Counteranion-controlled regioselectivity in palladium-catalyzed allylic amination of dienyl allylic carbonates

Article abstract of DOI:10.1016/j.tet.2021.131996

A regioselective Pd-catalyzed allylic amination reaction of dienyl allylic carbonates and aromatic amines has been developed by means of phosphoramidite-palladium catalysis. The regioselectivity could be altered by the counterion of the π-allylpalladium intermediate. As a result, either branched Z-dienyl allylic amines or linear conjugated allylic amines were generated in high levels of regioselectivity from the same substrates by tuning the reaction conditions.

Full text of DOI:10.1016/j.tet.2021.131996

Tetrahedron 84 (2021) 131996
Contents lists available at ScienceDirect
Tetrahedron
journal homepage: www.elsevier.com/locate/tet
Counteranion-controlled regioselectivity in palladium-catalyzed
allylic amination of dienyl allylic carbonates
,
, b, **
Meng-Lan Shen a, Pu-Sheng Wang a *, Liu-Zhu Gong a
a Hefei National Laboratory for Physical Sciences at the Microscale and Department of Chemistry, University of Science and Technology of China, Hefei,
230026, PR China
b Center for Excellence in Molecular Synthesis of CAS, Hefei, 230026, China
a r t i c l e i n f o
A
b s t r a c t
Article history:
A regioselective Pd-catalyzed allylic amination reaction of dienyl allylic carbonates and aromatic amines
has been developed by means of phosphoramidite-palladium catalysis. The regioselectivity could be
Received 19 December 2020
Received in revised form
28 January 2021
Accepted 31 January 2021
Available online 13 February 2021
altered by the counterion of the
p-allylpalladium intermediate. As a result, either branched Z-dienyl
allylic amines or linear conjugated allylic amines were generated in high levels of regioselectivity from
the same substrates by tuning the reaction conditions.
© 2021 Elsevier Ltd. All rights reserved.
Keywords:
Palladium catalysis
Allylic amination
Regioselectivity
Phosphoramidite
Allylic amine
1. Introduction
reaction temperature and reaction time. [5]. Then, Trost and co-
workers found that the nucleophile counterion held profound ef-
The palladium-catalyzed allylic substitution reaction is one of
the most powerful tools for efficient assembly of carbon-carbon
and carbon-heteroatom bonds. [1]. These reactions generally pro-
fect on the regioselectivity. [6]. Interestingly, Hou and coworkers
demonstrated that the use of 1,10-P,N-ferrocene derived ligands was
able to alter the C-3/C-5 regioselectivity. [7]. To the best of our
knowledge, a controllable C-1/C-5 regioselectivity in Pd-catalyzed
allylic substitution of dienyl allylic substrates has not been
described, yet.
ceed via a (p-allyl)palladium intermediate, on which the nucleo-
phile can attack at either of terminus to principally provide two
regioisomeric allylation products. [2]. In the past few decades,
significant efforts have been made to regulate the regioselectivity
in the Pd-catalyzed allylic substitution reaction. [3]. However, much
less attention has been paid to the regioselectivity issue in the
allylic substitution of dienyl allylic substrates [4], wherein the
Allylic amines are not only widely amenable building blocks in
organic synthesis [8], but also motifs frequently appearing within
many biologically active natural products and pharmaceuticals. [9].
Based on our recent work on the palladium-catalyzed allylic CeH
functionalization of 1,4-dienes [10], in which the geometry and
coordination pattern of nucleophiles were identified to vary the
bond-forming transition states and thereby to determine the E/Z-
and regioselectivities [10h,10j], we hypothesized that these mech-
anistic features might be viable to the Pd(0)-catalyzed allylic ami-
nation reactions, providing the insight into the access of versatile
allylic amine regioisomers. Herein, we will report a palladium-
catalyzed regiocontrollable allylic amination reaction of dienyl
allylic carbonates and amines, giving rise to either C-5-selective
thermodynamic unfavored Z-dienyl allylic amines with
palladium-phosphoramidite catalyst [11] or C-1-selective allylic
amines by virtue of phosphoric acid as a co-catalyst (Scheme 1B).
nucleophilic attack at C-1, C-3 and C-5 of the vinyl (p-allyl)palla-
dium intermediate is principally possible to afford three
€
regioisomers (Scheme 1A). At the early stage, Backvall and co-
workers disclosed that the C-1/C-3 regioselectivity in the reaction
of dienyl acetates with dialkyl malonates mainly depended on
* Corresponding author.
** Corresponding author. Hefei National Laboratory for Physical Sciences at the
Microscale and Department of Chemistry, University of Science and Technology of
China, Hefei, 230026, PR China.
E-mail addresses: pusher@ustc.edu.cn (P.-S. Wang), gonglz@ustc.edu.cn
(L.-Z. Gong).
https://doi.org/10.1016/j.tet.2021.131996
0040-4020/© 2021 Elsevier Ltd. All rights reserved.

M.-L. Shen, P.-S. Wang and L.-Z. Gong
Tetrahedron 84 (2021) 131996
Table 1
Optimization of reaction conditions.a
entry
L
HeB
3a (%)b,c
4a (%)b
5a (%)b
Scheme 1. Regioselectivity in the Pd-catalyzed allylic substitution reaction of dienyl
allylic substrates.
1
2
3
4
5
6
7
8
9
L1
L2
L3
L4
L5
L5
L5
L5
L5
L6
e
<1
<1
11
95
<1
<1
20
15
<1
<1
<1
<1
6
e
47d
33e
<1
e
2. Results and discussion
e
e
99 (91f)
<1
<1
17
16
HOAc
Our initial investigation focused on evaluating phosphorus-
based ligands for the reaction of (E)-methyl undeca-1,4-dien-3-yl
carbonate 1a and aniline 2a by using Pd(dba)2 (5 mol%) as pre-
catalyst in THF at 25 ꢀC (Table 1). In the presence of P,N-ligand L1
[12], none of the corresponding allylation products was observed
(entry 1). Performing the reaction with either the Trost modular
ligand L2 [13] or phosphoramidite ligand L3 mainly furnished C-1-
selective product 4a in accompany with linear bis-allylation prod-
uct 5a (entries 2e3). To our delight, the use of bulkier phosphor-
amidite ligands L4 and L5 [11b] (entries 4e5) with sterically
demanding 3,30,5,50-substituents at the biphenyl backbone
smoothly afforded a C-5 and Z-selective product 3a in excellent
yields and with high levels of Z/E and regioselectivities. To our
surprise, the addition of a Brønsted acid as cocatalyst (entries 6-9)
obviously altered the regioselectivity mainly to generate the linear
product 4a, and Ph2PO2H was superior to afford 4a in 65% yield.
Furthermore, fine-tuning of the amine moiety of the phosphor-
amidite ligand with a bulkier substituent offered an enhanced yield
of 4a, albeit accompanying with the formation of a small amount of
bis-allylation product 5a (entry 10).
Under the optimized reaction conditions, the generality with
respect to amines was explored (Scheme 2). A wide range of pri-
mary and secondary aromatic amines 2 were nicely tolerated to
afford either branched Z-dienyl products 3 under Conditions A or
linear product 4 under reaction Conditions B. Either electron-
donating or electron-withdrawing substituent at the ortho-, meta-
, or para-position on the phenyl ring of aromatic amine smoothly
furnished the corresponding regiomers (3b-j and 4b-j) in good to
excellent yields and with high levels of regioselectivity. Moreover,
1-naphthyl and quinolinyl groups were amenable to afford the
branch- and linear selective allylation products (3k-l and 4k-l) in
moderate yields, respectively. Notably, indolines and N-alkylani-
lines were also well tolerated to give the corresponding products
(3m-q and 4m-q) in good to excellent yields and with excellent
regioselectivities.
2-FC6H4CO2H
(PhO)2PO2H
Ph2PO2H
Ph2PO2H
<1
<1
11
<1
26g
65h
80 (72i)
<1
13
10
a
Reaction conditions: 1a (0.12 mmol), 2a (0.1 mmol), Pd(dba)2 (5 mol%), L (6 mol
%), HeB (10 mol%), THF (1 mL), 25 ꢀC, 36 h.
b
The yields were determined by 1H NMR analysis of the crude reaction mixture
based on 1,3,5-triacetylbenzene as the internal standard.
c
Z/E > 20:1.
E/Z > 20:1.
d
e
E/Z ¼ 4:1.
f
Isolated yield, Z/E > 20:1.
g
E/Z ¼ 5:1.
h
E/Z ¼ 4:1.
i
Isolated yield, E/Z ¼ 7:1.
desired reaction with decent results (3v-w and 4v-w). Cyclohexyl
and phenyl substituted substrates were also viable to provide the
corresponding regiomers (3x-y and 4x-y) in good to excellent
yields and with high levels of regioselectivity.
Based on our previous studies [10j], a plausible mechanism for
the counteranion-controlled regioselectivity in allylic amination
reaction was depicted in Scheme 4. The Pd(0)-phosphoramidite
catalyst initially undergoes oxidative addition to a dienyl allylic
carbonates 1, leading to a vinyl
hydrogen-bonding interaction between intermediate
amine 2 forms a -allyl-Pd complex II with s-trans geometry, which
can reversely convert to another -allyl-Pd complex III with s-cis
geometry. Due to s-cis diene fragment is shorter than the
corresponding s-trans fragment [10j], complex III is favored to
provide experimentally observed branch- and Z-selectivity via a
SN2’-type nucleophilic attack [6]. In the presence of Ph2PO2H,
p
-allyl-Pd intermediate I. The
I
and
p
p
however, the (
anion exchange to generate a
attacked by amine 2 via a counteranion-directed transition state to
afford the linear product 4.
p
-ally)palladium species I prefers to undergo an
-ally-Pd complex IV, and IV is
p
Then, the substrate scope with respect to the dienyl allylic car-
bonates was examined (Scheme 3). An array of dienyl carbonates
bearing different alkyl substituents were able to furnish either C-5
or C-1 amination products (3r-u and 4r-u) in moderate to high
yields and with excellent regioselectivities. In addition, functional
groups such as ether and alkyne were allowed to undergo the
3. Conclusion
In conclusion, we have developed a counteranion-controlled
regioselective allylic amination reaction between dienyl allylic
carbonates and aromatic amines enabled by phosphoramidite-
2

M.-L. Shen, P.-S. Wang and L.-Z. Gong
Tetrahedron 84 (2021) 131996
Scheme 4. Plausible mechanism.
spectra were recorded on a Nicolet MX-1E FT-IR spectrometer.
Starting materials and solvents were purchased from commercial
suppliers (Aldrich, Alfa, TCI, Adamas-beta) and used as supplied
unless otherwise stated.
4.2. General procedure for the synthesid of 3a-3y and 4a-4y
Condition A. To a flame-dried and Ar-purged Schlenk tube were
added Pd(dba)2 (0.01 mmol), L5 (0.012 mmol) and a stirring bar.
The Schlenk tube was then evacuated and filled with nitrogen. This
cycle was repeated for three times and followed by the sequential
addition of THF (2 mL), aniline (0.2 mmol) and dienyl carbonate
(0.24 mmol) via syringes. The mixture was stirred at 25 ꢀC for 36 h.
The product 3 was purified by column chromatography on silica gel.
Scheme 2. Scope of amines.
Condition B. To a flame-dried and Ar-purged Schlenk tube were
added Pd(dba)2 (0.01 mmol), L6 (0.012 mmol), diphenylphosphinic
acid (0.02 mmol) and a stirring bar. The Schlenk tube was then
evacuated and filled with nitrogen. This cycle was repeated for
three times and followed by the sequential addition of THF (2 mL),
aniline (0.2 mmol) and dienyl carbonate (0.24 mmol) via syringes.
The mixture was stirred at 25 ꢀC for 36 h. The product 4 was pu-
rified by column chromatography on silica gel.
4.2.1. (Z)-N-(undeca-1,3-dien-5-yl)aniline (3a)
Yield: 91%; red oil; b/l > 20:1; 1H NMR (400 MHz, CDCl3)
d 7.15
(dd, J ¼ 8.3, 7.5 Hz, 2H), 6.81e6.70 (m, 1H), 6.68 (t, J ¼ 7.4 Hz, 1H),
6.57 (d, J ¼ 7.7 Hz, 2H), 6.11 (t, J ¼ 10.9 Hz, 1H), 5.36e5.13 (m, 3H),
4.30e4.17 (m, 1H), 3.63 (s, 1H), 1.76e1.65 (m,1H), 1.57e1.45 (m,1H),
1.42e1.22 (m, 8H), 0.89 (t, J ¼ 6.7 Hz, 3H); 13C NMR (101 MHz,
Scheme 3. Scope of dienyl allylic carbonates. aA 2:1 mixture of branched and linear
dienyl allylic carbonates was used. bA 2.5:1 mixture of branched and linear dienyl
allylic carbonates was used. cLinear dienyl allylic carbonate was used.
CDCl3)
d 147.57, 135.47, 131.82, 130.38, 129.18, 118.83, 117.34, 113.31,
51.15, 36.25, 31.80, 29.28, 25.79, 22.64, 14.12; IR (KBr):
g 3408, 2927,
1601, 1502, 1260, 992, 747, 690 cmꢁ1; HRMS (ESI) calculated for
palladium catalysis. Regioselection to respectively access branched
Z-dienyl and linear E-dienyl amines can be controlled by tuning the
counterions. This protocol tolerates a wide scope of substrates,
giving rise to both regiomers from the same substrates.
C
17H25N [MþH]þ: 244.2060, found 244.2061.
4.2.2. (Z)-2-methoxy-N-(undeca-1,3-dien-5-yl)aniline (3b)
Yield: 88%; yellow oil; b/l > 20:1; 1H NMR (400 MHz, CDCl3)
d
6.87e6.73 (m, 3H), 6.66 (td, J ¼ 7.8, 1.3 Hz, 1H), 6.57 (d, J ¼ 7.8 Hz,
4. Experimental section
1H), 6.12 (t, J ¼ 11.1 Hz, 1H), 5.33e5.20 (m, 3H), 4.28e4.19 (m, 2H),
3.86 (s, 3H),1.82e1.71 (m, 1H),1.62e1.52 (m, 1H),1.45e1.27 (m, 8H),
4.1. General
0.90 (t, J ¼ 6.6 Hz, 3H); 13C NMR (101 MHz, CDCl3)
d 146.75, 137.51,
135.82, 131.91, 130.14, 121.20, 118.58, 116.35, 110.71, 109.41, 55.39,
NMR spectra were recorded on a Brucker-400 MHz spectrom-
eter. Mass spectra were recorded on a Thermo LTQ Orbitrap XL
(ESIþ) or a P-SIMS-Gly of Brucker Daltonics Inc (EIþ). Infrared
50.93, 36.23, 31.79, 29.29, 25.82, 22.63, 14.09; IR (KBr): g 3425,
2928, 1602, 1455, 1221, 1030, 905, 733 cmꢁ1; HRMS (ESI) calculated
for C18H27NO [MþH]þ: 274.2165, found 274.2165.
3

M.-L. Shen, P.-S. Wang and L.-Z. Gong
Tetrahedron 84 (2021) 131996
4.2.3. (Z)-2-chloro-N-(undeca-1,3-dien-5-yl)aniline (3c)
J ¼ 9.0 Hz, 2H), 6.13 (t, J ¼ 11.0 Hz, 1H), 5.37e5.14 (m, 3H), 4.22e4.12
(m, 1H), 3.70 (s, 1H), 1.74e1.63 (m, 1H), 1.57e1.45 (m, 1H), 1.41e1.22
Yield: 90%; red oil; b/l > 20:1; 1H NMR (400 MHz, CDCl3)
d 7.24
(dd, J ¼ 7.7, 1.3 Hz, 1H), 7.09 (td, J ¼ 7.9, 1.4 Hz, 1H), 6.75 (dt, J ¼ 16.7,
10.2 Hz, 1H), 6.61 (dd, J ¼ 12.2, 4.6 Hz, 2H), 6.13 (t, J ¼ 11.2 Hz, 1H),
5.34e5.21 (m, 3H), 4.31 (s, 1H), 4.29e4.21 (m, 1H), 1.83e1.70 (m,
1H), 1.65e1.52 (m, 1H), 1.47e1.25 (m, 8H), 0.90 (t, J ¼ 6.8 Hz, 3H);
(m, 8H), 0.89 (t, J ¼ 6.7 Hz, 3H); 13C NMR (101 MHz, CDCl3)
d 146.34,
140.32, 134.85, 131.51, 130.70, 122.33, 119.29, 113.41, 51.35, 36.16,
31.77, 29.23, 25.74, 22.61, 14.09; IR (KBr):
g 3421, 2930, 1612, 1513,
1256, 1160, 914, 826 cmꢁ1; HRMS (ESI) calculated for C18H24F3NO
13C NMR (101 MHz, CDCl3)
d
143.39, 134.92, 131.56, 130.55, 129.07,
[MþH]þ: 328.1883, found 328.1881.
127.68, 119.20, 119.12, 117.12, 112.07, 51.09, 36.10, 31.77, 29.23, 25.76,
22.64, 14.13; IR (KBr):
g
3415, 2928, 1597, 1509, 1322, 1033, 907,
4.2.9. (Z)-3,4-dimethyl-N-(undeca-1,3-dien-5-yl)aniline (3i)
739 cmꢁ1; HRMS (ESI) calculated for C17H24NCl [MþH]þ: 278.1670,
Yield: 81%; yellow oil; b/l > 20:1; 1H NMR (400 MHz, CDCl3)
found 278.1673.
d
6.92 (d, J ¼ 8.1 Hz, 1H), 6.83e6.71 (m, 1H), 6.42 (d, J ¼ 2.2 Hz, 1H),
6.35 (dd, J ¼ 8.1, 2.4 Hz, 1H), 6.11 (t, J ¼ 10.8 Hz, 1H), 5.32e5.17 (m,
3H), 4.26e4.13 (m, 1H), 2.18 (s, 3H), 2.14 (s, 3H), 1.74e1.65 (m, 1H),
1.54e1.44 (m, 1H), 1.42e1.26 (m, 8H), 0.90 (t, J ¼ 6.8 Hz, 3H); 13C
4.2.4. (Z)-3-ethyl-N-(undeca-1,3-dien-5-yl)aniline (3d)
Yield: 93%; red oil; b/l > 20:1; 1H NMR (400 MHz, CDCl3)
d 7.07
(t, J ¼ 7.7 Hz, 1H), 6.86e6.68 (m, 1H), 6.55 (d, J ¼ 7.4 Hz, 1H), 6.44 (s,
1H), 6.41 (d, J ¼ 8.0 Hz, 1H), 6.12 (t, J ¼ 11.0 Hz, 1H), 5.39e5.14 (m,
3H), 4.37e4.14 (m, 1H), 3.57 (s, 1H), 2.56 (q, J ¼ 7.6 Hz, 2H), 1.71 (dt,
J ¼ 20.4, 6.8 Hz, 1H), 1.55 (d, J ¼ 7.0 Hz, 1H), 1.46e1.27 (m, 8H), 1.21
(t, J ¼ 7.6 Hz, 3H), 0.91 (t, J ¼ 6.6 Hz, 3H); 13C NMR (101 MHz, CDCl3)
NMR (101 MHz, CDCl3) d 145.69, 137.19, 135.76, 131.96, 130.27,
130.20, 125.38, 118.60, 115.34, 110.80, 51.32, 36.24, 31.82, 29.29,
25.81, 22.65, 20.08, 18.70, 14.14; IR (KBr):
g 3403, 2927, 1617, 1583,
1317, 1216, 1173, 801 cmꢁ1; HRMS (ESI) calculated for C19H29
N
[MþH]þ: 272.2373, found 272.2371.
d
147.63,145.26,135.55,131.89,130.25,129.05,118.64,117.12,113.05,
110.69, 51.16, 36.25, 31.79, 29.27, 29.00, 25.78, 22.62, 15.39, 14.09; IR
4.2.10. (Z)-3,4-dimethoxy-N-(undeca-1,3-dien-5-yl)aniline (3j)
(KBr):
g
3404, 2928, 1605, 1466, 1264, 1098, 906, 789 cmꢁ1; HRMS
Yield: 85%; yellow oil; b/l > 20:1; 1H NMR (400 MHz, CDCl3)
6.82e6.72 (m, 1H), 6.71 (d, J ¼ 8.6 Hz, 1H), 6.23 (d, J ¼ 2.6 Hz, 1H),
(ESI) calculated for C19H29N [MþH]þ: 272.2373, found 272.2371.
d
6.16e6.08 (m, 2H), 5.31e5.15 (m, 3H), 4.22e4.11 (m, 1H), 3.79 (s,
3H), 3.78 (s, 3H), 1.74e1.62 (m, 1H),1.56e1.44 (m, 1H),1.42e1.24 (m,
4.2.5. (Z)-3-isopropyl-N-(undeca-1,3-dien-5-yl)aniline (3e)
Yield: 89%; yellow oil; b/l > 20:1; 1H NMR (400 MHz, CDCl3)
8H), 0.88 (t, J ¼ 6.8 Hz, 3H); 13C NMR (101 MHz, CDCl3)
d 149.82,
d
7.09 (t, J ¼ 7.8 Hz, 1H), 6.80 (dt, J ¼ 16.7, 10.7 Hz, 1H), 6.59 (d,
142.48, 141.37, 135.90, 131.78, 130.32, 118.88, 113.10, 104.50, 99.17,
56.66, 55.66, 51.90, 36.25, 31.78, 29.29, 25.80, 22.62, 14.12; IR (KBr):
J ¼ 7.5 Hz, 1H), 6.48 (s, 1H), 6.42 (dd, J ¼ 7.9, 1.9 Hz, 1H), 6.13 (t,
J ¼ 11.0 Hz, 1H), 5.34e5.21 (m, 3H), 4.36e4.17 (m, 1H), 3.60 (s, 1H),
2.91e2.73 (m, 1H), 1.80e1.65 (m, 1H), 1.59e1.47 (m, 1H), 1.46e1.28
(m, 8H), 1.23 (dd, J ¼ 6.9, 2.0 Hz, 6H), 0.92 (t, J ¼ 6.6 Hz, 3H); 13C
g
3383, 2928, 1615, 1515, 1230, 1137, 1025, 904 cmꢁ1; HRMS (ESI)
calculated for C19H29NO2 [MþH]þ: 304.2271, found 304.2270.
NMR (101 MHz, CDCl3)
d
149.95, 147.61, 135.63, 131.91, 130.23,
4.2.11. (Z)-N-(undeca-1,3-dien-5-yl)naphthalen-1-amine (3k)
129.03, 118.66, 115.79, 111.64, 110.87, 51.19, 36.27, 34.25, 31.80,
Yield: 45%; yellow solid; b/l > 20:1; 1H NMR (400 MHz, CDCl3)
29.29, 25.80, 23.97, 23.92, 22.63, 14.10; IR (KBr):
g
3404, 2958, 1605,
d
7.85e7.75 (m, 2H), 7.49e7.40 (m, 2H), 7.31 (t, J ¼ 7.9 Hz, 1H), 7.22
1484, 1271, 1073, 905, 775 cmꢁ1; HRMS (ESI) calculated for C20H31
N
(d, J ¼ 8.2 Hz, 1H), 6.89e6.76 (m, 1H), 6.56 (d, J ¼ 7.2 Hz, 1H), 6.17 (t,
J ¼ 11.1 Hz, 1H), 5.39e5.28 (m, 2H), 5.25 (d, J ¼ 10.1 Hz, 1H),
4.47e4.37 (m, 2H), 1.92e1.80 (m, 1H), 1.72e1.59 (m, 1H), 1.52e1.43
(m, 2H), 1.41e1.24 (m, 6H), 0.90 (t, J ¼ 6.9 Hz, 3H); 13C NMR
[MþH]þ: 286.2529, found 286.2528.
4.2.6. (Z)-3-chloro-N-(undeca-1,3-dien-5-yl)aniline (3f)
Yield: 82%; red oil; b/l > 20:1; 1H NMR (400 MHz, CDCl3)
d
7.03
(101 MHz, CDCl3) d 142.65, 135.51, 134.47, 131.94, 130.82, 128.85,
(t, J ¼ 8.0 Hz, 1H), 6.73 (dt, J ¼ 16.8, 10.4 Hz, 1H), 6.63 (dd, J ¼ 7.9,
1.1 Hz, 1H), 6.53 (t, J ¼ 2.0 Hz, 1H), 6.41 (dd, J ¼ 8.2, 1.7 Hz, 1H), 6.13
(t, J ¼ 11.0 Hz, 1H), 5.35e5.16 (m, 3H), 4.22e4.13 (m, 1H), 3.71 (s,
1H), 1.72e1.62 (m, 1H), 1.55e1.45 (m, 1H), 1.42e1.26 (m, 8H), 0.89 (t,
d 148.65, 134.87, 134.49,
131.52, 130.75, 130.11, 119.32, 117.12, 113.02, 111.42, 51.06, 36.07,
126.71, 125.73, 124.74, 123.53, 119.87, 119.12, 117.37, 105.41, 51.46,
36.39, 31.93, 29.44, 26.00, 22.77, 14.25; IR (KBr):
g 3426, 2955, 1581,
1523, 1466, 1103, 783, 767 cmꢁ1; HRMS (ESI) calculated for C21H27
N
[MþH]þ: 294.2216, found 294.2217.
J ¼ 6.8 Hz, 3H); 13C NMR (101 MHz, CDCl3)
4.2.12. (Z)-N-(undeca-1,3-dien-5-yl)quinolin-5-amine (3l)
31.77, 29.21, 25.72, 22.62, 14.11; IR (KBr):
g
3415, 2927, 1595, 1497,
Yield: 40%; yellow solid; b/l > 20:1; 1H NMR (400 MHz, CDCl3)
8.87 (d, J ¼ 2.9 Hz, 1H), 8.16 (d, J ¼ 8.5 Hz, 1H), 7.55e7.49 (m, 1H),
1322, 1075, 988, 760 cmꢁ1; HRMS (ESI) calculated for C17H24NCl
d
[MþH]þ: 278.1670, found 278.1673.
7.46 (d, J ¼ 8.3 Hz, 1H), 7.32 (dd, J ¼ 8.6, 4.2 Hz, 1H), 6.84e6.71 (m,
1H), 6.58 (d, J ¼ 7.5 Hz, 1H), 6.18 (t, J ¼ 11.1 Hz, 1H), 5.36e5.22 (m,
3H), 4.43e4.33 (m, 2H), 1.90e1.78 (m, 1H), 1.70e1.60 (m, 1H),
1.50e1.41 (m, 2H), 1.40e1.23 (m, 6H), 0.89 (t, J ¼ 6.8 Hz, 3H); 13C
4.2.7. (Z)-3-bromo-N-(undeca-1,3-dien-5-yl)aniline (3g)
Yield: 65%; red oil; b/l > 20:1; 1H NMR (400 MHz, CDCl3)
d 6.97
(t, J ¼ 8.0 Hz, 1H), 6.78 (d, J ¼ 7.2 Hz, 1H), 6.75e6.66 (m, 2H), 6.45
(dd, J ¼ 8.2, 1.7 Hz, 1H), 6.12 (t, J ¼ 11.0 Hz, 1H), 5.38e5.11 (m, 3H),
4.18 (dd, J ¼ 15.3, 6.7 Hz, 1H), 3.69 (s, 1H), 1.72e1.62 (m, 1H),
1.54e1.45 (m, 1H), 1.40e1.24 (m, 8H), 0.89 (t, J ¼ 6.8 Hz, 3H); 13C
NMR (101 MHz, CDCl3) d 150.00, 142.82, 134.72, 131.70, 131.21,
130.51, 128.74, 119.56, 119.36, 118.56, 105.86, 51.57, 36.30, 31.91,
29.40, 25.96, 22.75, 14.23; IR (KBr):
g 3447, 2925, 1574, 1465, 1413,
1326, 1097, 788 cmꢁ1; HRMS (ESI) calculated for C20H26N2 [MþH]þ:
NMR (101 MHz, CDCl3)
d
148.80, 134.40, 131.51, 130.75, 130.37,
295.2169, found 295.2170.
123.13, 120.03, 119.28, 115.99, 111.81, 51.06, 36.06, 31.73, 29.17,
25.67, 22.57, 14.04; IR (KBr):
g
3411, 2925, 1592, 1493, 1319, 1067,
4.2.13. (Z)-6-chloro-1-(undeca-1,3-dien-5-yl)indoline (3 m)
985, 799 cmꢁ1; HRMS (ESI) calculated for C17H24NBr [MþH]þ:
Yield: 52%; red oil; b/l > 20:1; 1H NMR (400 MHz, CDCl3)
d 6.89
322.1165, found 322.1169.
(d, J ¼ 7.7 Hz, 1H), 6.75e6.63 (m, 1H), 6.53 (dd, J ¼ 7.7, 1.8 Hz, 1H),
6.31 (d, J ¼ 1.7 Hz, 1H), 6.16 (t, J ¼ 11.0 Hz, 1H), 5.41 (t, J ¼ 10.1 Hz,
1H), 5.26 (dd, J ¼ 17.6, 13.4 Hz, 2H), 4.34e4.23 (m, 1H), 3.52e3.39
(m, 2H), 2.90 (t, J ¼ 8.3 Hz, 2H), 1.78e1.68 (m, 1H), 1.56e1.48 (m,
1H), 1.39e1.24 (m, 8H), 0.89 (t, J ¼ 6.9 Hz, 3H); 13C NMR (101 MHz,
4.2.8. (Z)-4-(trifluoromethoxy)-N-(undeca-1,3-dien-5-yl)aniline
(3h)
Yield: 97%; yellow oil; b/l > 20:1; 1H NMR (400 MHz, CDCl3)
d
7.00 (d, J ¼ 8.5 Hz, 2H), 6.73 (dt, J ¼ 16.3, 10.8 Hz, 1H), 6.50 (d,
CDCl3) d 152.64, 133.06, 131.84, 129.44, 128.46, 124.86, 119.49,
4

M.-L. Shen, P.-S. Wang and L.-Z. Gong
Tetrahedron 84 (2021) 131996
116.47, 107.10, 52.81, 47.51, 32.83, 31.92, 29.32, 27.79, 26.47, 22.77,
4.2.19. (Z)-N-(hepta-4,6-dien-3-yl)aniline (3s)
14.23; IR (KBr):
g
3418, 2928,1606,1489, 1472,1262, 905, 802 cmꢁ1
;
Yield: 84%; yellow oil; b/l > 20:1; 1H NMR (400 MHz, CDCl3)
7.15 (dd, J ¼ 8.5, 7.4 Hz, 2H), 6.81e6.71 (m, 1H), 6.69 (t, J ¼ 7.3 Hz,
HRMS (ESI) calculated for C19H26NCl [MþH]þ: 304.1827, found
d
304.1829.
1H), 6.60e6.56 (m, 2H), 6.14 (t, J ¼ 11.0 Hz, 1H), 5.33e5.18 (m, 3H),
4.22e4.11 (m, 1H), 1.81e1.69 (m, 1H), 1.61e1.50 (m, 1H), 0.99 (t,
J ¼ 7.4 Hz, 3H); 13C NMR (101 MHz, CDCl3)
d 147.71, 135.16, 132.01,
130.81, 129.30, 118.94, 117.50, 113.47, 52.75, 29.20, 10.43; IR (KBr):
4.2.14. (Z)-6-nitro-1-(undeca-1,3-dien-5-yl)indoline (3n)
Yield: 56%; yellow oil; b/l > 20:1; 1H NMR (400 MHz, CDCl3)
g
3403, 2928, 1602, 1503, 1315, 1264, 748, 691 cmꢁ1; HRMS (ESI)
d
7.46 (dd, J ¼ 7.9, 1.9 Hz, 1H), 7.07 (dd, J ¼ 13.8, 4.9 Hz, 2H), 6.71 (dt,
calculated for C13H17N [MþH]þ: 188.1434, found 188.1431.
J ¼ 16.7, 10.7 Hz, 1H), 6.18 (t, J ¼ 11.0 Hz, 1H), 5.38 (t, J ¼ 10.1 Hz, 1H),
5.33e5.24 (m, 2H), 4.44e4.31 (m, 1H), 3.62e3.48 (m, 2H), 3.02 (t,
J ¼ 8.6 Hz, 2H), 1.80e1.68 (m, 1H), 1.63e1.49 (m, 1H), 1.40e1.22 (m,
4.2.20. (Z)-N-(deca-1,3-dien-5-yl)aniline (3t)
Yield: 93%; yellow oil; b/l > 20:1; 1H NMR (400 MHz, CDCl3)
8H), 0.88 (t, J ¼ 6.8 Hz, 3H); 13C NMR (101 MHz, CDCl3)
d 152.32,
d
7.20e7.10 (m, 2H), 6.83e6.72 (m, 1H), 6.70 (dd, J ¼ 11.6, 4.2 Hz,
148.68, 137.79, 132.33, 131.54, 128.63, 123.91, 120.12, 113.07, 100.52,
52.79, 47.38, 32.79, 31.90, 29.30, 28.23, 26.44, 22.75, 14.22; IR (KBr):
1H), 6.58 (d, 2H), 6.13 (t, J ¼ 10.9 Hz, 1H), 5.33e5.20 (m, 3H),
4.28e4.20 (m, 1H), 3.58 (s, 1H), 1.76e1.65 (m, 1H), 1.59e1.46 (m,
1H), 1.44e1.28 (m, 6H), 0.91 (t, J ¼ 9.1, 4.6 Hz, 3H); 13C NMR
g
3400, 2925, 1589, 1492, 1440, 1263, 1075, 907 cmꢁ1; HRMS (ESI)
calculated for C19H26N2O2 [MþH]þ: 315.2067, found 315.2069.
(101 MHz, CDCl3)
d 147.68, 135.57, 131.92, 130.48, 129.28, 118.92,
117.45, 113.42, 51.25, 36.31, 31.89, 25.60, 22.72, 14.18; IR (KBr):
g
4.2.15. (Z)-N-ethyl-N-(undeca-1,3-dien-5-yl)aniline (3ꢀ)
3407, 2928, 1601, 1502, 1262, 881, 747, 691 cmꢁ1; HRMS (ESI)
Yield: 74%; red oil; b/l > 20:1; 1H NMR (400 MHz, CDCl3)
d 7.22
calculated for C16H23N [MþH]þ: 230.1903, found 230.1900.
(t, J ¼ 7.8 Hz, 2H), 6.76 (d, J ¼ 8.4 Hz, 2H), 6.69 (t, J ¼ 7.2 Hz,1H), 6.55
(dt, J ¼ 16.8,10.6 Hz,1H), 6.12 (t, J ¼ 11.0 Hz,1H), 5.45 (t,1H), 5.22 (d,
J ¼ 16.8 Hz, 1H), 5.12 (d, J ¼ 10.1 Hz, 1H), 4.56e4.45 (m, 1H),
3.35e3.21 (m, 2H), 1.77e1.67 (m, 1H), 1.55e1.45 (m, 1H), 1.34e1.23
(m, 8H), 1.12 (t, J ¼ 7.0 Hz, 3H), 0.87 (t, J ¼ 6.7 Hz, 3H); 13C NMR
4.2.21. (Z)-N-(tetradeca-1,3-dien-5-yl)aniline (3u)
Yield: 84%; yellow oil; b/l > 20:1; 1H NMR (400 MHz, CDCl3)
d
7.15 (dd, J ¼ 8.3, 7.4 Hz, 2H), 6.82e6.71 (m, 1H), 6.67 (t, J ¼ 7.3 Hz,
1H), 6.59e6.55 (m, 2H), 6.12 (t, J ¼ 10.8 Hz, 1H), 5.34e5.15 (m, 3H),
4.28e4.17 (m, 1H), 3.61 (s, 1H), 1.76e1.65 (m, 1H), 1.57e1.46 (m, 1H),
1.44e1.23 (m, 14H), 0.89 (t, J ¼ 6.8 Hz, 3H); 13C NMR (101 MHz,
(101 MHz, CDCl3)
d 148.48, 132.45, 132.05, 131.61, 129.27, 118.97,
116.52, 113.84, 55.67, 39.76, 33.92, 31.94, 29.45, 26.58, 22.76, 14.33,
14.23; IR (KBr):
g 3433, 2927, 1596, 1502, 1266, 1180, 1037,
CDCl3) d 147.72, 135.60, 131.97, 130.48, 129.29, 118.89, 117.48, 113.47,
905 cmꢁ1; HRMS (ESI) calculated for C19H29N [MþH]þ: 272.2373,
51.31, 36.38, 32.02, 29.72, 29.69, 29.44, 25.94, 22.81, 14.24; IR (KBr):
found 272.2373.
g
3407, 2925, 1602, 1503, 1261, 993, 747, 691 cmꢁ1; HRMS (ESI)
calculated for C20H31N [MþH]þ: 286.2529, found 286.2526.
4.2.16. (Z)-4-methoxy-N-methyl-N-(undeca-1,3-dien-5-yl)aniline
(3p)
4.2.22. (Z)-N-(10-(benzyloxy)deca-1,3-dien-5-yl)aniline (3v)
Yield: 71%; red oil; b/l > 20:1; 1H NMR (400 MHz, CDCl3)
Yield: 84%; red oil; b/l > 20:1; 1H NMR (400 MHz, CDCl3)
d
6.88e6.77 (m, 4H), 6.60e6.46 (m, 1H), 6.11 (t, J ¼ 11.1 Hz, 1H), 5.42
d
7.37e7.33 (m, 4H), 7.32e7.27 (m, 1H), 7.15 (dd, J ¼ 8.4, 7.4 Hz, 2H),
(t, J ¼ 9.8 Hz, 1H), 5.20 (d, 1H), 5.11 (d, J ¼ 10.1 Hz, 1H), 4.44e4.33
(m, 1H), 3.77 (s, 3H), 2.72 (s, 3H), 1.76e1.65 (m, 1H), 1.55e1.44 (m,
1H), 1.34e1.24 (m, 8H), 0.88 (t, J ¼ 6.8 Hz, 3H); 13C NMR (101 MHz,
6.80e6.71 (m, 1H), 6.69 (t, J ¼ 7.3 Hz, 1H), 6.57 (d, 2H), 6.11 (t,
J ¼ 10.9 Hz, 1H), 5.32e5.18 (m, 3H), 4.51 (s, 2H), 4.29e4.17 (m, 1H),
3.53e3.42 (m, 2H), 1.74e1.61 (m, 3H), 1.57e1.48 (m, 1H), 1.46e1.37
CDCl3) d 152.42,145.22,132.36,131.45,131.24,118.69,116.90,114.65,
(m, 4H); 13C NMR (101 MHz, CDCl3)
d
147.61, 138.74, 135.42, 131.87,
130.55, 129.28, 128.48, 127.75, 127.63, 119.02, 117.48, 113.42, 72.98,
70.36, 51.18, 36.26, 29.77, 26.31, 25.76; IR (KBr): 3402, 2933, 1601,
57.87, 55.81, 33.51, 32.98, 31.94, 29.40, 26.57, 22.74, 14.20; IR (KBr):
g
3451, 2928, 1618, 1510, 1243, 1180, 1040, 907 cmꢁ1; HRMS (ESI)
g
calculated for C19H29NO [MþH]þ: 288.2322, found 288.2319.
1503, 1260, 1100, 748, 695 cmꢁ1; HRMS (ESI) calculated for
C
23H29NO [MþH]þ: 336.2322, found 336.2318.
4.2.17. (Z)-4-(methyl(undeca-1,3-dien-5-yl)amino)benzonitrile
(3q)
4.2.23. (Z)-N-(10-phenyldeca-1,3-dien-9-yn-5-yl)aniline (3w)
Yield: 66%; red oil; b/l > 20:1; 1H NMR (400 MHz, CDCl3)
d 7.45
Yield: 90%; yellow solid; b/l > 20:1; 1H NMR (400 MHz, CDCl3)
(d, J ¼ 9.0 Hz, 2H), 6.70 (d, J ¼ 9.0 Hz, 2H), 6.45 (dt, J ¼ 16.8, 10.7 Hz,
1H), 6.14 (t, J ¼ 11.0 Hz,1H), 5.40 (t,1H), 5.27 (d, J ¼ 16.7 Hz,1H), 5.18
(d, J ¼ 10.1 Hz, 1H), 4.69e4.59 (m, 1H), 2.81 (s, 3H), 1.77e1.67 (m,
d
7.43e7.38 (m, 2H), 7.31e7.27 (m, 3H), 7.18e7.12 (m, 2H),
6.83e6.72 (m, 1H), 6.70 (dd, J ¼ 10.5, 4.1 Hz, 1H), 6.59 (dd, J ¼ 8.6,
0.9 Hz, 2H), 6.14 (t, J ¼ 11.1 Hz, 1H), 5.32e5.25 (m, 2H), 5.21 (d,
J ¼ 10.1 Hz, 1H), 4.37e4.28 (m, 1H), 3.65 (s, 1H), 2.48 (t, J ¼ 6.6 Hz,
2H), 1.96e1.87 (m, 1H), 1.79e1.67 (m, 3H); 13C NMR (101 MHz,
1H),1.64e1.54 (m,1H),1.34e1.19 (m, 8H), 0.86 (t, J ¼ 6.7 Hz, 3H); 13
C
NMR (101 MHz, CDCl3)
d 152.48, 133.68, 132.21, 131.63, 129.73,
120.75, 120.25, 111.80, 97.60, 55.09, 33.55, 31.81, 31.57, 29.22, 26.30,
CDCl3)
d 147.50, 135.06, 131.79, 131.70, 130.82, 129.32, 128.34,
22.65, 14.13; IR (KBr):
g 3390, 2927, 1604, 1517, 1385, 1179, 1094,
127.77, 123.91, 119.29, 117.59, 113.47, 89.70, 81.36, 50.83, 35.23,
814 cmꢁ1; HRMS (ESI) calculated for C19H26N2 [MþNa]þ: 305.1988,
25.03, 19.36; IR (KBr):
g 3401, 2925, 1601, 1503, 1315, 1250, 754,
691 cmꢁ1; HRMS (ESI) calculated for C22H23N [MþH]þ: 302.1903,
found 305.1988.
found 302.1905.
4.2.18. (Z)-N-(hexa-3,5-dien-2-yl)aniline (3r)
Yield: 78%; yellow oil; b/l > 20:1; 1H NMR (400 MHz, CDCl3)
4.2.24. (Z)-N-(1-cyclohexylpenta-2,4-dien-1-yl)aniline (3x)
d
7.16 (t, J ¼ 7.5 Hz, 2H), 6.82e6.71 (m, 1H), 6.71e6.67 (m, 1H), 6.58
Yield: 72%; yellow oil; b/l > 20:1; 1H NMR (400 MHz, CDCl3)
(d, 2H), 6.06 (t, J ¼ 11.1 Hz, 1H), 5.34 (t, 1H), 5.30e5.20 (m, 2H),
d
7.13 (dd, J ¼ 8.4, 7.4 Hz, 2H), 6.79e6.69 (m, 1H), 6.65 (t, J ¼ 7.3 Hz,
4.46e4.35 (m, 1H), 1.33 (d, J ¼ 6.6 Hz, 3H); 13C NMR (101 MHz,
1H), 6.55 (d, J ¼ 7.7 Hz, 2H), 6.15 (t, J ¼ 11.0 Hz, 1H), 5.31e5.16 (m,
3H), 4.05 (dd, J ¼ 9.6, 6.3 Hz, 1H), 1.90 (d, J ¼ 12.4 Hz, 1H), 1.82e1.62
CDCl3)
d 147.54, 136.74, 131.67, 129.58, 129.30, 118.97, 117.61, 113.51,
46.86, 22.30; IR (KBr):
g
3404, 2925, 1602, 1285, 1179, 994, 792,
(m, 6H), 1.21e1.02 (m, 4H); 13C NMR (101 MHz, CDCl3)
d 147.89,
748 cmꢁ1; HRMS (ESI) calculated for C12H15N [MþH]þ: 174.1277,
133.63, 132.20, 131.08, 129.29, 118.86, 117.27, 113.34, 56.01, 43.31,
30.02, 29.12, 26.65, 26.44; IR (KBr): 3415, 2923, 1601, 1502, 1258,
found 174.1273.
g
5

M.-L. Shen, P.-S. Wang and L.-Z. Gong
Tetrahedron 84 (2021) 131996
1003, 746, 690 cmꢁ1; HRMS (ESI) calculated for C17H23N [MþH]þ:
5.74e5.64 (m, 2H), 3.79 (d, J ¼ 6.0 Hz, 2H), 2.87e2.79 (m, 1H),
2.12e2.04 (m, 2H), 1.41e1.28 (m, 8H), 1.24 (d, J ¼ 6.9 Hz, 6H), 0.90 (t,
242.1903, found 242.1899.
J ¼ 6.8 Hz, 3H); 13C NMR (101 MHz, CDCl3)
d 150.19, 148.32, 135.15,
4.2.25. (Z)-N-(1-phenylpenta-2,4-dien-1-yl)aniline (3y)
132.48, 129.61, 129.28, 128.05, 115.96, 111.61, 110.53, 46.18, 34.37,
Yield: 90%; yellow solid; b/l > 20:1; 1H NMR (400 MHz, CDCl3)
32.76, 31.86, 29.37, 29.01, 24.10, 22.75, 14.23; IR (KBr): g 3415, 2925,
d
7.44 (d, J ¼ 7.3 Hz, 2H), 7.37 (t, J ¼ 7.5 Hz, 2H), 7.29 (t, J ¼ 7.2 Hz,
1605, 1466, 1336, 988, 776, 698 cmꢁ1; HRMS (ESI) calculated for
1H), 7.16 (dd, J ¼ 8.4, 7.5 Hz, 2H), 6.86 (dt, J ¼ 16.7, 10.7 Hz, 1H), 6.74
(t, J ¼ 7.3 Hz, 1H), 6.61 (d, J ¼ 7.7 Hz, 2H), 6.18 (t, J ¼ 10.9 Hz, 1H),
5.61 (t, J ¼ 9.8 Hz, 1H), 5.40e5.33 (m, 2H), 5.28 (d, J ¼ 10.1 Hz, 1H),
C
20H31N [MþH]þ: 286.2529, found 286.2530.
4.2.31. 3-chloro-N-((2E,4E)-undeca-2,4-dien-1-yl)aniline (4f)
4.05 (s, 1H); 13C NMR (101 MHz, CDCl3)
d
147.35, 142.75, 133.38,
Yield: 95%; yellow oil; E/Z ¼ 9:1; 1H NMR (400 MHz, CDCl3)
131.71, 130.51, 129.27, 128.96, 127.43, 126.70, 120.15, 117.90, 113.72,
d
7.07 (t, J ¼ 8.0 Hz, 1H), 6.69e6.65 (m, 1H), 6.58 (t, J ¼ 2.1 Hz, 1H),
55.92; IR (KBr):
g
3407, 2924, 1601, 1501, 1313, 1265, 749, 699 cmꢁ1
;
6.49e6.45 (m, 1H), 6.22 (dd, J ¼ 15.1, 10.4 Hz, 1H), 6.04 (dd, J ¼ 15.1,
10.4 Hz, 1H), 5.74e5.60 (m, 2H), 3.75 (d, J ¼ 5.9 Hz, 2H), 2.11e2.03
(m, 2H), 1.42e1.24 (m, 8H), 0.89 (t, J ¼ 6.8 Hz, 3H); 13C NMR
HRMS (ESI) calculated for C17H17N [MþH]þ: 236.1434, found
236.1430.
(101 MHz, CDCl3)
d 149.31, 135.62, 135.09, 132.75, 130.28, 129.36,
4.2.26. N-((2E,4E)-undeca-2,4-dien-1-yl)aniline (4a)
127.04, 117.37, 112.63, 111.36, 45.74, 32.77, 31.85, 29.32, 29.02, 22.75,
Yield: 72%; yellow oil; E/Z ¼ 7:1; 1H NMR (400 MHz, CDCl3)
14.25; IR (KBr): g ;
3418, 2925, 1500, 1323, 1265, 988, 909, 740 cmꢁ1
d
7.18 (t, J ¼ 7.8 Hz, 2H), 6.72 (t, J ¼ 7.3 Hz, 1H), 6.63 (d, J ¼ 7.8 Hz,
HRMS (ESI) calculated for C17H24NCl [MþH]þ: 278.1670, found
2H), 6.24 (dd, J ¼ 15.1, 10.5 Hz, 1H), 6.04 (dd, J ¼ 15.1, 10.5 Hz, 1H),
5.74e5.62 (m, 2H), 3.78 (d, J ¼ 5.9 Hz, 2H), 2.13e2.04 (m, 2H),
1.40e1.34 (m, 2H), 1.33e1.24 (m, 8H), 0.89 (t, J ¼ 6.7 Hz, 3H); 13C
278.1673.
4.2.32. 3-bromo-N-((2E,4E)-undeca-2,4-dien-1-yl)aniline (4g)
NMR (101 MHz, CDCl3)
d
148.23, 135.26, 132.43, 129.52, 129.35,
Yield: 91%; red oil; E/Z ¼ 10:1; 1H NMR (400 MHz, CDCl3)
d 7.01
127.89, 117.60, 113.11, 46.01, 32.77, 31.86, 29.36, 29.02, 22.75, 14.25;
(t, J ¼ 8.0 Hz, 1H), 6.83e6.79 (m, 1H), 6.74 (t, J ¼ 2.1 Hz, 1H),
6.53e6.50 (m, 1H), 6.22 (dd, J ¼ 15.2, 10.4 Hz, 1H), 6.04 (dd, J ¼ 15.1,
10.4 Hz, 1H), 5.73e5.60 (m, 2H), 3.75 (d, J ¼ 5.9 Hz, 2H), 2.12e2.03
(m, 2H), 1.45e1.23 (m, 8H), 0.89 (t, J ¼ 6.8 Hz, 3H); 13C NMR
IR (KBr):
g
3410, 2955, 1602, 1504, 1094, 987, 747, 690 cmꢁ1; HRMS
(ESI) calculated for C17H25N [MþH]þ: 244.2060, found 244.2060.
4.2.27. 2-methoxy-N-((2E,4E)-undeca-2,4-dien-1-yl)aniline (4b)
(101 MHz, CDCl3) d 149.46, 135.64, 132.78, 130.58, 129.36, 126.99,
Yield: 98%; red oil; E/Z ¼ 11:1; 1H NMR (400 MHz, CDCl3)
123.36, 120.27, 115.54, 111.76, 45.72, 32.77, 31.85, 29.32, 29.01,
d
6.91e6.86 (m, 1H), 6.79 (dd, J ¼ 7.9, 1.3 Hz, 1H), 6.69 (td, J ¼ 7.7,
22.75, 14.25; IR (KBr): g 3415, 2924, 1594, 1495, 1320, 985, 919,
1.5 Hz, 1H), 6.63 (dd, J ¼ 7.8, 1.4 Hz, 1H), 6.26 (dd, J ¼ 15.2, 10.4 Hz,
1H), 6.06 (dd, J ¼ 15.1, 10.4 Hz, 1H), 5.77e5.64 (m, 2H), 4.33 (s, 1H),
3.85 (s, 3H), 3.81 (d, J ¼ 5.9 Hz, 2H), 2.12e2.04 (m, 2H), 1.42e1.26
887 cmꢁ1; HRMS (ESI) calculated for C17H24NBr [MþH]þ: 322.1165,
found 322.1168.
(m, 8H), 0.90 (t, J ¼ 6.8 Hz, 3H); 13C NMR (101 MHz, CDCl3)
d
146.96,
4.2.33. 4-(trifluoromethoxy)-N-((2E,4E)-undeca-2,4-dien-1-yl)
aniline (4h)
138.16, 135.02, 132.23, 129.62, 128.11, 121.37, 116.63, 110.24, 109.45,
55.48, 45.70, 32.76, 31.85, 29.36, 29.01, 22.75, 14.24; IR (KBr):
g
Yield: 99%; red oil; E/Z ¼ 7:1; 1H NMR (400 MHz, CDCl3)
d 7.04
3425, 2955, 1602, 1511, 1244, 1125, 987, 733 cmꢁ1; HRMS (ESI)
(d, 2H), 6.56 (d, 2H), 6.24 (dd, J ¼ 15.1,10.4 Hz,1H), 6.05 (dd, J ¼ 15.0,
10.4 Hz, 1H), 5.74e5.62 (m, 2H), 3.76 (d, J ¼ 6.0 Hz, 2H), 2.12e2.04
(m, 2H), 1.42e1.23 (m, 8H), 0.90 (t, J ¼ 8.0, 5.7 Hz, 3H); 13C NMR
calculated for C18H27NO [MþH]þ: 274.2165, found 274.2167.
4.2.28. 2-chloro-N-((2E,4E)-undeca-2,4-dien-1-yl)aniline (4c)
(101 MHz, CDCl3) d 147.00, 135.60, 132.74, 129.39, 127.27, 122.52,
Yield: 96%; yellow oil; E/Z ¼ 8:1; 1H NMR (400 MHz, CDCl3)
113.30, 113.24, 46.12, 32.78, 31.86, 29.33, 29.03, 22.76, 14.23; IR
d
7.27e7.22 (m, 1H), 7.14e7.09 (m, 1H), 6.68e6.59 (m, 2H), 6.23 (dd,
(KBr): g
3418, 2957, 1612, 1514, 1222, 1159, 1116, 987 cmꢁ1; HRMS
J ¼ 15.2, 10.5 Hz, 1H), 6.04 (dd, J ¼ 15.1, 10.5 Hz, 1H), 5.72e5.62 (m,
2H), 4.41 (s, 1H), 3.82 (d, J ¼ 5.3 Hz, 2H), 2.11e2.02 (m, 2H),
1.40e1.25 (m, 8H), 0.88 (t, J ¼ 6.8 Hz, 3H); 13C NMR (101 MHz,
(ESI) calculated for C18H24F3NO [MþH]þ: 328.1883, found 328.1885.
4.2.34. 3,4-dimethyl-N-((2E,4E)-undeca-2,4-dien-1-yl)aniline (4i)
CDCl3)
d
144.01, 135.51, 132.64, 129.44, 129.21, 127.89, 127.14, 119.27,
Yield: 71%; yellow oil; E/Z ¼ 10:1; 1H NMR (400 MHz, CDCl3)
117.35, 111.59, 45.60, 32.77, 31.86, 29.34, 29.03, 22.75, 14.23; IR
d
6.94 (d, J ¼ 8.0 Hz, 1H), 6.46 (d, 1H), 6.41 (dd, J ¼ 8.0, 2.5 Hz, 1H),
(KBr):
g
3418, 2925, 1598, 1510, 1321, 1033, 986, 739 cmꢁ1; HRMS
6.23 (dd, J ¼ 15.2, 10.4 Hz, 1H), 6.04 (dd, J ¼ 15.1, 10.4 Hz, 1H),
5.73e5.63 (m, 2H), 3.75 (d, J ¼ 5.9 Hz, 2H), 2.20 (s, 3H), 2.16 (s, 3H),
2.10e2.04 (m, 2H), 1.41e1.26 (m, 8H), 0.89 (t, J ¼ 6.8 Hz, 3H); 13C
(ESI) calculated for C17H24NCl [MþH]þ: 278.1670, found 278.1673.
4.2.29. 3-ethyl-N-((2E,4E)-undeca-2,4-dien-1-yl)aniline (4d)
NMR (101 MHz, CDCl3) d 146.43, 137.40, 135.07, 132.23, 130.38,
Yield: 82%; yellow oil; E/Z ¼ 9:1; 1H NMR (400 MHz, CDCl3)
129.61, 128.28, 125.67, 115.07, 110.61, 46.41, 32.77, 31.86, 29.37,
d
7.11 (t, J ¼ 7.7 Hz, 1H), 6.58 (d, J ¼ 7.7 Hz, 1H), 6.50e6.45 (m, 2H),
29.02, 22.76, 20.19, 18.84, 14.25; IR (KBr): g 3404, 2925, 1617, 1509,
6.25 (dd, J ¼ 15.1, 10.6 Hz, 1H), 6.05 (dd, J ¼ 15.0, 10.5 Hz, 1H),
5.75e5.64 (m, 2H), 3.78 (d, J ¼ 6.0 Hz, 2H), 2.58 (q, J ¼ 7.6 Hz, 2H),
2.11e2.04 (m, 2H), 1.39e1.28 (m, 8H), 1.23 (t, J ¼ 7.6 Hz, 3H), 0.90 (t,
1318, 1261, 1122, 987 cmꢁ1; HRMS (ESI) calculated for C19H29
N
[MþH]þ: 272.2373, found 272.2370.
J ¼ 6.8 Hz, 3H); 13C NMR (101 MHz, CDCl3)
d
148.36, 145.54, 135.16,
4.2.35. 3,4-dimethoxy-N-((2E,4E)-undeca-2,4-dien-1-yl)aniline
(4j)
132.42, 129.60, 129.29, 128.04, 117.39, 112.86, 110.48, 46.13, 32.76,
31.86, 29.37, 29.16, 29.01, 22.75, 15.66, 14.23; IR (KBr):
g
3412, 2960,
Yield: 68%; red oil; E/Z ¼ 10:1; 1H NMR (400 MHz, CDCl3)
d 6.74
1605, 1507, 1332, 1104, 987, 694 cmꢁ1; HRMS (ESI) calculated for
(d, J ¼ 8.5 Hz, 1H), 6.26e6.19 (m, 2H), 6.16 (dd, J ¼ 8.5, 2.6 Hz, 1H),
6.03 (dd, J ¼ 15.1, 10.5 Hz, 1H), 5.72e5.63 (m, 2H), 3.83 (s, 3H), 3.80
(s, 3H), 3.73 (d, J ¼ 6.0 Hz, 2H), 2.09e2.03 (m, 2H), 1.40e1.25 (m,
C
19H29N [MþH]þ: 272.2373, found 272.2373.
4.2.30. 3-isopropyl-N-((2E,4E)-undeca-2,4-dien-1-yl)aniline (4e)
8H), 0.88 (t, J ¼ 6.7 Hz, 3H); 13C NMR (101 MHz, CDCl3)
d 150.02,
Yield: 93%; yellow oil; E/Z ¼ 8:1; 1H NMR (400 MHz, CDCl3)
143.11, 141.71, 135.22, 132.46, 129.53, 128.05, 113.21, 103.91, 99.21,
56.76, 55.80, 46.91, 32.74, 31.83, 29.33, 28.99, 22.73, 14.22; IR (KBr):
d
7.12 (t, J ¼ 7.8 Hz, 1H), 6.62 (d, J ¼ 7.6 Hz, 1H), 6.54e6.44 (m, 2H),
6.25 (dd, J ¼ 15.1, 10.5 Hz, 1H), 6.05 (dd, J ¼ 15.0, 10.4 Hz, 1H),
g
3387, 2926, 1615, 1515, 1209, 1027,897, 790 cmꢁ1; HRMS (ESI)
6

M.-L. Shen, P.-S. Wang and L.-Z. Gong
Tetrahedron 84 (2021) 131996
calculated for C19H29NO2 [MþH]þ: 304.2271, found 304.2270.
4.2.41. 4-methoxy-N-methyl-N-((2E,4E)-undeca-2,4-dien-1-yl)
aniline (4p)
Yield: 90%; red oil; E/Z ¼ 11:1; 1H NMR (400 MHz, CDCl3)
d 6.83
4.2.36. N-((2E,4E)-undeca-2,4-dien-1-yl)naphthalen-1-amine (4k)
Yield: 99%; yellow solid; E/Z ¼ 8:1; 1H NMR (400 MHz, CDCl3)
(d, J ¼ 9.2 Hz, 2H), 6.73 (d, J ¼ 9.2 Hz, 2H), 6.14 (dd, J ¼ 15.1, 10.4 Hz,
1H), 6.02 (dd, J ¼ 14.9, 10.5 Hz, 1H), 5.69e5.54 (m, 2H), 3.84 (d,
J ¼ 5.9 Hz, 2H), 3.76 (s, 3H), 2.83 (s, 3H), 2.09e2.01 (m, 2H),
1.38e1.25 (m, 8H), 0.88 (t, J ¼ 6.8 Hz, 3H); 13C NMR (101 MHz,
d
7.84e7.78 (m, 2H), 7.49e7.42 (m, 2H), 7.36 (t, J ¼ 7.9 Hz, 1H),
7.27e7.25 (m, 1H), 6.64 (d, J ¼ 7.1 Hz, 1H), 6.33 (dd, J ¼ 15.2, 10.4 Hz,
1H), 6.10 (dd, J ¼ 15.1,10.4 Hz,1H), 5.87e5.79 (m,1H), 5.76e5.67 (m,
1H), 4.43 (s, 1H), 3.96 (d, J ¼ 6.0 Hz, 2H), 2.14e2.05 (m, 2H),
1.44e1.21 (m, 8H), 0.91 (t, J ¼ 9.1, 4.5 Hz, 3H); 13C NMR (101 MHz,
CDCl3) d 151.88, 144.74,134.72,132.40,129.63,127.10,115.04,114.79,
55.96, 55.89, 38.83, 32.77, 31.87, 29.38, 29.04, 22.76, 14.25; IR (KBr):
g
3440, 2925, 1614, 1511, 1243, 1103, 1040, 988 cmꢁ1; HRMS (ESI)
CDCl3)
d 143.33, 135.51, 134.39, 132.89, 129.52, 128.79, 127.48,
calculated for C19H29NO [MþH]þ: 288.2322, found 288.2319.
126.74, 125.82, 124.82, 123.57, 120.01, 117.61, 104.81, 46.23, 32.79,
31.87, 29.35, 29.03, 22.76, 14.26; IR (KBr):
g 3445, 2926, 1622, 1524,
1278, 1114, 987, 767 cmꢁ1; HRMS (ESI) calculated for C21H27
N
4.2.42. 4-(methyl((2E,4E)-undeca-2,4-dien-1-yl)amino)
benzonitrile (4q)
[MþH]þ: 294.2216, found 294.2217.
Yield: 72%; yellow oil; E/Z ¼ 9:1; 1H NMR (400 MHz, CDCl3)
d
7.45 (d, J ¼ 9.1 Hz, 2H), 6.64 (d, J ¼ 9.0 Hz, 2H), 6.11e5.96 (m, 2H),
4.2.37. N-((2E,4E)-undeca-2,4-dien-1-yl)quinolin-5-amine (4l)
5.70e5.61 (m, 1H), 5.55e5.47 (m, 1H), 3.98 (d, J ¼ 5.4 Hz, 2H), 3.00
(s, 3H), 2.08e2.02 (m, 2H), 1.36e1.23 (m, 8H), 0.87 (t, J ¼ 6.8 Hz,
Yield: 50%; yellow solid; E/Z ¼ 8:1; 1H NMR (400 MHz, CDCl3)
8.87 (dd, J ¼ 4.2,1.6 Hz,1H), 8.20e8.14 (m, 1H), 7.56 (t,1H), 7.49 (d,
d
3H); 13C NMR (101 MHz, CDCl3)
d 151.86, 135.79, 133.61, 132.48,
J ¼ 8.4 Hz, 1H), 7.32 (dd, J ¼ 8.5, 4.2 Hz, 1H), 6.65 (d, J ¼ 6.9 Hz, 1H),
6.31 (dd, J ¼ 15.2, 10.4 Hz, 1H), 6.08 (dd, J ¼ 15.1, 10.5 Hz, 1H),
5.82e5.66 (m, 2H), 4.43 (s, 1H), 3.94 (d, J ¼ 5.7 Hz, 2H), 2.08 (t, 2H),
129.09, 124.51, 111.68, 97.56, 53.89, 38.13, 32.75, 31.83, 29.27, 29.01,
22.73, 14.23; IR (KBr):
g 3389, 2924, 1605, 1382, 1177, 987, 921,
815 cmꢁ1; HRMS (ESI) calculated for C19H26N2 [MþNa]þ: 305.1988,
1.40e1.24 (m, 8H), 0.88 (t, 3H); 13C NMR (101 MHz, CDCl3)
d 150.12,
found 305.1989.
149.32, 143.49, 135.89, 133.27, 130.50, 129.35,128.79, 126.83, 119.45,
118.78, 118.61, 105.18, 46.24, 32.79, 31.85, 29.32, 29.02, 22.75, 14.25;
4.2.43. N-((2E,4E)-hexa-2,4-dien-1-yl)aniline (4r)
IR (KBr):
g
3441, 2923, 1586, 1530, 1325, 1109, 937, 788 cmꢁ1; HRMS
Yield: 58%; yellow oil; E/Z ¼ 8:1; 1H NMR (400 MHz, CDCl3)
(ESI) calculated for C20H26N2 [MþH]þ: 295.2169, found 295.2171.
d
7.18 (t, J ¼ 7.8 Hz, 2H), 6.72 (t, J ¼ 7.3 Hz, 1H), 6.63 (d, J ¼ 7.8 Hz,
2H), 6.24 (dd, J ¼ 15.0,10.5 Hz,1H), 6.07 (dd,1H), 5.73e5.64 (m, 2H),
4.2.38. 6-chloro-1-((2E,4E)-undeca-2,4-dien-1-yl)indoline (4 m)
3.78 (d, J ¼ 5.9 Hz, 2H), 1.76 (d, J ¼ 6.6 Hz, 3H); 13C NMR (101 MHz,
Yield: 90%; red oil; E/Z ¼ 9:1; 1H NMR (400 MHz, CDCl3)
d 6.94
CDCl3) d 148.23, 132.26, 130.95, 129.53, 129.35, 127.74, 117.61, 113.11,
(dd, J ¼ 7.7, 1.0 Hz, 1H), 6.59 (dd, J ¼ 7.7, 1.9 Hz, 1H), 6.43 (d,
J ¼ 1.8 Hz, 1H), 6.21 (dd, J ¼ 15.1, 10.4 Hz, 1H), 6.04 (dd, J ¼ 15.1,
10.5 Hz, 1H), 5.73e5.55 (m, 2H), 3.69 (d, J ¼ 6.4 Hz, 2H), 3.37 (t,
J ¼ 8.4 Hz, 2H), 2.91 (dd, J ¼ 12.3, 4.5 Hz, 2H), 2.11e2.03 (m, 2H),
1.40e1.22 (m, 8H), 0.89 (t, J ¼ 6.9 Hz, 3H); 13C NMR (101 MHz,
45.99, 18.24; IR (KBr):
g 3409, 2926, 1602, 1504, 1320, 1262, 748,
691 cmꢁ1; HRMS (ESI) calculated for C12H15N [MþH]þ: 174.1277,
found 174.1274.
4.2.44. N-((2E,4E)-hepta-2,4-dien-1-yl)aniline (4s)
CDCl3)
d 153.49, 135.39, 133.53, 133.13, 129.42, 128.86, 125.79,
Yield: 64%; yellow oil; E/Z ¼ 11:1; 1H NMR (400 MHz, CDCl3)
125.03, 117.13, 107.45, 53.39, 50.67, 32.78, 31.87, 29.34, 29.04, 28.06,
d
7.18 (dd, J ¼ 8.5, 7.4 Hz, 2H), 6.71 (t, J ¼ 7.3 Hz,1H), 6.63 (dd, J ¼ 8.6,
22.76, 14.26; IR (KBr):
g 3417, 2925, 1606, 1489, 1327, 1073, 988,
1.0 Hz, 2H), 6.25 (dd, J ¼ 15.2, 10.2 Hz,1H), 6.05 (dd, J ¼ 15.1, 10.3 Hz,
1H), 5.76e5.66 (m, 2H), 3.78 (d, J ¼ 5.9 Hz, 2H), 2.14e2.06 (m, 2H),
789 cmꢁ1; HRMS (ESI) calculated for C19H26NCl [MþH]þ: 304.1827,
found 304.1830.
1.01 (t, J ¼ 7.5 Hz, 3H); 13C NMR (101 MHz, CDCl3)
d 148.27, 136.59,
132.43, 129.36, 128.66, 128.01, 117.63, 113.14, 46.03, 25.75, 13.61; IR
(KBr):
g
3411, 2928, 1602, 1504, 1317, 988, 747, 691 cmꢁ1; HRMS
4.2.39. 6-nitro-1-((2E,4E)-undeca-2,4-dien-1-yl)indoline (4n)
Yield: 92%; red solid; E/Z ¼ 8:1; 1H NMR (400 MHz, CDCl3)
d 7.51
(ESI) calculated for C13H17N [MþH]þ: 188.1434, found 188.1431.
(dd, J ¼ 7.9, 2.1 Hz,1H), 7.17 (d, J ¼ 2.1 Hz,1H), 7.09 (d, J ¼ 8.0 Hz,1H),
6.23 (dd, J ¼ 15.2, 10.4 Hz, 1H), 6.03 (dd, J ¼ 15.1, 10.4 Hz, 1H),
5.74e5.65 (m, 1H), 5.61e5.53 (m, 1H), 3.78 (d, J ¼ 6.4 Hz, 2H), 3.48
(t, J ¼ 8.5 Hz, 2H), 3.02 (t, J ¼ 8.5 Hz, 2H), 2.12e2.01 (m, 2H),
1.42e1.22 (m, 8H), 0.88 (t, J ¼ 6.9 Hz, 3H); 13C NMR (101 MHz,
4.2.45. N-((2E,4E)-deca-2,4-dien-1-yl)aniline (4t)
Yield: 70%; yellow oil; E/Z ¼ 7:1; 1H NMR (400 MHz, CDCl3)
d
7.18 (t, J ¼ 7.8 Hz, 2H), 6.72 (t, J ¼ 7.3 Hz, 1H), 6.63 (d, J ¼ 8.1 Hz,
2H), 6.24 (dd, J ¼ 15.1, 10.4 Hz, 1H), 6.05 (dd, J ¼ 15.1, 10.5 Hz, 1H),
5.73e5.62 (m, 2H), 3.78 (d, J ¼ 5.9 Hz, 2H), 2.11e2.04 (m, 2H),
1.43e1.24 (m, 6H), 0.90 (t, J ¼ 6.8 Hz, 3H); 13C NMR (101 MHz,
CDCl3)
d 153.01, 148.69, 138.10, 135.81, 133.98, 129.21, 124.75,
124.05, 113.48, 100.70, 52.95, 50.13, 32.75, 31.83, 29.27, 29.01, 28.46,
22.73, 14.23; IR (KBr):
g 3409, 2925, 1615, 1494, 1338, 1145, 988,
CDCl3) d 148.27,135.24,132.45,129.56,129.36, 127.92,117.62, 113.13,
736 cmꢁ1
;
HRMS (ESI) calculated for C19H26N2O2 [MþH]þ:
46.03, 32.72, 31.54, 29.07, 22.66, 14.17; IR (KBr):
g 3414, 2926, 1602,
1505, 1261, 988, 747, 691 cmꢁ1; HRMS (ESI) calculated for C16H23
N
315.2067, found 315.2070.
[MþH]þ: 230.1903, found 230.1899.
4.2.40. N-ethyl-N-((2E,4E)-undeca-2,4-dien-1-yl)aniline (4ꢀ)
Yield: 96%; yellow oil; E/Z ¼ 10:1; 1H NMR (400 MHz, CDCl3)
4.2.46. N-((2E,4E)-tetradeca-2,4-dien-1-yl)aniline (4u)
d
7.20 (dd, J ¼ 8.8, 7.3 Hz, 2H), 6.69 (d, J ¼ 8.1 Hz, 2H), 6.65 (t,
Yield: 71%; yellow oil; E/Z ¼ 6:1; 1H NMR (400 MHz, CDCl3)
7.19 (dd, J ¼ 8.6, 7.3 Hz, 2H), 6.75e6.69 (m, 1H), 6.63 (dd, J ¼ 8.6,
J ¼ 7.3 Hz, 1H), 6.13 (dd, J ¼ 15.0, 10.4 Hz, 1H), 6.02 (dd, J ¼ 14.9,
10.5 Hz, 1H), 5.65e5.54 (m, 2H), 3.90 (d, J ¼ 5.1 Hz, 2H), 3.36 (q,
J ¼ 7.0 Hz, 2H), 2.08e2.01 (m, 2H), 1.37e1.23 (m, 8H), 1.15 (t,
J ¼ 7.1 Hz, 3H), 0.87 (t, J ¼ 6.8 Hz, 3H); 13C NMR (101 MHz, CDCl3)
d
1.0 Hz, 2H), 6.25 (dd, J ¼ 15.2,10.6 Hz,1H), 6.05 (dd, J ¼ 15.0,10.6 Hz,
1H), 5.73e5.64 (m, 2H), 3.79 (d, J ¼ 6.1 Hz, 2H), 2.11e2.04 (m, 2H),
1.45e1.24 (m, 14H), 0.90 (t, J ¼ 6.9 Hz, 3H); 13C NMR (101 MHz,
d
148.37, 134.56, 131.57, 129.62, 129.31, 127.45, 115.86, 112.22, 51.83,
CDCl3) d 148.27, 135.23, 132.45, 129.56, 129.35, 127.91, 117.62, 113.13,
44.66, 32.77, 31.86, 29.38, 29.04, 22.75, 14.24, 12.34; IR (KBr):
g
46.03, 32.76, 32.04, 29.70, 29.64, 29.46, 29.40, 29.35, 22.82, 14.25;
3444, 2925, 1598, 1505, 1374, 1189, 988, 745 cmꢁ1; HRMS (ESI)
IR (KBr): g
3416, 2925, 1602, 1504, 1264, 988, 747, 691 cmꢁ1; HRMS
calculated for C19H29N [MþH]þ: 272.2373, found 272.2374.
(ESI) calculated for C20H31N [MþH]þ: 286.2529, found 286.2524.
7

M.-L. Shen, P.-S. Wang and L.-Z. Gong
Tetrahedron 84 (2021) 131996
4.2.47. N-((2E,4E)-10-(benzyloxy)deca-2,4-dien-1-yl)aniline (4v)
References
Yield: 99%; red oil; E/Z ¼ 7:1; 1H NMR (400 MHz, CDCl3)
d 7.35 (s,
[1] (a) B.M. Trost, D.L. Van Vranken, Chem. Rev. 96 (1996) 395;
(b) B.M. Trost, Chem. Pharm. Bull. 50 (2002) 1;
5H), 7.19 (t, 2H), 6.72 (t, J ¼ 7.3 Hz, 1H), 6.63 (d, J ¼ 7.7 Hz, 2H), 6.24
(dd, J ¼ 15.2, 10.4 Hz, 1H), 6.04 (dd, J ¼ 15.2, 10.5 Hz, 1H), 5.73e5.65
(m, 2H), 4.51 (s, 2H), 3.78 (d, J ¼ 5.9 Hz, 2H), 3.47 (t, J ¼ 6.6 Hz, 2H),
2.10e2.06 (m, 2H), 1.67e1.59 (m, 2H), 1.47e1.33 (m, 4H); 13C NMR
(c) B.M. Trost, J. Org. Chem. 69 (2004) 5813;
(d) B.M. Trost, M.R. Machacek, A. Aponick, Acc. Chem. Res. 39 (2006) 747;
(e) Z. Lu, S. Ma, Angew. Chem. Int. Ed. 47 (2008) 258.
[2] (a) Y. Dong, P. Teesdale-Spittle, J.O. Hoberg, Tetrahedron Lett. 46 (2005) 353;
(b) U. Kazmaier, D. Stolz, K. Kramer, F.L. Zumpe, Chem. Eur J. 14 (2008) 1322.
[3] (a) S.G. Pyne, Z. Dong, Tetrahedron Lett. 41 (2000) 5387;
(b) S.L. You, X.Z. Zhu, Y.M. Luo, X.L. Hou, L.X. Dai, J. Am. Chem. Soc. 123 (2001)
7471;
(101 MHz, CDCl3)
d 148.22, 138.77, 134.89, 132.34, 129.71, 129.35,
128.48, 128.04, 127.76, 127.62, 117.59, 113.09, 73.00, 70.49, 45.98,
32.66, 29.73, 29.19, 25.87; IR (KBr):
g 3410, 2929, 1602, 1504, 1262,
989, 747, 695 cmꢁ1; HRMS (ESI) calculated for C23H29NO [MþH]þ:
(c) G.R. Cook, H. Yu, S. Sankaranarayanan, P.S. Shanker, J. Am. Chem. Soc. 125
(2003) 5115;
336.2322, found 336.2317.
(d) J.P. Chen, Q. Peng, B.L. Lei, X.L. Hou, Y.D. Wu, J. Am. Chem. Soc. 133 (2011)
14180;
(e) X.F. Yang, W.H. Yu, C.H. Ding, Q.P. Ding, S.L. Wan, X.L. Hou, L.X. Dai,
P.J. Wang, J. Org. Chem. 78 (2013) 6503;
(f) M.H. Yang, D.L. Orsi, R.A. Altman, Angew. Chem. Int. Ed. 54 (2015) 2361;
(g) A. Cai, W. Guo, L. Martinez-Rodriguez, A.W. Kleij, J. Am. Chem. Soc. 138
(2016) 14194;
(h) W. Guo, A. Cai, J. Xie, A.W. Kleij, Angew. Chem. Int. Ed. 56 (2017) 11797;
(i) J. Xie, W. Guo, A. Cai, E.C. Escudero-Adan, A.W. Kleij, Org. Lett. 19 (2017)
6388;
(j) Y.N. Wang, L.Q. Lu, W. Xiao, J. Chem. Asian J. 13 (2018) 2174;
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14694.
4.2.48. N-((2E,4E)-10-phenyldeca-2,4-dien-9-yn-1-yl)aniline (4w)
Yield: 67%; red oil; E/Z ¼ 8:1; 1H NMR (400 MHz, CDCl3)
d
7.42e7.38 (m, 2H), 7.30e7.26 (m, 3H), 7.19 (dd, J ¼ 8.5, 7.4 Hz, 2H),
6.72 (t, J ¼ 7.3 Hz, 1H), 6.63 (d, J ¼ 7.7 Hz, 2H), 6.25 (dd, J ¼ 15.1,
10.4 Hz, 1H), 6.11 (dd, J ¼ 15.0, 10.5 Hz, 1H), 5.76e5.65 (m, 2H), 3.79
(d, J ¼ 5.9 Hz, 2H), 2.43 (t, J ¼ 7.1 Hz, 2H), 2.30e2.23 (m, 2H), 1.71 (t,
2H); 13C NMR (101 MHz, CDCl3)
d 148.20, 133.65, 132.14, 131.67,
130.49, 129.36, 128.50, 128.33, 127.68, 124.06, 117.62, 113.10, 89.98,
81.09, 45.96, 31.80, 28.34, 18.97; IR (KBr):
g 3411, 2927, 1602, 1504,
1251, 989, 753, 691 cmꢁ1; HRMS (ESI) calculated for C22H23
N
[MþH]þ: 302.1903, found 302.1899.
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6609.
4.2.49. N-((2E,4E)-5-cyclohexylpenta-2,4-dien-1-yl)aniline (4x)
Yield: 73%; yellow oil; E/Z ¼ 13:1; 1H NMR (400 MHz, CDCl3)
7.18 (dd, J ¼ 8.6, 7.3 Hz, 2H), 6.74e6.69 (m, 1H), 6.63 (dd, J ¼ 8.6,
d
1.0 Hz, 2H), 6.23 (dd, J ¼ 15.0,10.5 Hz,1H), 6.02 (dd, J ¼ 15.5,10.3 Hz,
1H), 5.75e5.60 (m, 2H), 3.78 (dd, J ¼ 6.0, 1.1 Hz, 2H), 2.03e1.95 (m,
1H), 1.77e1.63 (m, 4H), 1.31e1.04 (m, 6H); 13C NMR (101 MHz,
CDCl3) d 148.27, 140.92, 132.71, 129.36, 128.08, 127.04, 117.61, 113.12,
46.04, 40.82, 32.94, 26.28, 26.13; IR (KBr):
g 3413, 2923, 1602, 1504,
[6] B.M. Trost, R.C. Bunt, J. Am. Chem. Soc. 120 (1998) 70.
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(2014) 484.
1257, 988, 747, 691 cmꢁ1; HRMS (ESI) calculated for C17H23
N
[MþH]þ: 242.1903, found 242.1898.
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4.2.50. N-((2E,4E)-5-phenylpenta-2,4-dien-1-yl)aniline (4y)
Yield: 71%; yellow oil; E/Z ¼ 11:1; 1H NMR (400 MHz, CDCl3)
7.39e7.36 (m, 2H), 7.30 (dd, J ¼ 8.3, 6.9 Hz, 2H), 7.24e7.15 (m, 3H),
d
6.77 (dd, J ¼ 15.8, 10.6 Hz, 1H), 6.74e6.70 (m, 1H), 6.64 (dd, J ¼ 8.6,
1.0 Hz, 2H), 6.51 (d, J ¼ 15.7 Hz, 1H), 6.42 (dd, J ¼ 15.2, 10.5, 0.6 Hz,
1H), 5.97e5.86 (m, 1H), 3.86 (dd, J ¼ 5.8,1.2 Hz, 2H), 3.81 (s, 1H); 13
C
(b) P.S. Wang, P. Liu, Y.J. Zhai, H.C. Lin, Z.Y. Han, L.Z. Gong, J. Am. Chem. Soc.
137 (2015) 12732;
(c) H.C. Lin, P.S. Wang, Z.L. Tao, Y.G. Chen, Z.Y. Han, L.Z. Gong, J. Am. Chem. Soc.
138 (2016) 14354;
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56 (2017) 16032;
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(2018) 4740;
(g) Z. Xiao-Le, S. Yong-Liang, W. Pu-Sheng, G. Liu-Zhu, Hua Hsueh Hsueh Pao
76 (2018) 857;
(h) L.-F. Fan, S.-W. Luo, S.-S. Chen, T.-C. Wang, P.-S. Wang, L.-Z. Gong, Angew.
Chem. Int. Ed. 58 (2019) 16806;
(i) L.-F. Fan, T.-C. Wang, P.-S. Wang, L.-Z. Gong, Organometallics 38 (2019)
4014;
NMR (101 MHz, CDCl3)
d 148.10, 137.31, 132.25, 132.07, 131.33,
129.39, 128.73,128.42, 127.64, 126.44,117.72, 113.13, 46.02; IR (KBr):
g
3413, 2924, 1602, 1503, 1260, 989, 747, 691 cmꢁ1; HRMS (ESI)
calculated for C17H17N [MþH]þ: 236.1434, found 236.1430.
Declaration of competing interest
The authors declare that they have no known competing
financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
(j) H.C. Lin, P.P. Xie, Z.Y. Dai, S.Q. Zhang, P.S. Wang, Y.G. Chen, T.C. Wang,
X. Hong, L.Z. Gong, J. Am. Chem. Soc. 141 (2019) 5824;
(k) T.C. Wang, P.S. Wang, L.Z. Gong, Sci. China Chem. 63 (2020) 454;
(l) P.S. Wang, L.Z. Gong, Acc. Chem. Res. (2020), https://doi.org/10.1021/
acs.accounts.0c00477.
Acknowledgments
We are grateful for financial support from the Ministry of Sci-
ence and Technology of China (2015CB856600), the NSFC
(21831007, 21672197), the Chinese Academy of Sciences (Grant No.
XDB20020000) and Youth Innovation Promotion Association CAS is
gratefully acknowledged.
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Appendix A. Supplementary data
[12] M.P. Carroll, P.J. Guiry, Chem. Soc. Rev. 43 (2014) 819.
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Supplementary data to this article can be found online at
https://doi.org/10.1016/j.tet.2021.131996.
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