 mol equiv. of 2a and 6 mol
* Corresponding author. Tel/Fax: +86‐10‐62516660; E‐mail: zilichen@ruc.edu.cn
# Corresponding author. E‐mail: zzg63129@163.com
This work was supported by the National Natural Science Foundation of China (21472237).
DOI: 10.1016/S1872‐2067(18)63088‐8 | http://www.sciencedirect.com/science/journal/18722067 | Chin. J. Catal., Vol. 39, No. 10, October 2018

Bai‐Ling Chen et al. / Chinese Journal of Catalysis 39 (2018) 1594–1598
1595
Fig. 1. The X‐Ray structure of compound 4aa.
Scheme 1. Ag(I) and Rh(III) mediated carbene transfer reaction.
Table 1
3S*) configuration, as determined by its X‐ray chromatograph,
shown in Fig. 1 [26].
Silver‐mediated ammonium ylide trapping reaction with
Further optimization of the reaction conditions was then
performed. It was found that the removal of IPrAgCl (no IPr
ligand condition) would reduce the yield of 4a (Table 1, entry
2). After solvent screening (Table 1, entries 3–6), DCM was
found to be the best reaction medium. The effect of molecular
sieves was tested, 10 mg of the 4‐Å molecular sieve additive
was the optimal amount (Table 1, entry 7and 8). Except for IPr,
other ligands were explored. Both PPh3 and the dioxazoline
ligand L1 proved to be inferior to IPr (Table 1, entries 9 and
10). Luckily, L2‐ligated silver salts afforded the desired product
4aa in a high yield (Table 1, entry 11). However, the tricoordi‐
nated L3 proved to be a poor ligand (Table 1, entry 12). Utiliz‐
ing L2 as the ligand, various silver salts were scrutinized, in
which the AgOTf activity is much better than those of the other
silver salts (Table 1, entries 13–19). In addition, raising or low‐
ering the reaction temperature was found to be ineffective (Ta‐
ble 1, entries 20 and 21).
4‐nitrophenyl‐N‐ phenylmethanimine 3a.a
Ag catalyst
(mol%)
IPrAgCl (5)
AgOTf (5)
Additive
(mol%)
AgOTf (5)
None
Solvent/
4Å MS(mg)
DCM/50
Yield of
4aa/5a b (%)
33/26
Entry
1
2
DCM/50
18/31
3
4
5
6
7
8
IPrAgCl (5)
IPrAgCl (5)
IPrAgCl (5)
IPrAgCl (5)
IPrAgCl (5)
IPrAgCl (5)
AgOTf (5)
AgOTf (5)
AgOTf (5)
AgOTf (5)
AgNTf2 (5)
AgSbF6 (5)
AgPF6 (5)
AgBF4 (5)
AgClO4 (5)
Ag2O (5)
AgOTf (5)
AgOTf (5)
AgOTf (5)
AgOTf (5)
AgOTf (5)
AgOTf (5)
PPh3 (5)
L1 (5)
L2 (5)
L3 (5)
L2 (5)
L2 (5)
CHCl3/50
DCE/50
Toluene/50
Dioxane/50
DCM/10
DCM/0
22/25
20/23
11/23
5/16
60/21
42/15
19/27
41/18
91/5
<5/14
88/11
51/17
17/25
45/14
69/12
NR
With the optimized reaction conditions determined, the
various substrate scopes were then explored. As shown in Ta‐
9
DCM/10
DCM/10
DCM/10
DCM/10
DCM/10
DCM/10
DCM/10
DCM/10
DCM/10
DCM/10
DCM/10
DCM/10
DCM/10
10
11
12
13
14
15
16
17
18
19
20 c
Table 2
Ammonium ylide trapping reaction of various diazo esters via silver
catalysis a, b, c
.
NO2
N2
Ag(I), L2,
CH2Cl2
PhHN
Ar
L2 (5)
L2 (5)
L2 (5)
L2 (5)
L2 (5)
L2 (5)
2a
3a
+
+
Ar
COOMe
NHPh
MeOOC
H
1
4
NO2
NO2
NO2
R
Ag2CO3 (5)
AgOTf (5)
AgOTf (5)
NR
47/15
21 d
NHPh
H
NHPh
H
NHPh
H
L2 (5)
65/13
EtOOC
MeOOC
EtOOC
PhHN
PhHN
PhHN
a Unless noted, all reactions were carried out on 0.1 mmol scale in 2 mL
solvent at room temperature. b The reaction yields were determined by
1H NMR spectral data. c The reaction was performed at 0 °C. d The reac‐
tion was performed at 40 °C. In Table 1 scheme, 4aa, 5a, L2 and L3
structures only show relative configurations.
4da, R=EtO, 84% yield,
dr = 27/1
4ea, R=MeO, 85% yield,
4ba, 83% yield
dr = 25/1
4ca, 95% yield
dr = 24/1
dr = 22/1
NO2
NO2
NO2
F
S
NHPh
NHPh
NHPh
EtOOC
PhHN
EtOOC
PhHN
MeOOC
H
H
H
equiv. of 3a in CH2Cl2 was treated with 5 mol% equiv. of
IPrAgCl/AgOTf using 50‐mg 4‐Å molecular sieves. We found
that the diamine product 4aa could be obtained in 33% yield,
together with the N–H insertion product 5a (26% yield, Table 1,
entry 1). The diastereoselectivity of 4aa was very high (dr =
20/1).
PhHN
4fa, 70% yield
dr = 29/1
4ga, 55% yield
dr = 19/1
4ha, 37% yield
dr = 10/1
Unless noted, all reactions were carried out on 0.1 mmol scale in 2 mL
solvent at room temperature with the addition of 10‐mg 4‐Å molecular
sieves. Isolated yields. c The dr values were determined by H NMR
spectral data of the crude product. In Table 2, the 4ba–4ha structures
only show their relative configurations.
b
1
The relative stereochemistry of 4aa was found to be a (2S*,

1596
Bai‐Ling Chen et al. / Chinese Journal of Catalysis 39 (2018) 1594–1598
ble 2, a series of diazo esters were investigated by using phe‐
nylamine 2a and 4‐nitrophenyl‐N‐phenylmethanimine 3a as
the ammonium ylide trapping partner. The ethyl phenyldiazo‐
acetate ester 1b behaved like methyl ester 1a, giving 4ba in
83% yield with dr = 25/1 (Table 2). Different phenyl substitu‐
tion patterns were tested, in which the electro‐rich substituents
(Table 2, 4ca–4ea) performed better than the electro‐poor an‐
alogs (Table 2, 4fa). The bulky 2‐naphthalenyl diazoester and
heteroaromatic 2‐thiophenyl diazo ester were also investigat‐
ed, providing the desired diamine products 4ga and 4ha in
moderate yields with high diastereoselectivities (Table 2) [27].
Then, various amine and imine substrates were investigat‐
ed. It was found that an amine exchange could occur between
the amine and imine substrates. In order to avoid the formation
of an amine‐exchanging side product, the same amine subunit
(Ar1NH2) was employed in the amine substrate 2 and imine
substrate 3 (Table 3). It has been proposed that the imine sub‐
strates act as ammonium ylide trapping reagents. Thus, its
electrophilicity might affect the result of this three‐component
coupling reaction. As shown in Table 3, when the highly elec‐
trophilic imines, derived from p‐nitro benzaldehyde, were uti‐
lized, the reactions of 1a with different amine substrates, such
as p‐fluoro, p‐chloro and p‐trifluoromethyl amines, provided
diamine products 4ab–4ad in moderate yields with high dia‐
stereoselectivities, which were higher than that of Rh(III) ca‐
talysis (Table 3) [3].
separated in 31% yield, with dr = 2/1 (Table 3).
Then, the amine‐exchange process was explored in the sil‐
ver‐mediated ammonium ylide trapping reaction. As shown in
Scheme 2, when the p‐fluorophenyl amine 2b was utilized to
react with the diazo ester 1a and imine 3a, two ammonium
ylide trapping adducts 4ah and 4aa were synthesized, in which
the normal coupling adduct 4ah was obtained in only 23%
yield (Scheme 2, Eq. (3)). It was obvious that an amine ex‐
change reaction occurred between 2b and 3a, which led to the
formation of the amine exchange coupling product 4aa [29].
Similarly, in the reaction of the p‐trifluoromethylphenyl amine
2d, both 4am and amine‐exchange product 4aa could be sepa‐
rated from the Ag(I)/L2 mediated reaction (Scheme 2, Eq. (4)).
As a comparison, the Rh(III) catalyst was used to catalyze the
reactions in Eqs. (3) and (4), in which an amine‐exchange
product 4aa could also be obtained, though with relatively low
yields (Scheme 2).
Then, we explored the asymmetric three‐component reac‐
tion by using the chiral ligand (R)‐L2, however, no enantiose‐
lectivity was obtained in the reaction shown in Eq. (5) (Scheme
3). In the N‐H insertion reaction, only 11% ee was obtained (Eq.
(6), Scheme 3).
The mechanism of the Ag(I)‐catalyzed ammonium ylides
trapping reaction was then discussed. Based on previous re‐
search, a process of the nucleophilic addition of ammonium
ylides onto electrophilic imines would be involved, in which the
product diastereoselectivities are determined by intermolecu‐
lar hydrogen bonding between the ArNH2 group and the imine
nitrogen atom, and the π‐π interactions of the phenyl group[3].
Because of the Lewis acidity of the Ag(I) salt, we considered
that an additional intermolecular silver coordination might be
However, when the less electrophilic p‐trifluoromethyl
phenyl substituted imine 3e was utilized, two diamine dia‐
stereomers 4ae and 4ae’ could be obtained in 43% yield, with
dr = 1.5/1 (Table 3) [28]. Similarly, the reaction of the unsub‐
stituted diphenyl imine 3f afforded the two diastereomers 4af
and 4af’ with a relatively low diastereoselectivity (4af/4af’=
3/1, Table 3). In the reaction of the p‐methyl diphenyl imine 3g,
the corresponding diamine diastereomers 4ag and 4ag’ were
NO2
NO2
Ag(I), L2,
CH2Cl2
1a
+
F
NH2
+
3a
+
(3)
NHPh
H
MeOOC
NHPh
NH
MeOOC
PhHN
H
F
Table 3
2b
4ah
4aa
Silver‐mediated ammonium ylide trapping reaction by using the same
Ag(I), L2
Rh(OAc)2, reflux
23 % yield
42 % yield
41 % yield
12 % yield
Ar1 unit in the amine and imine substratesa, b, c
.
NO2
NO2
Ar1
Ar2
NHAr1
Ar1HN
hp
N
Ag(I), L2,
CH2Cl2
1a
+
Ar1 NH2
+
CH2Cl2
1a
+
F3C
NH2
+
3a
+
Ar2
NHPh
H
(4)
MeOOC
MeOOC
H
NHPh
NH
MeOOC
2
3
4
H
PhHN
F3C
NO2
NO2
NO2
NH
2d
4ai
4aa
Ag(I), L2
Rh(OAc)2, reflux
28% yield
36% yield
28% yield
18% yield
MeOOC
MeOOC
MeOOC
NH
NH
Scheme 2. Amine exchange process involved in the
H
H
H
NH
F3C
NH
F
NH
Cl
Ag(I)/Rh(III)‐mediated ammonium ylide trappingreaction.
CF3
F
Cl
4ab, 69% yield
dr = 27/1
4ac, 73% yield
dr = 25/1
4ad, 68% yield
dr = 19/1
CF3
MeOOC
MeOOC
NH
MeOOC
NH
NH
H
NH
H
NH
H
NH
Ag(I): (4ae+4ae'), 43%
yield, dr = 1.5/1
Ag(I): (4af+4af'),
51% yield, dr = 3/1
Ag(I): (4ag+4ag'),
31% yield, dr = 2/1
a Unless noted, all reactions were carried out on 0.1 mmol scale in 2 mL
CH2Cl2 at room temperature with the addition of 10‐mg 4‐Å molecular
b
1
sieves. Isolated yields. c The dr values were determined from the H
NMR spectral data of the crude product. The product 4ab–4ag struc‐
tures only show their relative configurations.
Scheme 3. Exploring the asymmetric three‐component reaction and
the N–H insertion reaction.

Bai‐Ling Chen et al. / Chinese Journal of Catalysis 39 (2018) 1594–1598
1597
er enantioselectivities for the reactions of less electrophilic
substrates. Moreover, it was found that the dioxazoline L2 lig‐
and greatly enhanced the Ag(I) catalytic activities in the car‐
bene transfer reaction. The detailed research of the sil‐
ver‐catalyzed ammonium ylide trapping reaction and its fur‐
ther application is ongoing in our laboratory and will be re‐
ported in due course.
L2
Ag
O
Ph
OMe
H
L2Ag
O
OMe
H
O
N
N
O
H
H
N
Ar
N
Ph
Ph
Ph
Ar
N
H
H
R
R = NO2, CF3, H, CH3
Favored
Unfavored
Supplementary data
Scheme 4. Plausible transition state for ammonium ylide trapping
reaction.
Supplementary data associated with this article include: a
brief experimental details, and spectral data for all new prod‐
ucts and NOESY spectra for compound 4aa is available free of
charge via the Internet.
involved, which led to the high diastereoselectivity of
p‐nitrophenyl imine in the Ag(I)‐mediated reaction (favored
transition state, Scheme 4). When other imine substrates, such
as p‐trifluoromethylphenyl, p‐methylphenyl and unsubstituted
phenyl imines, were tested, poor diastereoselectivities were
observed, possibly because of the coordination of silver salts
with the imine nitrogen atom (unfavored transition state,
Scheme 4). In addition, the amine exchange process between
the amine and imine substrates might also be a result of the
Lewis acidity of the Ag(I) salt, leading to the amine‐exchange
three‐component reaction.
In summary, we have reported the first example of the
Ag(I)‐catalyzed three‐component reaction of a diazo ester with
arylamine and diaryl imine by using dioxazoline L2 as the lig‐
and to synthesize a series of polysubstituted 1,2‐diamine com‐
pounds in moderate to good yields. The Lewis acidity of Ag(I)
affected the diastereoselectivities of the 1,2‐diamine molecule,
and led to the formation of amine‐exchange diamine adducts.
Compared with the previously reported Rh(III)‐mediated reac‐
tion, the silver catalyst performed better for the reactions of the
p‐nitrophenyl imine substrates, while providing relatively low‐
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Graphical Abstract
Chin. J. Catal., 2018, 39: 1594–1598 doi: 10.1016/S1872‐2067(18)63088‐8
Silver‐catalyzed three‐component reaction of
phenyldiazoacetate with arylamine and imine
Bai‐Ling Chen,Zhen Wang, You‐Can Zhang, Zhi‐Gang Zhao *,
Zili Chen *
Renmin University of China; Southwest University for Nationalities
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1
(from the 5 mmol scale reaction) and characterized by using H
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银催化重氮酯与苯胺, 亚胺的三组分反应
陈佰灵a,b, 王 振a, 张有灿a, 赵志刚b,#, 陈自立a,*
a中国人民大学化学系, 北京100872
b西南民族大学化学与环境保护工程学院, 四川成都610041
摘要: 过渡金属催化重氮化合物的卡宾转移反应是有机合成反应的重要研究对象. 在这一类反应中, 包括环丙烷化、X-H
(X = C, N, O, Si, S)插入以及羰基/亚胺叶立德环加成等反应得到了广泛的研究. 2003年, 胡文浩和Doyle课题组报道了一种
新型的反应, 即亚胺捕获看似不稳定的氨基叶立德中间体, 合成具有高非对映选择性的1,2-二胺化合物. 之后, 他们又报道
了一系列有关氨基叶立德和氧叶立德的研究, 与不同的捕获剂, 如酮, 醛, β, γ-不饱和α羰基羧酸酯和偶氮二酸酸酯等发生
反应, 生成多种多样的产物类型, 基本上都是采用Rh(III)催化剂. 迄今为止, 没有采用其他类型的过渡金属催化剂的报道.
最近, 本课题组研究发现, 银盐可以作为重氮化合物卡宾转移反应的催化剂, 实现了重氮化合物与醛的[2+1]环加成反
应合成环氧乙烷类化合物, 及重氮化合物与醛、炔/烯三组分的[2+2+1]环加成反应合成二氢呋喃/四氢呋喃类化合物, 在这
些反应中, 加入不同的配体可以调节Ag(I)催化剂的催化活性, 从而实现不同的反应过程. 基于此, 本文将探索Ag(I)做催化
剂催化重氮化合物与芳基胺及亚胺的三组分反应合成一系列1,2-二胺类化合物.
研究发现, 采用AgOTf/ 双噁唑啉配体配体作为催化剂组合, 可以顺利地实现Ag(I)催化重氮酯、芳基胺及亚胺的三组分
反应. 尝试了不同的配体, 包括膦配体、卡宾配体以及双噁唑啉配体, 最后发现, 双噁唑啉配体配位的Ag(I)催化反应的效果
最好, 极大地提高了Ag(I)催化剂的催化活性, 其具体的作用机理值得进一步研究. 反应中, Ag(I)催化剂的Lewis酸性对二胺
产物的非对映选择性有较大的影响. 其中, 在对硝基苯基亚胺的反应中, 产物的非对映选择性很高, 大于铑催化反应的结
果；而在其他类型亚胺的反应中, 反应的非对映选择性较差. 另一方面, 由于Ag(I)的Lewis酸性, 反应过程中发生亚胺与芳
基胺的氨基交换反应, 从而导致氨基交换的二胺副产物的生成. 本文对不同反应底物的各种效应进行了比较详细的研究.
关键词: 银催化; 卡宾转移反应; 三组分反应; 铵基叶立德; 二胺化合物
收稿日期: 2018-03-26. 接受日期: 2018-04-23. 出版日期: 2018-10-05.
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基金来源: 国家自然科学基金(21472237).
本文的电子版全文由Elsevier出版社在ScienceDirect上出版(http://www.sciencedirect.com/science/journal/18722067).