One-pot synthesis of allylamine derivatives by iodine-catalyzed three-component reaction of N-heterocycles, paraformaldehyde and styrenes

Article abstract of DOI:10.1002/adsc.201201097

The molecular iodine-catalyzed three-component reaction of amides or amide derivatives, paraformaldehyde and styrenes allows for the clean generation of allylamine derivatives in good yields and high regioselectivities. The reaction, forming water as the

Full text of DOI:10.1002/adsc.201201097

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DOI: 10.1002/adsc.201201097
One-Pot Synthesis of Allylamine Derivatives by Iodine-
Catalyzed Three-Component Reaction of N-Heterocycles,
Paraformaldehyde and Styrenes
Zheng-Jun Quan,a,* Wang-Hua Hu,a Zhang Zhang,a Yu-Xia Da,a Xiao-Dong Jia,a
and Xi-Cun Wanga,*
a
Key Laboratory of Eco-Environment-Related Polymer Materials, Ministry of Education, China. Gansu Key Laboratory of
Polymer Materials, College of Chemistry and Chemical Engineering, Northwest Normal University, Lanzhou, Gansu
730070, Peopleꢀs Republic of China
Fax : (+86)-931-797-2626; e-mail: quanzhengjun@hotmail.com or wangxicun@nwnu.edu.cn
Received: December 17, 2012; Revised: January 20, 2013; Published online: March 15, 2013
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201201097.
Abstract: The molecular iodine-catalyzed three-
component reaction of amides or amide derivatives,
paraformaldehyde and styrenes allows for the clean
generation of allylamine derivatives in good yields
and high regioselectivities. The reaction, forming
water as the sole co-product, is an experimentally
easy to conduct transformation in the absence of
transition metals under mild conditions.
tion of allylic alcohols[4] and their derivatives,[5–8] as
one of the most important processes for allylamines,
has been studied intensively [Scheme 1, path (a)].
However, with respect to green chemistry, it is impor-
tant to note that most such substitutions used allylic
alcohol derivatives as substrates generating at least
stoichiometric amounts of waste. Moreover, the corre-
sponding activated substrates have to be prepared in
additional steps lowering the overall efficiency of
a given synthesis. In the last two decades the direct al-
lylic amination of free allylic alcohols has been inten-
sively studied using acids[9–11] and various transition
metals[12–14] as catalysts. Alternatively, the reductive
amination of cinnamaldehyde giving allylamines has
been reported by some groups [Scheme 1, path
(b)].[15–17]
À
À
Keywords: allylamines; C C bond formation; C N
bond formation; multi-component reaction; N-het-
erocycles
The allylamines are of great importance in organic
Therefore, a method without preactivation of the
synthesis. They are found in a wide variety of bioac- starting materials generating small amounts of by-
tive products,[1,2] and are valuable synthetic intermedi- products such as water as the only co-product to
ates to a range of products.[2,3] Therefore, developing streamline organic synthesis and to improve the atom
chemical synthesis methods for allylamines is an im- efficiency is still needed in this area. A highly valua-
portant research field in industry as well as in aca- ble alternative reaction pathway would be direct ami-
demia. The transition metal-mediated allylic amina- noalkylation of a styrene/olefin. While reports of such
Scheme 1. Synthesis of allylamine derivatives.
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Table 1. Optimization of the three-component reaction conditions.[a]
Entry
Catalysis (mol/%)
Solvent
Temperature [8C]
Time [h]
Yield [%][b]
1
2
3
4
5
6
7
8
p-TSA (10)
TFA
xylene
xylene
xylene
xylene
DMSO
DMF
dioxane
dioxane
dioxane
dioxane
dioxane
dioxane
dioxane
toluene
DMF
150
150
150
120
150
150
110
110
110
110
110
110
110
110
110
110
90
12
12
12
12
12
12
12
12
12
12
12
12
12
24
12
12
24
40
35
45
trace
35
30
30
trace
trace
trace
76
72
75
60
trace
50
TfOH (10)
TfOH (10)
TfOH (10)
TfOH (10)
TfOH (10)
FeCl3 (20)
TMSCl (20)
BF3·OEt2 (20)
I2(20)/TfOH (20)
FeCl3(20)/TfOH (20)
I2 (20)
9
10
11
12
13
14
15
16
17
I2 (20)
I2 (20)
I2 (10)
I2 (20)
dioxane
dioxane
45
[a]
Reaction conditions: 1a (0.5 mmol), paraformaldehyde (2.0 mmol), 2a (1.0 mmol), catalyst, solvent (3 mL).
Isolated yield of 3a after purification by flash chromatography.
[b]
process directly using styrenes or olefins as substrates
A few methods for allylamine derivatives with
are rare, and only a few examples were reported amides or electron-deficient heterocycles are known
using the palladium-catalyzed Heck reaction of allyl- by applying transition metals or Lewis acids as cata-
ACHTUNGTRENNUNG
amines with aryl iodide or arenediazonium salts.[18] To lysts, whereby most of these existing methods require
this date, simple styrene has never been used for the large catalyst loadings, high reaction temperature or
direct allylic alkylation. involve the use of additives for the amination reac-
On the other hand, reactions between N-acylimini- tion.[22]
um ions and nucleophiles have been frequently used
Based on the wide ranging biological activity of 3,4-
to introduce substituents at the a-carbon of an dihydropyrimidinones (DHPMs)[23] and their utiliza-
amine.[19] The aza-Prins cyclization, which uses al- tion as important precursors in the synthesis of pyri-
kenes or alkynes as intramolecular nucleophile midine bases,[24] combined with our previous experi-
through formaldiminium ions, was also widely ap- ence on the synthesis of 3,4-dihydropyrimidinone de-
plied.[20] In particularly, almost no intermolecular re- rivatives,[25] we initially chose the reaction of the
actions of nucleophilic styrenes into iminium cations easily available 3,4-dihydropyrimidinones as a typical
for the construction of allylamines are known. Al- reaction to optimize the reaction conditions.
though the allylation of imines was reported, most of
Reaction optimization studies were conducted with
these existing methods require electron-rich precur- DHPM (1a), paraformaldehyde and styrene (2a)
sors (allylboronic acid ester and cyclic boronates), (Table 1). When p-toluenesulfonic acid (p-TSA), tri-
strong bases, involve the use of additives for the addi- fluoroacetic acid (TFA), and trifluoromethanesulfonic
tion reaction or are accompanied by the formation acid (TfOH) (entries 1–7) were used as the catalysts,
unexpected by-products.[21]
the product 3a was obtained at 1508C, albeit in lower
Herein we present the first I2-catalyzed one-pot yields (35–45%). Only a trace amount of product was
multi-component synthesis of allylamine derivatives observed when the reaction was carried out at 1208C
from N-heterocycles or amides, paraformaldehyde using TfOH as catalyst (entry 4). Lewis acid catalysts
and styrenes [Scheme 1, path (c)]. This direct method such FeCl3, trimethylsilyl chloride (TMSCl) as
from unactivated styrenes does not need any additives BF3·OEt were not effective for this reaction (en-
and proceeds with high regioselectivity, which forms tries 8–10). Good reaction yield and activity were ob-
water as the sole by-product and can be considered as served when using I2 or FeCl3 combined with TfOH
an environmental friendly, sustainable and atom eco- (entries 11 and 12) as the catalysts, which provided
nomical process.
the product in good yields of 76% and 72%, respec-
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One-Pot Synthesis of Allylamine Derivatives by Iodine-Catalyzed Three-Component Reaction
A variety of amides were investigated next using
paraformaldehyde and styrenes (2a–c) in the three-
component reaction (Table 3). It turned out that dif-
ferent amides including cyclic amides and acyclic
amides can used to give products in good yields and
high stereochemical selectivities under modified reac-
tion conditions. Using a combined catalyst system of
30 mol% I2 and 2 mol% of TfOH in xylene at 1108C,
the amides, piperidin-2-one (5a), and azepan-2-one
(5b), with paraformaldehyde and styrenes reacted
smoothly to afford the allylamine derivatives 6a–6e in
good yields (70–83%). The reaction also works with
N-phenylacetamide (5c) and N-(2,6-dimethylpheny-
l)acetamide (5d) to give the desired products in good
yields (6f, 6g). The amides with a non-bulky group on
the N-atom such as N-methylbenzamide (5e) and N-
benzylbenzamide (5f) also produced the (E)-allyla-
mides 6h and 6i, however, the NMR spectra of 6h and
6i at ambient temperature are complicated. Most
probably, the reaction of 5e or 5f gives two epimers
À
Figure 1. X-ray structure of compound 3a.
tively. It revealed that the reaction was best-conduct- due to the rotation around the C N bond. The epi-
ed using 0.2 equivalents of molecular iodine as the mers behave very similar and separation by simple
catalyst in 1,4-dioxane as the solvent at 1108C for column chromatography was not possible. Later, the
12 h, and the desired product was isolated in 75% structure of 6h was confirmed by H,H-COSY,
yield (entry 13). In toluene, the reaction gave a lower HMQC, HMBC and NOESY experiments. Finally,
yield of 60% within 24 h (entry 14), but solvent DMF 1H NMR spectrum of 6h was simplified at 508C
has a negative effect on the reaction, and only a trace (Figure 2), which confirmed the appearance of epi-
amount of product was observed (entry 15). Decreas- mers. In every cases, the reaction proceeded with very
ing the catalyst loading of I2 to 10 mol% resulted in high stereochemical control in favour of the E-isomer
considerably lower yield (entry 16). Other tempera- (E/Z>25:1) (only E-isomer was isolated by flash
tures were also screened but 1108C was necessary for chromatography).
successful reaction (entry 17). It should be noted that
The
reaction
using
electron-deficient
N-
in any case, the E-isomer 3a was the major product phenylbenzAHCTUNGTRaENNUNG mide (5g) provided only trace amount of
and only a trace amount of the Z-isomer 4a was de- 6j but gave as a cyclization product 3,4-dihydroquino-
1
termined by H NMR analysis of the crude reaction line 7 in 70% yield, suggesting a carbocation inter-
mixture (E/Z>25:1). The crude product after purifi- mediate and an aza-Prins cyclization/intramolecular
cation by flash chromatography was recrystallized Friedel–Crafts reaction (Scheme 2).
(EtOH) to give the pure E-isomer 3a. The structure
When the aliphatic olefin ethyl acrylate and cyclo-
of 3a was unambiguously determined by NMR spec- penta-1,3-diene were used, no reaction occurred and
troscopy and X-ray crystallography (Figure 1).[26]
Under the optimized conditions we explored the
the starting materials were obtained.
On the basis of the observations described above
scope of this transformation by varying DHPM and and reported previously,[25b,c] a possible mechanism for
styrene reaction partners. DHPM 1a–j with parafor- the present I2-catalyzed allylic alkylation of DHPMs
maldehyde and styrene (2a), 4-methyl-substituted sty- can be proposed as shown in Scheme 3. 3,4-Dihydro-
rene (2b) or 4-bromo-substituted styrene (2c) to give pyrimidinone 1 reacts with paraformaldehyde leading
the regioselective E-type products 3b–p in good yields to the formation of acyliminium ion A as a strong
(52–82%) (Table 2). Both electron-withdrawing (NO2, electrophile, whose formation is supported by the
Cl and F) and electron-donating groups (Me and HR-MS experimental results (A was detected at
MeO) on the aryl ring of DHPMs were well tolerated. m/z=273, 274 for the reaction of 1a with paraformal-
Steric effects due to the installation of ortho substitu- dehyde and styrene 2a). Intermediate A can be stabi-
ents (2-MeO, and 2-Cl) were negligible. The reaction lized by the conjugation of the carbonyl C=O double
of electron-deficient 4-bromostyrene 2c gave the ally- bond.[20b,22] An electrophilic addition of A to the sty-
lated products (3o, 3p) in moderate yields. Remarka- rene would be preferred because of possible forma-
bly, in every case, the three-component reaction pro- tion of a stable benzallylic species such as B and C,
ceeded with very high regio- and stereochemical con- which on subsequent deprotonation should be steri-
trol in favour of the E-isomer (only E-isomer was iso- cally favoured to afford the thermodynamically con-
lated).
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Table 2. Three-component reaction of DHPMs, styrenes and paraformaldehyde.[a]
[a]
1
Yields of isolated products. Ratio of E-isomer to Z-isomer determined by H NMR analysis of the extracted (EtOAc)
crude reaction mixture (E/Z>25:1).
trolled (E)-type product 3 as the dominant reaction
compared to the formation of (Z)-type 4.
In summary, we have developed an efficient metal-
free multi-component process for allylamine deriva-
Finally, we demonstrated the utility of this protocol tives with remarkable regio- and stereochemical selec-
in the synthesis of the key intermediate for Naftifine tivities. The procedure uses readily available DHPMs/
(Scheme 4). It is well known that Naftifine is a com- amides, paraformaldehyde and unactivated styrenes
mercial drug possessing high antifungal activity.[1a,b] as starting materials catalyzed by I2. The reaction is
To our delight, the three-component reaction of 9[27] atom-economic as water is the sole by-product and
with 2a and paraformaldehyde in the presence of does not need any additives. The extensive availability
20 mol% I2 and 2 mol% TfOH afforded a 65% yield of reaction partners suggests new possibilities for the
of 10a (E/Z>20:1), which is the key intermediate for synthesis of highly functionalized compounds under
the Naftifine. According to the literature,[18a] 10a can these three-component conditions. As an example for
be reduced by LiAlH4 giving Naftifine. Similarly, the the synthetic utility, the key intermediate for Naftifine
reaction of 9 with 2b yielded the allylic product 10b was shown.
in 70% yield (E/Z>25:1).
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One-Pot Synthesis of Allylamine Derivatives by Iodine-Catalyzed Three-Component Reaction
Table 3. Three-component reaction of amides, styrenes and paraformaldehyde.[a]
[a]
1
Yields of isolated products. The ratio of E-isomer to Z-isomer were determined by H NMR
analysis of the extracted (EtOAc) crude reaction mixture (E/Z> 25:1).
Figure 2. 1H NMR of 6h at room temperature (top) and 1H NMR at 508C (bottom).
1.0 mmol, 30.0 mg), styrene (2, 2 equiv., 1.0 mmol, 104.0 mg)
and 1,4-dioxane (3 mL). Then I2 (0.2 equiv., 0.1 mmol,
Experimental Section
25.4 mg) was added and the reaction mixture was stirred at
1108C. After the starting material 1 had been consumed
(monitored by TLC), 15 mL water were added and the mix-
ture was extracted with EtOAc 3 times (3ꢂ 15 mL). The ex-
General Procedure for MCR Reactions
To a round-bottomed flask, under air, were added DHPM
(1, 0.5 mmol, 130.0 mg), paraformaldehyde (4 equiv.,
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Scheme 2. Aza-Prins cyclization and intramolecular Friedel–
Crafts reaction.
Scheme 4. Synthesis of the Naftifine derivatives by the
MCR.
tract was washed with 10% Na2S2O3 solution (w/w), dried
over anhydrous Na2SO4 and evaporation. The product was
purified by flash chromatography on silica gel using petrole-
um ether/ethyl acetate as eluent to provide the correspond-
ing allylamine.
1H NMR (400 MHz, CDCl3): d=8.35 (brs, 1H, NH), 7.36–
7.24 (m, 7H), 6.84 (d, J=8.8 Hz, 2H), 6.49 (d, J=15.6 Hz,
1H), 6.12–6.04 (m, 1H), 5.29 (s, 1H), 4.63 (dd, J=15.4 Hz,
6.6 Hz, 1H), 4.14–3.99 (m, 2H), 3.78 (s, 3H), 3.46 (dd, J=
15.2 Hz, 8.0 Hz, 1H), 2.34 (s, 3H), 1.17 (t, J=7.2 Hz, 3H);
13C NMR (100 MHz, CDCl3): d=165.6, 159.2, 152.7, 145.9,
136.5, 134.0, 133.3, 128.7, 128.5, 127.7, 126.4, 124.0, 113.8,
101.7, 59.9, 58.8, 55.2, 46.2, 18.6, 14.2; HR-MS: m/z=
407.1968 [M+H]+, calcd. for C24H26N2O4: 407.1965.
(E)-Ethyl 3-cinnamyl-6-methyl-2-oxo-4-phenyl-1,2,3,4-tet-
rahydropyrimidine-5-carboxylate (3a): white solid; yield:
141.1 mg (0.38 mmol, 75%); mp 198–1998C; 1H NMR
(400 MHz, CDCl3): d=8.52 (brs, 1H, NH), 7.38–7.24 (m,
10H), 6.51 (d, J=16.0 Hz, 1H), 6.12–6.05 (m, 1H), 5.35 (s,
1H), 4.66 (dd, J=15.4 Hz, 5.0 Hz, 1H), 4.14–3.99 (m, 2H),
3.45 (dd, J=15.2 Hz, 8.0 Hz, 1H), 2.35 (s, 3H), 1.16 (t, J=
7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3): d=165.6, 152.9,
146.4, 146.3, 141.8, 136.5, 133.4, 128.5, 128.4, 128.0, 127.7,
127.5, 126.4, 123.9, 101.4, 59.9, 59.3, 46.4, 18.6, 14.1; HR-MS:
m/z= 377.1863 [M+H]+, calcd for C23H24N2O3: 377.1860.
(E)-Ethyl 3-cinnamyl-6-methyl-2-oxo-4-p-tolyl-1,2,3,4-tet-
rahydropyrimidine-5-carboxylate (3b): white solid; yield:
144.4 mg (0.37 mmol, 74%); mp 179–1808C; 1H NMR
(400 MHz, CDCl3): d=8.72 (brs, 1H, NH), 7.29–7.36 (m,
4H), 7.27–7.22 (m, 3H), 7.12 (d, J=8.0 Hz, 2H), 6.49 (d, J=
16.0 Hz, 1H), 6.12–6.04 (m, 1H), 5.31 (s, 1H), 4.64 (dd, J=
15.4 Hz, 5.0 Hz, 1H), 4.13–3.99 (m, 2H), 3.45 (dd, J=
15.8 Hz, 7.8 Hz, 1H), 2.34 (s, 3H), 2.32 (s, 3H), 1.17 (t, J=
7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3): d=165.6, 153.0,
146.3, 138.9, 137.7, 136.5, 133.3, 129.2 128.5, 127.6, 127.4,
126.4, 123.9, 101.5, 59.9, 59.0, 46.3, 21.1, 18.5, 14.1; HR-MS:
m/z=391.2020 [M+H]+, calcd. for C24H26N2O3: 391.2016.
(E)-Ethyl
3-cinnamyl-4-(3-methoxyphenyl)-6-methyl-2-
white
oxo-1,2,3,4-tetrahydropyrimidine-5-carboxylate(3d):
solid; yield: 132.0 mg (0.33 mmol, 65%); mp 188–1898C;
1H NMR (400 MHz, CDCl3): d=8.52 (brs, 1H, NH), 7.36–
7.29 (m, 4H), 7.27–7.22 (m, 2H), 6.97 (d, J=8.0 Hz, 1H),
6.92–6.91 (m, 1H), 6.81 (dd, J=8.0, 2.4 Hz, 1H), 6.51 (d, J=
15.6 Hz, 1H), 6.13–6.06 (m, 1H), 5.32 (s, 1H), 4.65 (dd, J=
15.4 Hz, 5.0 Hz, 1H), 4.15–4.00 (m, 2H), 3.78 (s, 3H), 3.46
(dd, J=15.9, 8.0 Hz, 1H), 2.35 (s, 3H), 1.17 (t, J=7.0 Hz,
3H); 13C NMR (100 MHz, CDCl3): d=165.6, 159.7, 152.8,
146.4, 143.4, 136.5, 133.4, 129.5, 128.5, 127.7, 126.4, 123.8,
119.7, 113.6, 112.8, 101.3, 59.9, 59.2, 55.2, 46.4, 18.6, 14.2;
HR-MS: m/z=407.1969 [M+H]+, calcd. for C24H26N2O4:
407.1965.
(E)-Ethyl
3-cinnamyl-4-(2-methoxyphenyl)-6-methyl-2-
oxo-1,2,3,4-tetrahydropyrimidine-5-carboxylate (3e): white
solid; yield: 146.2 mg (0.36 mmol, 72%); mp 189–1908C;
1H NMR (400 MHz, CDCl3): d=7.86 (brs, 1H, NH), 7.33–
7.28 (m, 5H), 7.24–7.21 (m, 2H), 6.93–6.84 (m, 2H), 6.48 (d,
J=16.0 Hz, 1H), 6.12–6.05 (m, 1H), 5.75 (s, 1H), 4.48 (dd,
(E)-Ethyl
oxo-1,2,3,4-tetrahydropyrimidine-5-carboxylate
solid; yield: 158.4 mg (0.39 mmol, 78%); mp 179–1808C;
3-cinnamyl-4-(4-methoxyphenyl)-6-methyl-2-
(3c):white
Scheme 3. The proposed mechanism.
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One-Pot Synthesis of Allylamine Derivatives by Iodine-Catalyzed Three-Component Reaction
J=15.2, 4.4 Hz, 1H), 4.05–3.92 (m, 2H), 3.85 (s, 3H), 3.52
(dd, J=14.2, 7.4 Hz, 1H), 2.36 (s, 3H), 1. 8 (t, J=7.2 Hz,
3H); 13C NMR (100 MHz, CDCl3): d=165.7, 157.0, 146.3,
136.8, 132.8, 129.8, 129.7, 129.2, 128.5, 127.5, 126.4, 124.4,
120.7, 110.6, 110.3, 59.7, 55.4, 54.4, 46.4, 18.5, 14.0; HR-MS:
m/z=407.1972 [M+H]+, calcd. for C24H26N2O4: 407.1965.
(E)-Ethyl 4-(4-chlorophenyl)-3-cinnamyl-6-methyl-2-oxo-
1,2,3,4-tetrahydropyrimidine-5-carboxylate (3f): white solid;
(s, 3H), 1.19 (t, J=7.2 Hz, 3H); 13C NMR (100 MHz,
CDCl3): d=165.1, 152.6, 148.2, 147.4, 144.1, 136.1, 134.1,
133.4, 129.8, 128.6, 128.0, 126.4, 123.2, 123.0, 122.6, 100.5,
60.3, 59.0, 46.9, 18.6, 14.1; HR-MS: m/z=422.1705 [M+H]+,
calcd. for C23H23N3O5: 422.1710.
(E)-Ethyl
6-methyl-2-oxo-4-phenyl-3-(3-p-tolylallyl)-
1,2,3,4-tetrahydropyrimidine-5-carboxylate (3k): white solid;
1
yield: 152.2 mg (0.39 mmol, 78%); mp. 219–2208C; H NMR
1
yield: 145.6 mg (0.36 mmol, 71%); mp 142–1438C; H NMR
(400 MHz, CDCl3): d=8.62 (brs, 1H, NH), 7.38–7.26 (m,
5H), 7.24 (d, J=8.4 Hz, 2H), 7.12 (d, J=8.0 Hz, 2H), 6.47
(d, J=16.0 Hz, 1H), 6.06–5.99 (m, 1H), 5.34 (s, 1H), 4.68–
4.63 (m, 1H), 4.13–3.98 (m, 2H), 3.36 (dd, J=15.2, 8.0 Hz,
1H), 2.35 (s, 3H), 2.34 (s, 3H), 1.16 (t, J=7.2 Hz, 3H);
13C NMR (100 MHz, CDCl3): d=165.6, 152.9 and 152.9
146.4 and 146.4, 141.8, 137.5, 133.7, 133.3, 129.2, 128.5, 127.9,
127.5, 126.3, 122.7, 101.4, 59.9, 59.2, 46.3, 21.2, 18.6, 14.1;
HR-MS: m/z=391.2029 [M+H]+, calcd. for C24H26N2O3:
391.2026.
(400 MHz, CDCl3): d=8.75 (brs, 1H, NH), 7.35–7.23 (m,
9H), 6.49 (d, J=16.0 Hz, 1H), 6.10–6.02 (m, 1H), 5.33 (s,
1H), 4.65 (dd, J=15.6 Hz, 5.2 Hz, 1H), 4.15–4.00 (m, 2H),
3.44 (dd, J=16.0 Hz, 8.0 Hz, 1H), 2.35 (s, 3H), 1.17 (t, J=
7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3): d=165.4, 152.9,
146.6, 140.4, 136.3, 133.7, 133.6, 128.8, 128.7, 128.6, 127.8,
126.4,123.6, 101.1, 60.0, 58.7, 46.4, 18.6, 14.2; HR-MS: m/z=
411.1466 [M+H]+, calcd. for C23H23ClN2O3: 411.1470.
(E)-Ethyl 4-(2-chlorophenyl)-3-cinnamyl-6-methyl-2-oxo-
1,2,3,4-tetrahydropyrimidine-5-carboxylate (3g): white solid;
(E)-Ethyl
6-methyl-2-oxo-4-p-tolyl-3-(3-p-tolylallyl)-
1
yield: 139.5 mg (0.34 mmol, 68%); mp 218–2198C; H NMR
1,2,3,4-tetrahydropyrimidine-5-carboxylate (3l): white solid;
1
(400 MHz, CDCl3): d=8.51 (brs, 1H, NH), 7.52 (dd, J=7.6,
1.6 Hz, 1H), 7.32–7.16 (m, 8H), 6.57 (d, J=15.6 Hz, 1H),
6.12–6.05 (m, 1H), 5.90 (s, 1H), 4.50–4.44 (m, 1H), 4.08–
3.96 (m, 2H), 3.59 (dd, J=15.2, 7.2 Hz, 1H), 2.40 (s, 3H),
1.11 (t, J=7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3): d=
165.3, 152.1, 147.2, 140.1, 136.7, 133.0, 132.9, 130.0, 129.3,
129.2, 128.4, 127.8, 127.6, 126.4, 123.8, 100.7, 59.9, 56.2, 46.6,
18.4, 14.0; HR-MS: m/z=411.1474 [M+H]+, calcd. for
C23H23ClN2O3: 411.1470.
yield: 165.7 mg (0.41 mmol, 82%); mp 192–1938C; H NMR
(400 MHz, CDCl3): d=8.37 (brs, 1H, NH), 7.26–7.23 (m,
3H), 7.12 (d, J=7.6 Hz, 5H), 6.46 (d, J=15.6 Hz, 1H),
6.06–5.99 (m, 1H), 5.30 (s, 1H), 4.65 (dd, J=15.2, 4.8 Hz,
1H), 4.11–3.00 (m, 2H), 3.40 (dd, J=15.2, 8.0 Hz, 1H), 2.33
(d, J=5.2 Hz, 9H), 1.17 (t, J=7.0 Hz, 3H); 13C NMR
(100 MHz, CDCl3): d=165.4, 147.2, 140.1, 137.4, 133.9,
132.9, 129.2, 129.1, 127.7, 126.3, 122.7, 109.7, 100.6, 59.9,
56.2, 46.6, 21.2, 18.4, 14.0; HR-MS: m/z=405.2176 [M+H]+,
calcd. for C25H28N2O3: 405.2173.
(E)-Ethyl 3-cinnamyl-4-(4-fluorophenyl)-6-methyl-2-oxo-
1,2,3,4-tetrahydropyrimidine-5-carboxylate (3h): white solid;
(E)-Ethyl 4-(4-fluorophenyl)-6-methyl-2-oxo-3-(3-p-toly-
1
yield: 197.1 mg (0.35 mmol, 69%); mp 172–1738C; H NMR
lallyl)-1,2,3,4-tetrahydropyrimidine-5-carboxylate
(3m):
(400 MHz, CDCl3): d=8.63 (brs, 1H, NH), 7.36–7.30 (m,
6H), 7.27–7.24 (m, 2H), 7.00 (t, J=8.6 Hz, 2H), 6.50 (d, J=
15.6 Hz, 1H), 6.11–6.03 (m, 1H), 5.33 (s, 1H), 4.64 (dd, J=
15.4 Hz, 5.0 Hz, 1H), 4.15–3.99 (m, 2H), 3.44 (dd, J=
15.4 Hz, 7.8 Hz, 1H), 2.36 (s, 3H), 1.16 (t, J=7.2 Hz, 3H);
13C NMR (100 MHz, CDCl3): d=165.5, 163.6, 161.1, 152.8,
146.4, 137.8, 137.7, 136.4, 133.5, 129.2, 129.1, 128.6, 127.8,
126.4, 123.7, 115.5, 115.3, 101.4, 60.0, 58.7, 46.4, 18.6, 14.2;
HR-MS: m/z=395.1770 [M+H]+, calcd. for C23H23FN2O3:
395.1765.
white solid; yield: 142.9 mg (0.35 mmol, 70%); mp 154–
1558C; H NMR (400 MHz, CDCl3): d=8.97 (brs, 1H, NH),
1
7.34 (dd, J=8.4, 5.2 Hz, 2H), 7.24 (d, J=8.4 Hz, 2H), 7.12
(d, J=8.0 Hz, 2H), 6.70 (t, J=8.6 Hz, 2H), 6.47 (d, J=
16.0 Hz, 1H), 6.05–5.98 (m, 1H), 5.33 (s, 1H), 4.65 (dd, J=
15.2, 4.8 Hz, 1H), 4.12–4.00 (m, 2H), 3.36 (dd, J=15.6,
8.0 Hz, 1H), 2.36 (s, 3H), 2.34 (s, 3H), 1.16 (t, J=7.2 Hz,
3H); 13C NMR (100 MHz, CDCl3): d=165.5, 163.5, 161.1,
152.9, 146.6, 137.8, 137.6, 133.6, 133.5, 129.2, 129.1, 126.3,
122.5, 115.5, 115.2, 101.3, 59.9, 58.6, 46.3, 21.2, 18.5, 14.1;
HR-MS: m/z=409.1925 [M+H]+, calcd. for C24H25FN2O3:
409.1922.
(E)-Ethyl 4-(2-chlorophenyl)-6-methyl-2-oxo-3-(3-p-toly-
lallyl)-1,2,3,4-tetrahydropyrimidine-5-carboxylate (3n): white
solid; yield: 144.2 mg (0.34 mmol, 68%); mp 227–2288C;
1H NMR (400 MHz, CDCl3): d=8.46 (brs, 1H, NH), 7.52 (d,
J=7.6 Hz, 1H), 7.31 (d, J=7.6 Hz, 1H), 7.24–7.16 (m, 4H),
7.10 (d, J=8.0 Hz, 2H), 6.54 (d, J=16.0 Hz, 1H), 6.07–6.00
(m, 1H), 5.89 (s, 1H), 4.46 (dd, J=15.2, 5.2 Hz, 1H), 4.07–
3.95 (m, 2H), 3.56 (dd, J=15.4, 7.4 Hz, 1H), 2.40 (s, 3H),
2.33 (s, 3H), 1.11 (t, J=7.2 Hz, 3H); 13C NMR (100 MHz,
CDCl3): d=165.4, 147.2, 140.1, 137.4, 133.9, 132.9, 129.2,
130.0, 129.1, 127.7, 126.3, 122.7, 109.7, 100.6, 59.9, 56.2, 46.6,
21.2, 18.4, 14.0; HR-MS: m/z=425.1630 [M+H]+, calcd. for
C24H25ClN2O3: 425.1626.
(E)-Ethyl 3-cinnamyl-6-methyl-4-(4-nitrophenyl)-2-oxo-
1,2,3,4-tetrahydropyrimidine-5-carboxylate (3i): white solid;
1
yield: 141.1 mg (0.34 mmol, 67%); mp 183–1848C; H NMR
(400 MHz, CDCl3): d=9.12 (brs, 1H, NH), 8.20–8.17 (m,
2H), 7.58–7.55 (m, 2H), 7.33–7.25 (m, 5H), 6.49 (d , J=
15.6 Hz, 1H), 6.10–6.02 (m, 1H), 5.48 (d, J=4.0 Hz, 1H),
4.67–4.63 (m, 1H), 4.15–4.05 (m, 2H), 3.52–3.46 (m, 1H),
2.38 (d, J=4.4 Hz, 3H), 1.22–1.17 (m, 3H); 13C NMR
(100 MHz, CDCl3): d=165.2, 152.8, 149.0, 147.5, 147.4,
136.0, 134.0, 128.6, 128.3, 128.0, 126.3, 123.9, 123.1, 100.5,
60.3, 58.9 46.9, 18.7, 14.2; HR-MS: m/z=422.1714 [M+H]+,
calcd. for C23H23N3O5: 422.1710.
(E)-Ethyl 3-cinnamyl-6-methyl-4-(3-nitrophenyl)-2-oxo-
1,2,3,4-tetrahydropyrimidine-5-carboxylate (3j): white solid;
1
yield: 126.4 mg (0.30 mmol, 60%); mp 149–1508C; H NMR
(400 MHz, CDCl3): d=8.91 (brs, 1H, NH), 8.22 (s, 1H),
8.14–8.12 (m, 1H), 7.74 (d, J=7.6 Hz, 1H), 7.52 (t, J=
8.0 Hz, 1H), 7.33–7.26 (m, 5H), 6.50 (d, J=15.6 Hz, 1H),
6.10–6.03 (m, 1H), 5.48 (s, 1H), 4.66 (dd, J=15.2, 5.2 Hz,
1H), 4.17–4.01 (m, 2H), 3.50 (dd, J=15.4, 7.8 Hz, 1H), 2.39
(E)-Ethyl
3-[3-(4-bromophenyl)allyl]-6-methyl-2-oxo-4-
(3o):
phenyl-1,2,3,4-tetrahydropyrimidine-5-carboxylate
white solid; yield: 118.1 mg (0.26 mmol, 52%); mp 234–
1
2358C; H NMR (400 MHz, CDCl3): d=8.38 (brs, 1H, NH),
7.44–7.42 (m, 2H), 7.37–7.28 (m, 5H), 7.18 (d, J=8.4 Hz,
Adv. Synth. Catal. 2013, 355, 891 – 900
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Zheng-Jun Quan et al.
COMMUNICATIONS
2H), 6.42 (d, J=15.6 Hz, 1H), 6.09–6.02 (m, 1H), 5.32 (s,
1H), 4.58 (dd, J=15.4, 5.0 Hz, 1H), 4.15–4.00 (m, 2H), 3.50
(dd, J=15.4, 7.8 Hz, 1H), 2.35 (s, 3H), 1.18 (t, J=7.0 Hz,
3H); 13C NMR (100 MHz, CDCl3): d=165.6, 152.9, 146.3,
141.8, 135.4, 132.0, 131.6, 128.6, 128.0, 127.9, 127.4, 124.8,
121.5, 101.5, 60.0, 59.6, 46.5, 18.6, 14.2; HR-MS: m/z=
455.0968 [M+H]+, calcd. for C23H23BrN2O3: 455.0965.
4.14 (d, J=6.4, 2H), 3.35–3.33 (m, 2H), 2.58 (d, J=6.0 Hz,
2H), 1.72 (s, 4H), 1.62 (s, 2H); 13C NMR (100 MHz,
CDCl3): d=175.7, 135.6, 131.6, 131.2, 127.9, 126.1, 121.3,
49.8, 48.8, 37.2, 29.9, 28.5, 23.4; HR-MS: m/z=308.0649
[M+H]+, calcd. for C15H18BrNO: 308.0645.
(E)-N-Phenyl-N-(3-phenylallyl)-acetamide (6f): colourless
oil; yield: 97.9 mg (0.39 mmol, 78%); 1H NMR (400 MHz,
CDCl3): d=7.42–7.13 (m, 10H), 6.37 (d, J=16.0 Hz, 1H),
6.31–6.24 (m, 1H), 4.45 (d, J=7.2 Hz, 1H), 1.87–1.83 (m,
3H); 13C NMR (100 MHz, CDCl3): d=170.1, 142.9, 136.6,
133.2, 129.6, 128.5, 128.1, 127.9, 127.6, 126.4, 124.4, 51.5,
22.7; HR-MS: m/z=252.1386 [M+H]+, calcd. for
C17H17NO: 252.1383.
(E)-N-Cinnamyl-N-(2,5-dimethylphenyl)-acetamide (6g):
colourless oil; yield: 97.9 mg (0.35 mmol, 70%); 1H NMR
(400 MHz, CDCl3): d=7.32–7.20 (m, 5H), 7.16 (d, J=
7.6 Hz, 1H), 7.06 (d, J=8.0 Hz, 1H), 6.89 (s, 1H), 6.37 (d,
J=16.0 Hz, 1H), 6.32–6.25 (m, 1H), 4.66 (dd, J=14.2,
6.2 Hz, 1H), 4.03 (dd, J=14.4, 6.8 Hz, 2H), 2.29 (s, 3H),
2.18 (s, 3H), 1.18 (s, 3H); 13C NMR (100 MHz, CDCl3): d=
170.4, 141.3, 136.9, 136.8, 133.3, 132.4, 131.1, 129.4, 129.1,
128.5, 127.5, 126.4, 124.3, 50.8, 22.1, 20.8, 17.2; HR-MS:
m/z=280.1700 [M+H]+, calcd. for C19H21NO: 280.1696.
(E)-N-Cinnamyl-N-methylbenzamide (6h): white solid;
yield: 99.2 mg (0.40 mmol, 79%); mp 82–838C; 1H NMR
(400 MHz, CDCl3, at room temperature): d=7.46–7.26 (m,
20H), 6.59 (d, J=15.2 Hz, 1H), 6.49 (d, J=15.2 Hz, 1H),
6.30–6.26 (m, 1H), 6.11–6.08 (m, 1H), 4.31 (d, J=5.2 Hz,
2H), 4.02 (d, J=3.6 Hz, 2H), 3.11 (s, 3H), 2.95 (s, 3H);
1H NMR (600 MHz, CDCl3, T=323 K): d=7.44–7.42 (m,
2H), 7.38–7.35 (m, 4H), 7.30 (t, J=7.80 Hz, 2H), 7.24–7.22
(E)-Ethyl 3-[3-(4-bromophenyl)allyl]-4-(3-methoxyphen-
yl)-6-methyl-2-oxo-1,2,3,4-tetrahydropyrimidine-5-carboxyl-
ate (3p): white solid; yield: 135.6 mg (0.28 mmol, 56%); mp
1
158–1598C; H NMR (400 MHz, CDCl3): d=8.62 (brs, 1H,
NH), 7.42 (d, J=8.4 Hz, 2H), 7.26–7.18 (m, 3H), 6.96 (d,
J=7.6 Hz, 1H), 6.91–6.90 (m, 1H), 6.80 (dd, J=8.2, 6.6 Hz,
1H), 6.43 (d, J=16.0 Hz, 1H), 6.10–6.03 (m, 1H), 5.30 (s,
1H), 4.58 (dd, J=15.6, 4.0 Hz, 1H), 4.15–4.01 (m, 2H), 3.78
(s, 3H), 3.52 (dd, J=15.6, 7.6 Hz, 1H), 2.34 (s, 3H), 1.19 (t,
J=7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3): d=165.6,
159.7, 152.9. 146.4, 143.3, 135.4, 131.9, 131.6, 129.6, 127.9,
124.8, 121.4, 119.7, 113.6, 112.7, 101.2, 60.0, 59.5, 55.2, 46.5,
18.6, 14.2; HR-MS: m/z=485.1073 [M+H]+, calcd. for
C24H25BrN2O4: 485.1070.
(E)-1-(3-Phenylallyl)-piperidin-2-one (6a): colourless oil;
yield: 75.3 mg (0.38 mmol, 70%); 1H NMR (400 MHz,
CDCl3): d=7.31–7.29 (m, 2H), 7.25–7.22 (m, 2H), 7.20–7.16
(m, 1H), 6.42 (d, J=15.6 Hz, 1H), 6.13–6.05 (m, 1H), 4.08
(dd, J=6.4, 1.2 Hz, 2H), 3.23–3.20 (m, 2H), 2.35 (t, J=
6.8 Hz, 2H), 1.75–1.71 (m, 4H); 13C NMR (100 MHz,
CDCl3): d=169.5, 136.5, 132.8, 128.5, 127.6, 126.3, 124.4,
48.8, 47.2, 32.3, 23.1, 21.3; HR-MS: m/z=216.1386 [M+H]+,
calcd. for C14H17NO: 216.1383.
(E)-1-(3-p-Tolylallyl)-piperidin-2-one (6b): white solid;
yield: 83.6 mg (0.37 mmol, 73%); mp 98–998C;1H NMR
(400 MHz, CDCl3): d=7.27 (s, 1H), 7.25 (s, 1H), 7.12 (d,
J=8.0 Hz, 2H), 6.46 (d, J=16.0 Hz, 1H), 6.14–6.07 (m,1H),
4.14 (d, J=5.6 Hz, 2H), 3.28 (s, 2H), 2.42 (s, 2H), 2.33 (s,
3H), 1.82–1.78 (m, 4H); 13C NMR (100 MHz, CDCl3): d=
169.5, 137.4, 133.7, 132.7, 129.2, 126.2, 123.3, 48.8, 47.1, 32.3,
23.1, 21.3, 21.1; HR-MS: m/z=230.1543 [M+H]+, calcd. for
C15H19NO: 230.1539.
(E)-1-(3-Phenylallyl)-azepan-2-one (6c): colourless oil;
yield: 91.7 mg (0.40 mmol, 80%); 1H NMR (400 MHz,
DMSO-d6): d=7.43–7.40 (m, 2H), 7.34–7.29 (m, 2H), 7.25–
7.21 (m, 1H), 6.51 (d, J=16.0 Hz, 1H), 6.20–6.13 (m, 1H),
4.05 (dd, J=6.4, 1.2 Hz, 2H), 3.35–3.33 (m, 2H), 2.47–2.45
(m, 2H), 1.67–1.62 (m, 2H), 1.58–1.50 (m, 4H); 13C NMR
(100 MHz, DMSO-d6): d=174.5, 136.5, 131.6, 128.7, 127.6,
126.3, 125.7, 48.9, 47.9, 36.5, 29.3, 28.2, 23.1; HR-MS: m/z=
230.1542 [M+H]+, calcd. for C15H19NO: 230.1539.
(m, 2H), 6.51 (s, 1H), 6.14ACTHNURGTNE(NUG s, 1H), 4.28–4.02 (m, 2H), 3.04
(s, 3H); 13C NMR (100 MHz, CDCl3): d=172.1, 171.3, 136.5,
136.2, 133.4, 132.5, 129.6, 128.7, 128.4, 128.0, 127.8, 127.1,
126.7, 126.4, 124.2, 53.5, 49.6, 36.9, 33.1; HR-MS: m/z=
252.1380 [M+H]+, calcd. for C17H17NO: 252.1383.
(E)-N-Benzyl-N-cinnamylbenzamide (6i): colourless oil;
yield: 114.5 mg (0.35 mmol, 70%); 1H NMR (400 MHz,
CDCl3): d=7.49–7.20 (m, 30H), 6.46–6.39 (m, 2H), 6.30–
6.27 (m, 1H), 6.06–6.02 (m, 1H), 4.83 (s, 2H), 4.53 (s, 2H),
4.26 (d, J=4.8 Hz, 2H), 3.93 (d, J=4.0 Hz, 2H); 13C NMR
(150 MHz, CDCl3): d=172.0, 137.1, 136.4, 136.1, 133.6,
132.9, 129.6, 128.6, 128.4, 128.3, 127.9, 127.2, 127.4, 126.8,
126.6, 126.4, 124.2, 124.0, 51.7, 50.2, 47.2, 46.3; HR-MS:
m/z=327.1700 [M+H]+, calcd. for C23H21NO: 328.1696.
Phenyl(4-phenyl-3,4-dihydroquinolin-1(2H)-yl)-metha-
none (7): white solid; yield: 109.6 mg (0.35 mmol, 70%); mp
145–1468C; 1H NMR (600 MHz, CDCl3): d=7.37–7.33 (m,
5H), 7.29–7.21 (m, 6H), 6.93–6.85 (m, 3H), 4.16 (q, J=
12 Hz, 1H), 4.06–4.02 (m, 1H), 3.92–3.88 (m, 1H), 2.42–2.37
(m, 1H), 2.20–2.14 (m, 1H); 13C NMR (150 MHz, CDCl3):
d=170.2, 143.8, 138.9, 136.2, 133.7, 130.2, 128.9, 128.7, 128.5,
128.4, 128.1, 126.8, 126.1, 125.3, 124.5, 43.7, 43.4, 32.5; HR-
MS: m/z=314.1542 [M+H]+, calcd. for C22H19NO:
314.1539.
(E)-1-(3-p-Tolylallyl)-azepan-2-one (6d): white solid;
yield: 100.9 mg (0.42 mmol, 83%); mp 60–618C; 1H NMR
(400 MHz, CDCl3): d=7.26 (d, J=1.3 Hz, 1H), 7.25 (s, 1H),
7.12 (d, J=8.0 Hz, 2H), 6.46 (d, J=16.0 Hz, 1H), 6.12–6.05
(m, 1H), 4.15 (d, J=6.4, 2H), 3.34–3.32 (m, 2H), 2.58–2.55
(m, 2H), 2.33 (s, 3H), 1.71 (s, 4H), 1.61 (d, J=4.8 Hz, 2H);
13C NMR (100 MHz, CDCl3): d=175.6, 137.4, 133.8, 132.4,
129.2, 126.2, 124.1, 49.8, 48.5, 37.1, 29.9, 28.4, 23.4, 21.1; HR-
MS: m/z=244.1702 [M+H]+, calcd. for C16H21NO:
244.1696.
(E)-Methyl cinnamyl(naphthalen-1-ylmethyl)-carbamate
(10a): colourless oil, yield: 107.6 mg (0.33 mmol, 65%);
1H NMR (600 MHz, CDCl3): d=8.16–7.97 (m, 1H), 7.88 (d,
J=7.2 Hz, 1H), 7.82 (d, J=8.4 Hz, 1H), 7.56–7.41 (m, 4H),
7.32–7.26 (m, 5H), 6.36 (d, J=16.2 Hz, 1H), 6.22–6.08 (m,
1H), 5.05–5.00 (m, 2H), 4.08 (s, 1H), 3.90 (s, 1H), 3.84 (s,
3H); 13C NMR (150 MHz, CDCl3): d=156.9, 136.5, 133.8,
(E)-1-[3-(4-Bromophenyl)-allyl]-azepan-2-one (6e): col-
ourless oil; yield: 116.7 mg (0.38 mmol, 76%); 1H NMR
(400 MHz, CDCl3): d=7.44–7.42 (m, 2H), 7.22 (d, J=
6.8 Hz, 2H), 6.43 (d, J=16.0 Hz, 1H), 6.18–6.10 (m, 1H),
898
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Adv. Synth. Catal. 2013, 355, 891 – 900

One-Pot Synthesis of Allylamine Derivatives by Iodine-Catalyzed Three-Component Reaction
132.6, 132.1, 131.8, 131.3, 128.5, 127.9, 127.6, 126.3, 125.8,
125.2, 124.6, 123.8, 122.8, 53.0, 47.6, 47.1; HR-MS: m/z=
331.1649 [M+H]+, calcd. for C22H21NO2: 332.1645.
[6] a) L. M. Stanley, J. F. Hartwig, J. Am. Chem. Soc. 2009,
131, 8971–8983; b) S. Spiess, C. Welter, G. Frank, J.-P.
Taquet, G. Helmchen, Angew. Chem. 2008, 120, 7764–
7767; Angew. Chem. Int. Ed. 2008, 47, 7652–7655; c) C.
Shi, I. Ojima, Tetrahedron 2007, 63, 8563–8570; d) O. V.
Singh, H. Han, J. Am. Chem. Soc. 2007, 129, 774–775;
e) J. W. Faller, J. C. Wilt, Org. Lett. 2005, 7, 633–636;
f) K. Tissot-Croset, D. Polet, A. Alexakis, Angew.
Chem. 2004, 116, 2480–2482; Angew. Chem. Int. Ed.
2004, 43, 2426–2428; g) D. B. Berkowitz, G. Maiti, Org.
Lett. 2004, 6, 2661–2664; h) Y. Matsushima, K. Onitsu-
ka, T. Kondo, T. Mitsudo, S. Takahashi, J. Am. Chem.
Soc. 2001, 123, 10405–10406.
(E)-Methyl (naphthalen-1-ylmethyl)[3-ACTHNUTRGENUG(N p-tolyl)allyl]-car-
bamate (10b): colourless oil; yield: 120.8 mg (0.35 mmol,
70%); 1H NMR (600 MHz, DMSO-d6): d=8.11–8.02 (m,
1H), 7.95–7.93ACHTUNGTRENNUNG(m, 1H), 7.85 (d, J=7.8 Hz, 1H), 7.56–7.52
(m, 2H), 7.49 (t, J=7.8 Hz, 1H), 7.39–7.31 (m, 1H), 7.20 (d,
J=6.6 Hz, 2H), 7.08 (d, J=7.8 Hz, 2H), 6.33 (d, J=13.8 Hz,
1H), 6.12 (s, 1H), 4.94 (s, 2H), 3.99–3.89 (m, 2H), 3.70–3.64
(m, 3H), 2.25 (s, 3H); 13C NMR (150 MHz, DMSO-d6): d=
156.1, 136.8, 133.6, 133.4, 132.8, 131.4, 129.1, 128.8, 128.6,
127.9, 126.3, 126.1, 126.0, 125.9, 125.7, 125.4, 123.8, 52.7,
48.5, 47,5; HR-MS: m/z=346.1805 [M+H]+, calcd for
C23H23NO2: 346.1802.
[7] K.-Y. Ye, H. He, W.-B. Liu, L.-X. Dai, G. Helmchen,
S.-L. You, J. Am. Chem. Soc. 2011, 133, 19006–19014.
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Acknowledgements
We are thankful for the financial support from the National
Nature Science Foundation of China (No. 20902073 and
21062017), and Scientific and Technological Innovation Engi-
neering program of Northwest Normal University (nwnu-
kjcxgc-03-64, nwnu-lkqn-10-15).
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900
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