Base-Promoted Carbonylative Cyclization of Propargylic Amines with Selenium under CO Gas-free Conditions

Article abstract of DOI:10.1002/adsc.201800109

We report here a new carbonylative procedure for the cyclization of propargylic amines with elemental selenium (Se). By using tBuOK as the promoter, various 1,3-selenazolidin-2-ones were produced without the usage of toxic CO gas. Benzene-1,3,5-triyl triformate (TFBen) was employed as a safe and convenient CO surrogate here, and a broad class of substrates (29 examples) were effectively transformed into the desired products in 50–97% yields under mild conditions. (Figure presented.).

Full text of DOI:10.1002/adsc.201800109

Title: Base-Promoted Carbonylative Cyclization of Propargylic Amines
with Selenium under CO gas-free Conditions
Authors: Xiao-Feng Wu, Ming lai, hai wang, jin-bao peng, xinxin qi, and
jun Ying
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To be cited as: Adv. Synth. Catal. 10.1002/adsc.201800109
Link to VoR: http://dx.doi.org/10.1002/adsc.201800109

10.1002/adsc.201800109
Advanced Synthesis & Catalysis
FULL PAPER
DOI: 10.1002/adsc.2018
Base-Promoted Carbonylative Cyclization of Propargylic
Amines with Selenium under CO gas-free Conditions
Hai Wang,a Jun Ying,a Ming Lai,a Xinxin Qi,a Jin-Bao Peng,a and Xiao-Feng Wua,b*
a
Department of Chemistry, Zhejiang Sci-Tech University, Xiasha Campus, Hangzhou 310018, People’s Republic of
China
E-mail: Xiao-Feng.Wu@catalysis.de
Leibniz-Institut für Katalyse e. V. an der Universität Rostock, Albert-Einstein-Straβe 29a, 18059 Rostock, Germany
b
Received: ((will be filled in by the editorial staff))
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.2018
Abstract. We report here a new carbonylative procedure for the cyclization of propargylic amines with elemental
selenium (Se). By using tBuOK as the promoter, various 1,3-selenazolidin-2-ones were produced without the usage of
toxic CO gas. Benzene-1,3,5-triyl triformate (TFBen) was employed as a safe and convenient CO surrogate here, and a
broad class of substrates (29 examples) were effectively transformed into the desired products in 50-97% yields under
mild conditions.
Keywords: Carbonylation; Cyclization; Domino reactions; Catalyst free; Heterocycle synthesis
7-ene (DBU).[9a] In 2013, Lu’s group developed a
facile access to 1,3-selenazolidin-2-ones (4 examples,
up to 79% yield) by the reaction of 2-chloroethyl
amine salts with Se and carbon monoxide (1 bar) in
the presence of NaOH.[11] However, the
disadvantages of these protocols are obvious as well:
1) the use of toxic and flammable CO gas; 2) the
limitation of substrates scope.
Introduction
The element selenium, an essential micronutrient,
plays a vital role in human health.[1] Although
selenium is toxic at high levels[1-2] and could lead to
cancer in certain forms,[3] selenium-containing
compounds are important intermediates in synthetic
chemistry,[4] and are present widely in biological and
medicinal chemistry.[4b,5] Among them, 1,3-
selenazolidines are interesting and have been reported
as inhibitors of NO-synthase,[6] antimutagenes[7] and
cancer preventing agents.[5m,8] As is shown in Figure
1, benzoselenazolinones was found to have anti-
inflammatory properties,[4b] and 2-oxoselenazolidine-
4-carboxylic acid (2-OxoSCA) has chemopreventive
activity.[5k,5m]
Due to their obvious importance, synthetic
methodologies have been developed for the
preparation of 1,3-selenazolidin-2-ones.[9] In 1984,
Woodgate and co-workers reported the use of trans-
1-iodo-2-isocyanatocyclohexane as the starting
material with NaHSe or Li2Se to give the
Figure 1. Selected examples of bio-active 1,3-
selenazolidines and 1,3-selenazolidin-2-ones motifs.
In order to avoid the manipulation of toxic CO gas
in carbonylative reactions, a number of alternative
CO sources such as transition metal carbonyl
complexes,[12] formaldehyde,[13] methanol,[14] formic
corresponding
(3aS,7aR)-
hexahydrobenzo[d][1,3]selenazol-2(3H)-one in 55%
and 42% yields, respectively.[10] In 2001, Robert’s
group prepared 2-oxoselenazolidine-4(R)-carboxylic
acid from chloroamino acid, Se and sodium
borohydride in about 36% overall yield through three
steps procedure.[8a] In 2002, Fujiwara et al. reported a
method for the synthesis of 5-alkylideneselenazolin-
2-ones from 3-aminoalkynes (9 examples, up to 95%
yield) under carbon monoxide gas atmospheric (1
bar) in the presence of 1,8-diazabicyclo(5.4.0)undec-
acid,[15]
formates,[16]
oxalyl
formamides,[17]
chloride,[19]
N-
car-
formylsaccharin,[18]
bamoylsilane,[20] chloroform[21] and others[22] have
been developed recently. Among them, TFBen,
developed by our group,[23] is a solid, stable, safe and
convenient CO source. Herein, we wish to report our
new results on tBuOK-promoted carbonylative
cyclization of propargylic amines with Se using
TFBen (benzene-1,3,5-triyl triformate) as the CO
1
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10.1002/adsc.201800109
Advanced Synthesis & Catalysis
surrogate. The desired 1,3-selenazolidin-2-ones (29
examples) were isolated in high yields (50-97%).
using n-dodecane as internal standard. [c] 0.2 mmol. [d] 0.1 mmol. [e]
Isolated yield. [f] 0.04 mmol.
Results and Discussion
Table 2. 1,3-Selenazolidin-2-ones synthesis.[a]
Initially, we carried out the carbonylative
cyclization of propargylic amine 1aa with TFBen and
Se at 35 °C and the results are summarized in Table 1.
When 1aa was treated with TFBen (0.4 mmol, 2
equiv.) and selenium powder (0.3 mmol, 1.5 equiv.)
using tBuOK (0.4 mmol, 2.0 equiv.) as the promoter
in 1.0 mL DMSO, the reaction afforded the
corresponding cyclic product 2aa in 99% yield (Table
1, entry 1). Then, a series of bases were screened
(Table 1, entries 2-6). It shows that the reaction using
DBU gave a slightly reduced yield (97%) of 2aa
(Table 1, entry 2). In the cases using NaOH, DABCO,
DAMP or K2CO3 as the base, the reaction gave
remarkably low yields of the product (Table 1, entries
3-6). When the solvent of the reaction was changed
from DMSO to DMF (Table 1, entry 8), over 99%
yield was obtained, while 1,4-dioxane, MeCN,
toluene and THF led to the formation of only a trace
or no product (Table 1, entries 7 and 9-11). Excellent
yields can still be obtained when the amounts of
TFBen and tBuOK were decreased (Table 1, entries
12 and 13), and 88% of isolated yield was obtained
(Table 1, entry 13). Unfortunately, further reducing
the amount of tBuOK to 0.04 mmol (0.2 equiv.), no
product was observed (Table 1, entry 14). It was
found that the yield was dramatically decreased to
78% when 0.1 mmol (0.5 equiv.) TFBen was
employed (Table 1, entry 15).
Table 1. Screening of optimal reaction conditions.[a]
Base
Entry
TFBen
Solvent
Yield[b]
(0.4 mmol)
1
2
3
4
5
6
7
8
9
0.4 mmol
0.4 mmol
0.4 mmol
0.4 mmol
0.4 mmol
0.4 mmol
0.4 mmol
0.4 mmol
0.4 mmol
0.4 mmol
0.4 mmol
0.2 mmol
tBuOK
DBU
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
dioxane
DMF
99%
97%
2%
11%
Trace
Trace
0
>99%
Trace
0
[a] Reaction conditions: substrate (0.2 mmol), Se (0.3 mmol, 1.5 equiv),
NaOH
DABCO
DMAP
K2CO3
tBuOK
tBuOK
tBuOK
tBuOK
tBuOK
tBuOK[c]
t
TFBen (0.2 mmol, 1.0 equiv.), BuOK (0.1 mmol, 0.5 equiv.), DMF (1.0
t
mL), 35 °C, 24 h. [b] 60 °C. [c] TFBen (0.4 mmol, 2.0 equiv.), BuOK
(0.2 mmol, 1.0 equiv.).
MeCN
Toluene
THF
10
11
12
0
DMF
>99%
98%
(88%)[e]
0
13
0.2 mmol
tBuOK[d]
tBuOK[f]
tBuOK[d]
DMF
14
15
0.2 mmol
0.1 mmol
DMF
DMF
78%
[a] Reaction conditions: 1aa (0.2 mmol), Se (0.3 mmol, 1.5 equiv.),
solvent (1.0 mL). [b] The yield of 2aa was determined by GC analysis
2
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10.1002/adsc.201800109
Advanced Synthesis & Catalysis
2h
2t
Scheme 1. Possible reaction pathway.
Based on the literature[9a,11] and our results, a
possible reaction pathway for this carbonylative
cyclization of propargylic amines with Se and TFBen
is shown in Scheme 1. By using tBuOK as the
promotor, Se reacts with CO which generated in-situ
from TFBen, to give the selenium carbonyl
compound 3. Deprotonation of propargylic amine 1
by tBuOK followed by the nucleophilic addition to
Figure 2. X-ray structure of 2h (CCDC 1817355) and 2t
(CCDC 1817678). Displacement ellipsoids correspond to
30% probability. Hydrogen atoms are omitted for
clarity.[24]
the
selenium
carbonyl
3
generates
the
selenocarbamate 6 as the key intermediate. Then, the
intramolecular nucleophilic attack of selenium anion
to the triple bond forms the desired product 2 as a Z-
isomer. It is likely that the steric hindrance of tBuOH
plays an important role in the observed
stereochemistry of product 2.
With the optimized reaction conditions (Table 1,
entry 13) in hand, we examined the scope with
various propargylic amines as follows (Table 2). It
shows that good to excellent yields (76-96%) were
achieved for both electron-rich (2ab-2ae) and
electron-deficient (2af-2ag) aromatic propargylic
amines. The reactions of substrates containing n-octyl
group on the nitrogen atom afforded the
corresponding product (2c) in 95% yield. However,
when the propargylic amine with an N-cyclohexyl
unit was carried out, a trace product 2d was observed,
which might due to the steric bulk on the nitrogen
atom. High yields of the desired products (2ba-2bc)
can be obtained by increasing the reaction
temperature (60 °C) and also the loading of tBuOK
(0.2 mmol, 1.0 equiv.) and TFBen (0.4 mmol, 2.0
equiv.). Compounds having a carbocycle on the triple
bond were converted to the desired products (2e-2h)
in good to excellent yields (59-92%). Notably,
thiophene substituted propargylic amine was also
transformed to the product 2i in 95% yield. For
substrates containing alkyl groups on the triple bond
were conducted at 60 °C, 56-78% yields of products
(2j-2m) were obtained. Interestingly, primary
propargylic amine can also be successfully
transformed into the desired product 2n in 86% yield.
Moreover, substrates with aryl and alkyl substituents
(R2 = aryl, alkyl and R3 = H) were tested as well, 50-
97% yields of the corresponding products 2o-2t can
be successfully achieved. In addition, it was found
that a compound without substituents (R2, R3 = H)
can also undergo carbonylative cyclization to provide
the product 2u in a good yield. In order to confirm
the structure, X-ray analysis of products 2h and 2t
have been performed as well (Figure 2).
Conclusion
In summary,
a
new and straightforward
carbonylation procedure toward 1,3-selenazolidin-2-
ones has been established. By using tBuOK as the
promotor, propargylic amines and elemental selenium
were carbonylatively cyclized with TFBen as the CO
source. Various desired 1,3-selenazolidin-2-ones with
broad functional groups are prepared in 50-97%
yields under mild conditions. Further synthetic
application of this method and more detailed study of
the reaction mechanism are under progress.
Experimental Section
Unless otherwise noted, all reactions were carried out
under a nitrogen atmosphere. All reagents were obtained
from commercial sources and used as received without
further purification. Column chromatography was
performed on silica gel (200-300 mesh) using petroleum
ether (bp 60-90 °C), ethyl acetate and dichloromethane as
1
eluent. H and 13C NMR spectra were taken on 400 MHz
instruments, and spectral data were reported in ppm
relative to tetramethylsilane (TMS) as internal standard
and CDCl3 as solvent.
Preparation of TFBen
Formic acid (8.4 mL, 222.8 mmol, 5.0 equiv.) was added
to acetic anhydride (16.8 mL, 178.2 mmol, 4.0 equiv.) at
room temperature. The mixture was stirred at 60 °C for 1 h
and cooled to room temperature. The resulting solution
was
poured
into
a
flask containing 1,3,5-
trihydroxybenzene (5.62 g, 44.6 mmol, 1.0 equiv.) and
AcONa (1.83 g, 22.3 mmol, 0.5 equiv.). The mixture was
3
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10.1002/adsc.201800109
Advanced Synthesis & Catalysis
1
stirred for 4 h in a water bath and then diluted with toluene
(100 mL), washed with H2O (50 mL) two times. Keep the
organic phase in fridge (2-8 °C) for overnight. Then
filtered and dried in vacuo to afford the desired product
benzene-1,3,5-triyl triformate (TFBen) as a white solid.
Black oil, 66%. H NMR (400 MHz, CDCl3) δ = 7.33 (dd,
J = 11.1, 4.7 Hz, 4H), 2.79 (t, J = 7.2 Hz, 2H), 1.72 (s, 1H),
1.50 (d, J = 7.6 Hz, 2H), 1.44 (s, 6H), 1.40 (d, J = 7.8 Hz,
2H), 1.29 (s, 9H), 0.94 (t, J = 7.3 Hz, 3H). 13C NMR (100
MHz, CDCl3) δ = 150.86, 131.23, 125.08, 120.43, 93.77,
81.96, 50.30, 43.98, 34.58, 32.55, 31.10, 29.58, 20.51,
13.92. [M+H+] calcd. for C19H30N+, 272.2373; found,
272.2370.
Benzene-1,3,5-triyl triformate, TFBen
1
5.1 g, 55% yield, white solid, mp 53.2–55.6 °C. H NMR
(400 MHz, CDCl3) δ = 8.24 (s, 3H), 6.97 (s, 3H). 13C
NMR (100 MHz, CDCl3) δ = 158.06, 150.30, 112.62.
N-Butyl-4-(4-fluorophenyl)-2-methylbut-3-yn-2-amine
(1af)
1
Black oil, 59%. H NMR (400 MHz, CDCl3) δ = 7.39 –
Procedure for the Synthesis of Propargylic Amines for
1aa-ah, 1ba-bc, 1c-1m, 1o-1t[25]
7.34 (m, 2H), 7.00 – 6.95 (m, 2H), 2.78 (t, J = 7.2 Hz, 2H),
1.67 (s, 1H), 1.51 (dd, J = 14.9, 7.5 Hz, 2H), 1.44 (s, 6H),
1.40 (dd, J = 15.0, 7.2 Hz, 2H), 0.94 (t, J = 7.3 Hz, 3H).
13C NMR (100 MHz, CDCl3) δ = 162.13 (d, J = 249.5 Hz),
133.33 (d, J = 8.3 Hz), 119.47 (d, J = 3.5 Hz), 115.35 (d, J
= 22.0 Hz), 94.14, 80.89, 50.28, 43.99, 32.52, 29.50, 20.51,
13.93. [M+H+] calcd. for C15H21FN+, 234.1653; found,
234.1658.
In a typical experiment, CuI (1.5 mmol, 30 mol%) was
added to a 15 mL tube equipped with a magnetic stirrer
which was then placed under vacuum and refilled with
nitrogen three times. Amine (5.0 mmol, 1.0 equiv.),
aldehyde/ketone (5.0 mmol, 1.0 equiv.) and alkyne (5.0
mmol, 1.0 equiv.) were added, then the tube was sealed
and the mixture was stirred at 75 °C for 16 h. After the
reaction was completed, the crude reaction mixture was
concentrated and purified by silica gel column
chromatography (PE/EtOAc=5/1) to provide the desired
propargylic amine 1.
N-Butyl-4-(4-chlorophenyl)-2-methylbut-3-yn-2-amine
(1ag)
Black oil, 50%. 1H NMR (400 MHz, CDCl3) δ = 7.31 (d, J
= 8.5 Hz, 2H), 7.25 (d, J = 8.5 Hz, 2H), 2.76 (t, J = 7.1 Hz,
2H), 1.57 (s, 1H), 1.53 – 1.47 (m, 2H), 1.43 (s, 6H), 1.42 –
1.34 (m, 2H), 0.94 (t, J = 7.2 Hz, 3H). 13C NMR (100 MHz,
CDCl3) δ = 133.59, 132.72, 128.40, 121.92, 95.63, 80.79,
50.20, 43.95, 32.54, 29.45, 20.48, 13.91. [M+H+] calcd. for
C15H21ClN+, 250.1357; found, 250.1358.
N-Butyl-2-methyl-4-phenylbut-3-yn-2-amine (1aa)
1
Black oil, 70%. H NMR (400 MHz, CDCl3) δ = 7.39 (dd,
J = 6.5, 3.1 Hz, 2H), 7.32 – 7.22 (m, 3H), 2.79 (t, J = 7.2
Hz, 2H), 1.69 (s, 1H), 1.52 (dd, J = 14.9, 7.1 Hz, 2H), 1.45
(s, 6H), 1.39 (dt, J = 14.2, 7.1 Hz, 2H), 0.94 (t, J = 7.3 Hz,
3H). 13C NMR (100 MHz, CDCl3) δ = 131.51, 128.11,
127.67, 123.41, 94.50, 81.91, 50.25, 43.98, 32.53, 29.52,
20.51, 13.93.
4-(4-Bromophenyl)-N-butyl-2-methylbut-3-yn-2-amine
(1ah)
Black oil, 63%. 1H NMR (400 MHz, CDCl3) δ = 7.41 (d, J
= 8.3 Hz, 2H), 7.25 (d, J = 8.3 Hz, 2H), 2.77 (t, J = 7.2 Hz,
2H), 2.34 (s, 1H), 1.55 – 1.49 (m, 2H), 1.45 (s, 6H), 1.39
(dd, J = 14.9, 7.5 Hz, 2H), 0.93 (t, J = 7.2 Hz, 3H). 13C
NMR (100 MHz, CDCl3) δ 132.98, 131.34, 122.33, 121.84,
95.54, 81.08, 50.43, 43.93, 32.37, 29.32, 20.46, 13.88.
N-Butyl-2-methyl-4-(p-tolyl)but-3-yn-2-amine (1ab)
Black oil, 63%. 1H NMR (400 MHz, CDCl3) δ = 7.28 (d, J
= 8.0 Hz, 2H), 7.07 (d, J = 7.9 Hz, 2H), 2.78 (t, J = 7.2 Hz,
2H), 2.31 (s, 3H), 1.60 (s, 1H), 1.54 – 1.47 (m, 2H), 1.44
(d, J = 14.3 Hz, 6H), 1.38 (d, J = 6.9 Hz, 2H), 0.94 (t, J =
7.2 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ = 137.56,
131.35, 128.80, 120.35, 93.71, 81.93, 50.22, 43.92, 32.53,
29.54, 21.24, 20.46, 13.87.
N-Benzyl-2-methyl-4-phenylbut-3-yn-2-amine (1ba)
1
Black oil, 76%. H NMR (400 MHz, CDCl3) δ = 7.46 –
7.42 (m, 2H), 7.38 (d, J = 7.2 Hz, 2H), 7.34 – 7.28 (m, 5H),
7.23 (d, J = 5.6 Hz, 1H), 3.96 (s, 2H), 1.63 (s, 1H), 1.50 (s,
6H). 13C NMR (100 MHz, CDCl3) δ = 140.67, 131.60,
128.43, 128.21, 127.81, 126.92, 123.39, 94.45, 82.36,
50.65, 49.13, 29.64.
N-Butyl-4-(4-methoxyphenyl)-2-methylbut-3-yn-2-
amine (1ac)
Black oil, 65%. 1H NMR (400 MHz, CDCl3) δ = 7.33 (d, J
= 8.8 Hz, 2H), 6.81 (d, J = 8.8 Hz, 2H), 3.78 (s, 3H), 2.78
(t, J = 7.2 Hz, 2H), 1.68 (s, 1H), 1.53 – 1.49 (m, 2H), 1.44
(s, 6H), 1.39 (dd, J = 15.1, 7.3 Hz, 2H), 0.94 (t, J = 7.3 Hz,
3H). 13C NMR (100 MHz, CDCl3) δ = 159.15, 132.86,
115.59, 113.75, 92.96, 81.68, 55.15, 50.29, 43.97, 32.55,
29.61, 20.51, 13.91. HRMS (ESI): [M+H+] calcd. for
C16H24NO+, 246.1852; found, 246.1855.
N-(4-Methoxybenzyl)-2-methyl-4-phenylbut-3-yn-2-
amine (1bb)
1
Black oil, 50%. H NMR (400 MHz, CDCl3) δ = 7.44 (dd,
J = 6.5, 3.1 Hz, 2H), 7.30 (dd, J = 5.1, 1.9 Hz, 5H), 6.86 (d,
J = 8.6 Hz, 2H), 3.90 (s, 2H), 3.79 (s, 3H), 1.61 (s, 1H),
1.49 (s, 6H). 13C NMR (100 MHz, CDCl3) δ = 158.62,
132.81, 131.61, 129.61, 128.23, 127.81, 123.42, 113.86,
94.54, 82.32, 55.25, 50.60, 48.51, 29.63.
N-Butyl-2-methyl-4-(4-propylphenyl)but-3-yn-2-amine
(1ad)
Black oil, 50%. 1H NMR (400 MHz, CDCl3) δ = 7.31 (d, J
= 8.1 Hz, 2H), 7.09 (d, J = 8.0 Hz, 2H), 2.79 (t, J = 7.2 Hz,
2H), 2.56 (t, J = 7.6 Hz, 2H), 1.66 – 1.59 (m, 4H), 1.55 –
1.47 (m, 4H), 1.4 (s, 6H), 1.40 (dd, J = 15.1, 7.1 Hz, 2H),
0.96 – 0.90 (m, 6H). 13C NMR (100 MHz, CDCl3) δ =
142.48, 131.41, 128.30, 120.63, 93.81, 82.04, 50.33, 44.03,
37.83, 32.60, 29.62, 24.29, 20.54, 13.94, 13.63. [M+H+]
calcd. for C18H28N+, 258.2216; found, 258.2218.
N-(4-Chlorobenzyl)-2-methyl-4-phenylbut-3-yn-2-
amine (1bc)
1
Black oil, 43%. H NMR (400 MHz, CDCl3) δ = 7.42 (dd,
J = 6.5, 3.2 Hz, 2H), 7.31 – 7.25 (m, 7H), 3.91 (s, 2H),
1.57 (s, 1H), 1.48 (s, 6H). 13C NMR (100 MHz, CDCl3) δ
= 139.21, 132.51, 131.54, 129.67, 128.42, 128.18, 127.83,
123.24, 94.17, 82.43, 50.57, 48.30, 29.60. [M+H+] calcd.
for C18H19ClN+, 284.1201; found, 284.1206.
N-Butyl-4-(4-(tert-butyl)phenyl)-2-methylbut-3-yn-2-
amine (1ae)
N-(2-Methyl-4-phenylbut-3-yn-2-yl)octan-1-amine (1c)
4
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10.1002/adsc.201800109
Advanced Synthesis & Catalysis
1
Yellow oil, 71%. H NMR (400 MHz, CDCl3) δ = 7.43 –
N-Butyl-2-methyldec-3-yn-2-amine (1j)
7.36 (m, 2H), 7.31 – 7.25 (m, 3H), 2.78 (t, J = 7.2 Hz, 2H),
1.82 (s, 1H), 1.56 – 1.48 (m, 2H), 1.45 (s, 6H), 1.32 (ddd, J
= 18.5, 10.1, 4.7 Hz, 10H), 0.88 (dd, J = 9.1, 4.6 Hz, 3H).
13C NMR (100 MHz, CDCl3) δ = 131.54, 128.12, 127.70,
123.42, 94.48, 81.98, 50.31, 44.34, 31.79, 30.41, 29.52,
29.45, 29.21, 27.41, 22.60, 14.04. [M+H+] calcd. for
C19H30N+, 272.2373; found, 272.2378.
1
Yellow oil, 63%. H NMR (400 MHz, CDCl3) δ = 2.67 (t,
J = 7.0 Hz, 2H), 2.14 (t, J = 6.9 Hz, 2H), 1.75 (s, 1H), 1.48
– 1.41 (m, 5H), 1.36 (dd, J = 13.9, 6.8 Hz, 5H), 1.30 (s,
6H), 1.27 – 1.26 (m, 2H), 0.92 – 0.84 (m, 6H). 13C NMR
(100 MHz, CDCl3) δ = 84.99, 81.90, 49.89, 43.89, 32.50,
31.28, 29.80, 28.93, 28.41, 22.51, 20.55, 18.54, 13.96,
13.93. [M+H+] calcd. for C15H30N+, 224.2373; found,
224.2378.
N-(2-Methyl-4-phenylbut-3-yn-2-yl)cyclohexanamine
(1d)
N-Butyl-2-methyl-6-phenylhex-3-yn-2-amine (1k)
1
Black oil, 58%. H NMR (400 MHz, CDCl3) δ = 7.38 (dd,
1
J = 6.5, 3.2 Hz, 2H), 7.28 (dd, J = 4.9, 1.7 Hz, 3H), 2.90 –
2.80 (m, 1H), 2.24 (s, 1H), 2.00 (d, J = 11.8 Hz, 2H), 1.74
(d, J = 12.8 Hz, 2H), 1.60 (d, J = 12.9 Hz, 1H), 1.49 (s,
6H), 1.38 – 1.09 (m, 6H). 13C NMR (100 MHz, CDCl3) δ =
131.42, 128.17, 127.73, 123.42, 94.84, 81.63, 53.76, 50.71,
35.90, 30.42, 25.60. [M+H+] calcd. for C17H24N+,
242.1903; found, 242.1906.
Yellow oil, 69%. H NMR (400 MHz, CDCl3) δ = 7.31 –
7.25 (m, 2H), 7.23 – 7.17 (m, 3H), 2.79 (t, J = 7.4 Hz, 2H),
2.62 (s, 2H), 2.47 (t, J = 7.4 Hz, 2H), 2.02 (s, 1H), 1.49 –
1.40 (m, 2H), 1.39 – 1.33 (m, 2H), 1.31 (s, 6H), 0.92 (t, J =
7.2 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ = 140.73,
128.45, 128.16, 126.10, 85.71, 81.19, 49.92, 43.80, 35.32,
32.36, 29.62, 20.76, 20.49, 13.94. [M+H+] calcd. for
C17H26N+, 244.2060; found, 244.2062.
N-Butyl-1-(phenylethynyl)cyclopentan-1-amine (1e)
N-Butyl-4-cyclopropyl-2-methylbut-3-yn-2-amine (1l)
1
Black oil, 78%. H NMR (400 MHz, CDCl3) δ = 7.41 –
1
7.39 (m, 2H), 7.30 – 7.26 (m, 3H), 2.78 (t, J = 7.1 Hz, 2H),
2.02 (dd, J = 13.4, 7.1 Hz, 2H), 1.80 (s, 6H), 1.50 (dt, J =
14.1, 7.0 Hz, 2H), 1.39 (dq, J = 14.0, 7.0 Hz, 3H), 0.93 (t,
J = 7.3 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ = 131.48,
128.10, 127.55, 123.66, 94.66, 82.44, 61.04, 44.95, 40.61,
32.67, 23.72, 20.54, 13.96.
Yellow oil, 51%. H NMR (400 MHz, CDCl3) δ = 2.59 (s,
2H), 1.88 (s, 1H), 1.39 (d, J = 5.7 Hz, 2H), 1.32 – 1.27 (m,
2H), 1.23 (s, 6H), 1.16 – 1.09 (m, 1H), 0.84 (t, J = 7.1 Hz,
3H), 0.68 – 0.60 (m, 2H), 0.55 – 0.48 (m, 2H). 13C NMR
(100 MHz, CDCl3) δ = 85.01, 80.00, 49.76, 43.67, 32.33,
29.64, 20.38, 13.77, 8.11, -0.78. [M+H+] calcd. for
C12H22N+, 180.1747; found, 180.1748.
N-Butyl-1-(phenylethynyl)cyclohexan-1-amine (1f)
N-Butyl-4-(cyclohex-1-en-1-yl)-2-methylbut-3-yn-2-
amine (1m)
1
Yellow oil, 80%. H NMR (400 MHz, CDCl3) δ = 7.45 –
7.38 (m, 2H), 7.32 – 7.21 (m, 3H), 2.80 (t, J = 7.1 Hz, 2H),
1.94 (d, J = 12.0 Hz, 2H), 1.66 (dd, J = 19.4, 9.8 Hz, 5H),
1.56 – 1.33 (m, 7H), 1.30 – 1.16 (m, 1H), 0.94 (t, J = 7.2
Hz, 3H). 13C NMR (100 MHz, CDCl3) δ = 131.44, 128.02,
127.50, 123.61, 93.48, 84.30, 54.87, 42.76, 38.08, 32.64,
25.81, 22.93, 20.46, 13.88.
1
Yellow oil, 75%. H NMR (400 MHz, CDCl3) δ = 6.03 (s,
1H), 2.72 (s, 2H), 2.14 – 1.99 (m, 5H), 1.65 – 1.55 (m, 4H),
1.48 (dd, J = 14.3, 7.2 Hz, 2H), 1.39 (d, J = 13.3 Hz, 8H),
0.93 (t, J = 7.2 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ =
133.60, 120.48, 91.41, 83.72, 50.16, 43.80, 32.37, 29.53,
29.47, 25.43, 22.23, 21.42, 20.43, 13.83. [M+H+] calcd. for
C15H26N+, 220.2060; found, 220.2065.
N-Butyl-1-(phenylethynyl)cycloheptan-1-amine (1g)
Yellow oil, 60%. 1H NMR (400 MHz, CDCl3) δ = 7.39 (dd, 2-Methyl-4-phenylbut-3-yn-2-amine (1n)
J = 16.9, 5.1 Hz, 2H), 7.28 (d, J = 5.3 Hz, 3H), 2.78 (t, J =
Yellow oil, 52%. 1H NMR (400 MHz, CDCl3) δ = 7.38 (dd,
J = 6.5, 3.0 Hz, 2H), 7.29 – 7.19 (m, 3H), 2.02 (s, 2H),
1.46 (s, 6H). 13C NMR (100 MHz, CDCl3) δ = 131.07,
127.78, 127.39, 122.97, 96.58, 79.67, 45.19, 31.35.
6.5 Hz, 2H), 2.59 – 2.33 (m, 1H), 2.03 – 1.92 (m, 2H), 1.69
(s, 8H), 1.60 – 1.46 (m, 4H), 1.39 (dq, J = 14.1, 7.1 Hz,
2H), 0.93 (t, J = 7.2 Hz, 3H). 13C NMR (100 MHz, CDCl3)
δ = 131.48, 128.09, 127.57, 123.60, 94.31, 83.60, 58.17,
43.77, 43.46, 40.56, 32.54, 30.33, 28.00, 24.24, 22.61,
20.52, 13.93.
N-(1,3-Diphenylprop-2-yn-1-yl)butan-1-amine (1o)
N-Butyl-4-methyl-1-(phenylethynyl)cyclohexan-1-
amine (1h)
Yellow oil, 60%. 1H NMR (400 MHz, CDCl3) δ = 7.58 (d,
J = 7.4 Hz, 2H), 7.45 (dd, J = 6.6, 2.9 Hz, 2H), 7.35 (t, J =
7.4 Hz, 2H), 7.31 – 7.24 (m, 4H), 4.78 (s, 1H), 2.84 (dt, J =
11.2, 7.3 Hz, 1H), 2.71 (dt, J = 11.2, 6.9 Hz, 1H), 1.55 (s,
1H), 1.54 – 1.46 (m, 2H), 1.42 – 1.31 (m, 2H), 0.91 (t, J =
7.3 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ = 140.52,
131.57, 128.36, 128.12, 127.96, 127.55, 127.46, 123.10,
89.52, 85.15, 54.60, 46.93, 32.00, 20.38, 13.89.
1
Yellow oil, 71%. H NMR (400 MHz, CDCl3) δ = 7.46 –
7.39 (m, 2H), 7.34 – 7.25 (m, 3H), 2.82 (t, J = 7.2 Hz, 2H),
1.97 (d, J = 11.0 Hz, 2H), 1.67 (m, 3H), 1.55 – 1.46 (m,
3H), 1.45 – 1.36 (m, 6H), 0.99 – 0.90 (m, 6H). 13C NMR
(100 MHz, CDCl3) δ = 131.48, 128.09, 127.58, 123.63,
93.20, 84.69, 55.04, 43.02, 38.14, 32.65, 33.37, 31.84,
22.13, 20.49, 13.92. [M+H+] calcd. for C19H28N+,
270.2216; found, 270.2218.
N-(1-(4-Methoxyphenyl)-3-phenylprop-2-yn-1-
yl)butan-1-amine (1p)
N-Butyl-2-methyl-4-(thiophen-3-yl)but-3-yn-2-amine
1
Yellow oil, 68%. H NMR (400 MHz, CDCl3) δ = 7.55 –
(1i)
7.41 (m, 4H), 7.32 – 7.25 (m, 3H), 6.89 (d, J = 8.7 Hz, 2H),
4.75 (s, 1H), 3.78 (s, 3H), 2.83 (dt, J = 11.2, 7.2 Hz, 1H),
2.70 (dt, J = 11.2, 7.2 Hz, 1H), 1.80 (s, 1H), 1.57 – 1.45 (m,
2H), 1.42 – 1.31 (m, 2H), 0.91 (t, J = 7.3 Hz, 3H). 13C
NMR (100 MHz, CDCl3) δ = 159.07, 132.77, 131.59,
128.62, 128.13, 127.94, 123.20, 113.76, 89.80, 85.02,
55.17, 54.01, 46.85, 32.01, 20.41, 13.89.
Yellow oil, 56%. 1H NMR (400 MHz, CDCl3) δ = 7.35 (dd,
J = 2.9, 1.0 Hz, 1H), 7.22 (dd, J = 4.9, 3.0 Hz, 1H), 7.06
(dd, J = 5.0, 1.0 Hz, 1H), 2.76 (t, J = 7.0 Hz, 2H), 1.62 (s,
1H), 1.54 – 1.46 (m, 2H), 1.43 (s, 6H), 1.40 – 1.34 (m, 2H),
0.94 (t, J = 7.3 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ =
129.88, 127.69, 124.91, 122.34, 94.03, 76.85, 50.21, 43.90,
32.51, 29.48, 20.43, 13.87. [M+H+] calcd. for C13H20NS+,
222.1311; found, 222.1315.
N-(1-(4-Fluorophenyl)-3-phenylprop-2-yn-1-yl)butan-1-
amine (1q)
5
This article is protected by copyright. All rights reserved.

10.1002/adsc.201800109
Advanced Synthesis & Catalysis
Yellow oil, 63%. 1H NMR (400 MHz, CDCl3) δ 7.55 (dd, J
= 8.2, 5.7 Hz, 2H), 7.45 (dd, J = 6.3, 2.8 Hz, 2H), 7.26 (dd,
J = 4.4, 2.0 Hz, 3H), 7.01 (t, J = 8.6 Hz, 2H), 4.75 (s, 1H),
2.81 (dt, J = 11.0, 7.2 Hz, 1H), 2.68 (dt, J = 11.1, 7.2 Hz,
1H), 1.56 – 1.42 (m, 3H), 1.41 – 1.30 (m, 2H), 0.90 (t, J =
7.3 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ = 162.08 (d, J
= 246.7 Hz), 136.26 (d, J = 3.1 Hz), 131.49, 129.04 (d, J =
8.1 Hz), 128.04 (d, J = 9.9 Hz), 122.88, 115.11, 114.90,
89.20, 85.33, 53.76, 46.72, 31.92, 20.29, 13.80. [M+H+]
calcd. for C19H21FN+, 282.1653; found, 282.1656.
56.7 mg, 88% yield, yellow oil. 1H NMR (400 MHz,
CDCl3) δ = 7.36 (t, J = 7.6 Hz, 2H), 7.29 – 7.22 (m, 3H),
6.91 (s, 1H), 3.28 – 3.24 (m, 2H), 1.65 – 1.61 (m, 2H),
1.57 (s, 6H), 1.35 (dd, J = 15.2, 7.3 Hz, 2H), 0.94 (t, J =
7.3 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ = 165.75,
140.60, 137.03, 128.57, 127.64, 127.26, 122.39, 69.12,
43.28, 31.55, 28.19, 20.35, 13.72. HRMS (ESI): [M+H+]
calcd. for C16H22NOSe+, 324.0861; found, 324.0875.
(Z)-3-Butyl-4,4-dimethyl-5-(4-methylbenzylidene)-1,3-
selenazolidin-2-one (2ab)
N-Butyl-1,5-diphenylpent-1-yn-3-amine (1s)
60.5 mg, 90% yield, yellow oil. 1H NMR (400 MHz,
Yellow oil, 80%. 1H NMR (400 MHz, CDCl3) δ = 7.44 (dd, CDCl3) δ = 7.18 (m, 4H), 6.88 (s, 1H), 3.28 – 3.24 (m, 2H),
J = 6.7, 2.8 Hz, 2H), 7.33 – 7.21 (m, 7H), 7.18 (dd, J =
12.4, 5.4 Hz, 1H), 3.56 (t, J = 6.8 Hz, 1H), 2.97 – 2.76 (m,
3H), 2.63 (dd, J = 15.7, 9.0 Hz, 1H), 2.10 – 1.92 (m, 2H),
1.56 – 1.42 (m, 3H), 1.37 (dq, J = 13.9, 7.1 Hz, 2H), 0.92
(t, J = 7.3 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ =
141.62, 131.57, 128.45, 128.28, 128.15, 127.82, 125.79,
123.35, 90.92, 84.01, 50.18, 47.13, 37.60, 32.38, 32.15,
20.42, 13.90. [M+H+] calcd. for C21H26N+, 292.2060;
found, 292.2065.
2.34 (s, 3H), 1.67 – 1.61 (m, 2H), 1.57 (s, 6H), 1.36 (dq, J
= 14.8, 7.4 Hz, 2H), 0.95 (t, J = 7.3 Hz, 3H). 13C NMR
(100 MHz, CDCl3) δ = 165.89, 139.36, 137.11, 134.16,
129.25, 127.54, 122.26, 69.04, 43.23, 31.55, 28.15, 21.17,
20.35, 13.73. HRMS (ESI): [M+H+] calcd. for
C17H24NOSe+, 338.1018; found, 338.1029.
(Z)-3-Butyl-5-(4-methoxybenzylidene)-4,4-dimethyl-1,3-
selenazolidin-2-one (2ac)
59.9 mg, 85% yield, yellow oil. 1H NMR (400 MHz,
CDCl3) δ = 7.21 (d, J = 8.6 Hz, 2H), 6.90 (d, J = 8.6 Hz,
2H), 6.85 (s, 1H), 3.81 (s, 3H), 3.28 – 3.24 (m, 2H), 1.66 –
N-(1-Cyclohexyl-3-phenylprop-2-yn-1-yl)butan-1-
amine (1t)
Yellow oil, 65%. 1H NMR (400 MHz, CDCl3) δ = 7.41 (dd, 1.61 (m, 2H), 1.56 (s, 6H), 1.40 – 1.30 (m, 2H), 0.94 (t, J =
J = 7.6, 1.8 Hz, 2H), 7.29 – 7.18 (m, 3H), 3.37 (d, J = 5.5
Hz, 1H), 2.92 (dt, J = 10.7, 7.5 Hz, 1H), 2.62 (dt, J = 11.2,
7.6 Hz, 1H), 1.92 – 1.81 (m, 2H), 1.77 (m, 2H), 1.67 (d, J
= 11.0 Hz, 1H), 1.63 – 1.55 (m, 1H), 1.54 – 1.43 (m, 2H),
1.42 – 1.34 (m, 2H), 1.21 (ddd, J = 20.5, 17.0, 9.6 Hz, 6H),
0.93 (t, J = 7.3 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ =
131.31, 127.84, 127.36, 123.44, 90.21, 84.06, 56.11, 47.33,
42.44, 31.96, 30.05, 28.40, 26.29, 26.01, 25.87, 20.25,
13.71.
7.3 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ = 165.85,
158.61, 138.01, 129.57, 128.91, 121.85, 113.93, 69.00,
55.20, 43.20, 31.53, 28.10, 20.32, 13.71. HRMS (ESI):
[M+H+] calcd. for C17H24NO2Se+, 354.0967; found,
354.0978.
(Z)-3-Butyl-4,4-dimethyl-5-(4-propylbenzylidene)-1,3-
selenazolidin-2-one (2ad)
68.5 mg, 94% yield, yellow oil. 1H NMR (400 MHz,
CDCl3) δ = 7.22 – 7.17 (m, 4H), 6.89 (s, 1H), 3.29 – 3.25
(m, 2H), 2.60 – 2.56 (m, 2H), 1.69 – 1.60 (m, 4H), 1.57 (s,
6H), 1.36 (dq, J = 14.7, 7.4 Hz, 2H), 0.94 (td, J = 7.3, 4.9
Hz, 6H). 13C NMR (100 MHz, CDCl3) δ = 165.87, 141.93,
139.24, 134.33, 128.67, 127.54, 122.29, 69.08, 43.23,
37.66, 31.54, 28.17, 24.34, 20.34, 13.73. HRMS (ESI):
[M+H+] calcd. for C19H28NOSe+, 366.1331; found,
366.1342.
Procedures for the preparation of 1u[25c, 25d,26]
,
Propargyl bromide (3 mL, 27 mmol) was added to benzyl
amine (18 mL, 162 mmol) over half hours via addition
funnel, and allowed to stir overnight. The resulting mixture
was diluted in Et2O, and extracted with saturated aq.
NaHCO3 and dried over MgSO4. The reaction mixture was
concentrated and purified by silica gel column
chromatography (PE/EtOAc=10/1) to afford the
corresponding propargylic amine 1u.
(Z)-3-Butyl-5-(4-(tert-butyl)benzylidene)-4,4-dimethyl-
1,3-selenazolidin-2-one (2ae)
N-Benzylprop-2-yn-1-amine (1u)
72.7 mg, 96% yield, yellow oil. 1H NMR (400 MHz,
CDCl3) δ = 7.39 (d, J = 8.2 Hz, 2H), 7.23 (t, J = 5.8 Hz,
2H), 6.88 (s, 1H), 3.28 – 3.24 (m, 2H), 1.67 – 1.61 (m, 2H),
1.56 (s, 6H), 1.37 (dd, J = 15.1, 7.8 Hz, 2H), 1.31 (s, 9H),
0.94 (t, J = 7.3 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ =
165.82, 150.27, 139.27, 134.01, 127.37, 125.47, 122.11,
69.09, 43.22, 34.53, 31.52, 31.14, 28.17, 20.32, 13.71.
HRMS (ESI): [M+H+] calcd. for C20H30NOSe+, 380.1487;
found, 380.1500.
1
Yellow oil, 68%. H NMR (400 MHz, CDCl3) δ = 7.35 –
7.29 (m, 4H), 7.25 (td, J = 5.7, 2.6 Hz, 1H), 3.86 (s, 2H),
3.40 (d, J = 2.4 Hz, 2H), 2.25 (t, J = 2.4 Hz, 1H), 1.74 (s,
1H). 13C NMR (100 MHz, CDCl3) δ = 139.26, 128.32,
128.29, 127.05, 81.95, 71.48, 52.14, 37.19.
Typical Procedure for Reaction of Propargylic Amines
with Se and TFBen
(Z)-3-Butyl-5-(4-fluorobenzylidene)-4,4-dimethyl-1,3-
selenazolidin-2-one (2af)
Se (0.3 mmol, 1.5 equiv.), TFBen (0.2 mmol, 1.0 equiv.)
and tBuOK (0.1 mmol, 50 mol%) were added to a 15 mL
tube equipped with a magnetic stirrer which was then
placed under vacuum and refilled with nitrogen three times.
A solution of propargylic amine 1 (0.2 mmol) in DMF (1.0
mL) was added to the reaction tube, then the tube was
sealed and the mixture was stirred at 35 °C for 24 h. After
the reaction was completed, the reaction mixture was
diluted with 50 mL water and extracted with 30 mL EtOAc
three times. The combined organic phases were dried with
anhydrous Na2SO4, concentrated and purified by silica gel
column chromatography (PE/EtOAc=10/1) to obtain
desired (Z)-1,3-selenazolidin-2-one 2.
59.9 mg, 88% yield, yellow oil. 1H NMR (400 MHz,
CDCl3) δ = 7.27 – 7.24 (m, 2H), 7.06 (dd, J = 11.9, 5.3 Hz,
2H), 6.87 (s, 1H), 3.28 – 3.24 (m, 2H), 1.67 – 1.59 (m, 2H),
1.57 (s, 6H), 0.95 (t, J = 7.4 Hz, 3H). 13C NMR (100 MHz,
CDCl3) δ = 165.40, 161.63 (d, J = 246.4 Hz), 140.64,
133.22 (d, J = 3.2 Hz), 129.30 (d, J = 7.9 Hz), 121.30,
115.55 (d, J = 21.5 Hz), 69.04, 43.33, 31.54, 28.16, 20.35,
13.73. HRMS (ESI): [M+Na+] calcd. for C16H20FNNaOSe+,
364.0586; found, 364.0605.
(Z)-3-Butyl-5-(4-chlorobenzylidene)-4,4-dimethyl-1,3-
selenazolidin-2-one (2ag)
(Z)-5-Benzylidene-3-butyl-4,4-dimethyl-1,3-
selenazolidin-2-one (2aa)
6
This article is protected by copyright. All rights reserved.

10.1002/adsc.201800109
Advanced Synthesis & Catalysis
58.7 mg, 81% yield, yellow oil. 1H NMR (400 MHz,
7.5 Hz, 2H), 0.94 (t, J = 7.3 Hz, 3H). 13C NMR (100 MHz,
CDCl3) δ = 167.34, 141.69, 136.08, 128.51, 128.14, 127.11,
CDCl3) δ = 7.33 (d, J = 8.4 Hz, 2H), 7.21 (d, J = 8.4 Hz,
2H), 6.85 (s, 1H), 3.28 – 3.24 (m, 2H), 1.67 – 1.61 (m, 2H), 118.96, 77.89, 42.69, 38.82, 31.55, 25.35, 20.41, 13.70.
1.57 (s, 6H), 1.40 – 1.31 (m, 2H), 0.95 (t, J = 7.3 Hz, 3H).
13C NMR (100 MHz, CDCl3) δ = 165.25, 141.72, 135.55,
132.84, 128.89, 128.74, 121.23, 69.12, 43.36, 31.52, 28.18,
20.35, 13.73. HRMS (ESI): [M+Na+] calcd. for
C16H20ClNNaOSe+, 380.0291; found, 380.0310.
HRMS (ESI): [M+Na+] calcd. for C18H23NNaOSe+,
372.0837; found, 372.0835.
(Z)-4-Benzylidene-1-butyl-3-selena-1-
azaspiro[4.5]decan-2-one (2f)
(Z)-5-(4-Bromobenzylidene)-3-butyl-4,4-dimethyl-1,3-
selenazolidin-2-one (2ah)
60.9 mg, 84% yield, pale yellow solid, mp. 132.9-135.1 °C.
1H NMR (400 MHz, CDCl3) δ = 7.36 (t, J = 7.4 Hz, 2H),
7.30 – 7.26 (m, 3H), 7.24 (s, 1H), 3.28 – 3.24 (m, 2H),
2.17 (d, J = 9.2 Hz, 2H), 1.79 (dd, J = 22.8, 12.0 Hz, 6H),
1.58 – 1.51 (m, 2H), 1.38 – 1.26 (m, 4H), 0.94 (t, J = 7.3
61.0 mg, 76% yield, yellow oil. 1H NMR (400 MHz,
CDCl3) δ = 7.48 (d, J = 8.3 Hz, 2H), 7.15 (d, J = 8.3 Hz,
2H), 6.83 (s, 1H), 3.28 – 3.24 (m, 2H), 1.67 – 1.61 (m, 2H), Hz, 3H). 13C NMR (100 MHz, CDCl3) δ = 167.44, 140.68,
1.57 (s, 6H), 1.35 (dd, J = 15.1, 7.4 Hz, 2H), 0.94 (t, J =
7.3 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ = 165.19,
141.86, 135.98, 131.66, 129.16, 121.26, 120.95, 69.13,
43.35, 31.50, 28.14, 20.33, 13.72. HRMS (ESI): [M+Na+]
calcd. for C16H20BrNNaOSe+, 423.9786; found, 423.9770.
137.37, 128.41, 127.90, 127.54, 126.68, 70.86, 43.02,
33.30, 32.21, 24.66, 23.01, 20.26, 13.76. HRMS (ESI):
[M+Na+] calcd. for C19H25NNaOSe+, 386.0994; found,
386.0988.
(Z)-4-Benzylidene-1-butyl-3-selena-1-
azaspiro[4.6]undecan-2-one (2g)
(Z)-3-Benzyl-5-benzylidene-4,4-dimethyl-1,3-
selenazolidin-2-one (2ba)
44.4 mg, 59% yield, yellow oil. 1H NMR (400 MHz,
CDCl3) δ = 7.38 (t, J = 7.5 Hz, 2H), 7.29 (dd, J = 13.6, 8.8
Hz, 3H), 7.05 (s, 1H), 3.39 – 3.35 (m, 2H), 2.19 (dd, J =
15.5, 8.9 Hz, 2H), 2.08 (dd, J = 15.6, 7.4 Hz, 2H), 1.69 –
1.62 (m, 10H), 1.36 (dd, J = 15.0, 7.5 Hz, 2H), 0.95 (t, J =
7.3 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ = 166.06,
141.05, 137.21, 128.54, 127.95, 127.47, 124.31, 75.51,
43.57, 38.69, 31.60, 31.51, 24.23, 20.50, 13.75. HRMS
(ESI): [M+Na+] calcd. for C20H27NNaOSe+, 400.1150;
found, 400.1158.
42.8 mg, 60% yield, yellow oil. 1H NMR (400 MHz,
CDCl3) δ = 7.37 (t, J = 7.6 Hz, 2H), 7.32 – 7.24 (m, 8H),
6.90 (s, 1H), 4.62 (s, 2H), 1.52 (s, 6H). 13C NMR (100
MHz, CDCl3) δ = 167.03, 140.32, 137.88, 136.92, 128.61,
128.53, 127.67, 127.40, 127.19, 126.94, 122.58, 69.39,
45.90, 28.26. HRMS (ESI): [M+Na+] calcd. for
C19H19NNaOSe+, 380.0524; found, 380.0518.
(Z)-5-Benzylidene-3-(4-methoxybenzyl)-4,4-dimethyl-
1,3-selenazolidin-2-one (2bb)
(Z)-4-Benzylidene-1-butyl-8-methyl-3-selena-1-
azaspiro[4.5]decan-2-one (2h)
49.4 mg, 67% yield, yellow oil. 1H NMR (400 MHz,
CDCl3) δ = 7.37 (t, J = 7.6 Hz, 2H), 7.29 – 7.21 (m, 5H),
6.89 (s, 1H), 6.84 (d, J = 8.6 Hz, 2H), 4.56 (s, 2H), 3.78 (s,
64.3 mg, 92% yield, pale yellow solid, mp 103.1-106.5 °C.
3H), 1.51 (s, 6H). 13C NMR (100 MHz, CDCl3) δ = 166.96, 1H NMR (400 MHz, CDCl3) δ = 7.37 (t, J = 7.5 Hz, 2H),
158.77, 140.45, 136.94, 130.03, 128.60, 128.38, 127.67,
127.37, 122.48, 113.90, 69.41, 55.20, 45.40, 28.30. HRMS
(ESI): [M+Na+] calcd. for C20H21NNaO2Se+, 410.0630;
found, 410.0639.
7.26 (d, J = 5.0 Hz, 3H), 7.24 (s, 1H), 3.26 – 3.22 (m, 2H),
2.18 (d, J = 13.7 Hz, 2H), 1.87 – 1.77 (m, 4H), 1.58 – 1.50
(m, 2H), 1.44 (t, J = 9.8 Hz, 3H), 1.34 (dd, J = 15.0, 7.5 Hz,
2H), 0.98 – 0.91 (m, 6H). 13C NMR (100 MHz, CDCl3) δ =
167.56, 140.68, 137.33, 128.38, 127.89, 127.55, 126.79,
70.59, 42.90, 33.13, 32.18, 31.67, 31.47, 22.01, 20.22,
13.74. HRMS (ESI): [M+H+] calcd. for C20H28NOSe+,
378.1331; found, 378.1315.
(Z)-5-Benzylidene-3-(4-chlorobenzyl)-4,4-dimethyl-1,3-
selenazolidin-2-one (2bc)
64.1 mg, 82% yield, yellow oil. 1H NMR (400 MHz,
CDCl3) δ = 7.38 (t, J = 7.6 Hz, 2H), 7.26 (dt, J = 12.9, 5.5
Hz, 7H), 6.91 (s, 1H), 4.57 (s, 2H), 1.51 (s, 6H). 13C NMR
(100 MHz, CDCl3) δ = 167.23, 139.99, 136.83, 136.45,
133.04, 128.71, 128.65, 128.39, 127.67, 127.50, 122.80,
69.31, 45.28, 28.26. HRMS (ESI): [M+Na+] calcd. for
C19H18ClNNaOSe+, 414.0134; found, 414.0150.
(Z)-3-Butyl-4,4-dimethyl-5-(thiophen-3-ylmethylene)-
1,3-selenazolidin-2-one (2i)
62.4 mg, 95% yield, yellow oil. 1H NMR (400 MHz,
CDCl3) δ = 7.33 (dd, J = 5.0, 2.9 Hz, 1H), 7.18 (d, J = 1.8
Hz, 1H), 7.10 (dd, J = 5.0, 0.9 Hz, 1H), 6.93 (s, 1H), 3.27
– 3.23 (m, 2H), 1.63 (ddd, J = 11.9, 10.3, 6.6 Hz, 2H), 1.55
(s, 6H), 1.35 (dq, J = 14.8, 7.4 Hz, 2H), 0.94 (t, J = 7.3 Hz,
3H). 13C NMR (100 MHz, CDCl3) δ = 165.26, 139.82,
138.37, 127.47, 125.76, 122.27, 116.88, 68.84, 43.34,
31.49, 28.16, 20.33, 13.73. HRMS (ESI): [M+H+] calcd.
for C14H20NOSSe+, 330.0425; found, 330.0446.
(Z)-5-Benzylidene-4,4-dimethyl-3-octyl-1,3-
selenazolidin-2-one (2c)
71.9 mg, 95% yield, yellow oil. 1H NMR (400 MHz,
CDCl3) δ = 7.36 (t, J = 7.6 Hz, 2H), 7.29 – 7.22 (m, 3H),
6.91 (s, 1H), 3.27 – 3.23 (m, 2H), 1.64 – 1.62 (m, 2H),
1.57 (s, 6H), 1.31 – 1.27 (m, 10H), 0.88 (t, J = 6.7 Hz, 3H).
13C NMR (100 MHz, CDCl3) δ = 165.67, 140.57, 136.99,
128.55, 127.62, 127.23, 122.35, 69.08, 43.50, 31.72, 29.44,
29.16, 28.17, 27.11, 22.56, 14.04, 0.95. HRMS (ESI):
[M+Na+] calcd. for C20H29NNaOSe+, 402.1307; found,
402.1317.
(Z)-3-Butyl-5-heptylidene-4,4-dimethyl-1,3-
selenazolidin-2-one (2j)
44.9 mg, 68% yield, yellow oil. 1H NMR (400 MHz,
CDCl3) δ = 5.78 (t, J = 6.9 Hz, 1H), 3.19 – 3.15 (m, 2H),
1.93 (dd, J = 14.3, 7.1 Hz, 2H), 1.62 – 1.54 (m, 2H), 1.42
(s, 6H), 1.40 – 1.36 (m, 2H), 1.34 – 1.26 (m, 8H), 0.89 (dt,
J = 13.5, 7.1 Hz, 6H). 13C NMR (100 MHz, CDCl3) δ =
165.75, 139.13, 122.70, 67.57, 43.07, 33.63, 31.61, 31.59,
28.73, 28.62, 27.92, 22.52, 20.34, 14.02, 13.74. HRMS
(ESI): [M+H+] calcd. for C16H30NOSe+, 332.1487; found,
332.1504.
(Z)-4-Benzylidene-1-butyl-3-selena-1-
azaspiro[4.4]nonan-2-one (2e)
43.2 mg, 62% yield, yellow oil. 1H NMR (400 MHz,
CDCl3) δ = 7.36 (t, J = 7.6 Hz, 2H), 7.28 – 7.23 (m, 3H),
6.81 (s, 1H), 3.24 – 3.20 (m, 2H), 2.23 – 2.17 (m, 2H),
2.03 (dt, J = 13.8, 8.3 Hz, 2H), 1.88 (t, J = 7.2 Hz, 4H),
1.65 (ddd, J = 11.9, 10.4, 6.7 Hz, 2H), 1.35 (dd, J = 15.1,
(Z)-3-Butyl-4,4-dimethyl-5-(3-phenylpropylidene)-1,3-
selenazolidin-2-one (2k)
7
This article is protected by copyright. All rights reserved.

10.1002/adsc.201800109
Advanced Synthesis & Catalysis
39.2 mg, 56% yield, yellow oil. 1H NMR (400 MHz,
CDCl3) δ = 7.30 – 7.26 (m, 2H), 7.18 (dd, J = 15.0, 7.6 Hz,
3H), 5.81 (t, J = 6.9 Hz, 1H), 3.19 – 3.15 (m, 2H), 2.73 (t,
J = 7.6 Hz, 2H), 2.27 (dd, J = 14.9, 7.2 Hz, 2H), 1.58 (tt, J
= 8.0, 6.6 Hz, 2H), 1.40 (s, 6H), 1.32 (dd, J = 15.1, 7.5 Hz,
2H), 0.92 (t, J = 7.3 Hz, 3H). 13C NMR (100 MHz, CDCl3)
δ = 165.51, 140.99, 140.37, 128.40, 128.33, 126.01, 121.46,
67.60, 43.09, 35.25, 34.71, 31.57, 27.89, 20.32, 13.73.
HRMS (ESI): [M+Na+] calcd. for C18H25NNaOSe+,
374.0994; found, 374.1004.
49.7 mg, 64% yield, pale yellow solid, mp 83.9-86.5 °C.
1H NMR (400 MHz, CDCl3) δ = 7.39 (dd, J = 8.5, 5.2 Hz,
2H), 7.33 (t, J = 7.6 Hz, 2H), 7.22 (t, J = 7.4 Hz, 1H), 7.17
(d, J = 7.5 Hz, 2H), 7.10 (t, J = 8.6 Hz, 2H), 6.70 (s, 1H),
5.43 (s, 1H), 3.76 – 3.67 (m, 1H), 2.69 (ddd, J = 13.9, 8.3,
5.6 Hz, 1H), 1.48 (td, J = 15.8, 8.2 Hz, 2H), 1.31 – 1.28 (m,
2H), 0.88 (t, J = 7.3 Hz , 3H). 13C NMR (100 MHz,
CDCl3) δ = 166.46, 162.87 (d, J = 249.0 Hz), 136.26,
135.60 (d, J = 2.6 Hz), 132.85, 128.68 (d, J = 3.1 Hz),
128.61, 127.61, 127.52, 126.83, 116.20 (d, J = 21.8 Hz),
70.52, 43.53, 29.22, 19.93, 13.64. HRMS (ESI): [M+Na+]
calcd. for C20H20FNNaOSe+, 412.0586; found, 412.0602.
(Z)-3-Butyl-5-(cyclopropylmethylene)-4,4-dimethyl-1,3-
selenazolidin-2-one (2l)
(Z)-5-Benzylidene-3-butyl-4-ethyl-1,3-selenazolidin-2-
one (2r)
44.7 mg, 78% yield, yellow oil. 1H NMR (400 MHz,
CDCl3) δ = 5.29 (d, J = 8.4 Hz, 1H), 3.19 – 3.15 (m, 2H),
1.61 – 1.53 (m, 2H), 1.41 (s, 6H), 1.31 (dd, J = 15.1, 7.5
Hz, 2H), 1.11 – 1.03 (m, 1H), 0.91 (t, J = 7.3 Hz, 3H), 0.83
– 0.78 (m, 2H), 0.45 – 0.41 (m, 2H). 13C NMR (100 MHz,
CDCl3) δ = 165.81, 137.11, 125.86, 67.53, 43.08, 31.61,
27.80, 20.34, 15.02, 13.74, 6.92. HRMS (ESI): [M+Na+]
calcd. for C13H21NNaOSe+, 310.0681; found, 310.0688.
55.4 mg, 86% yield, yellow oil. 1H NMR (400 MHz,
CDCl3) δ = 7.39 – 7.35 (m, 2H), 7.27 – 7.23 (m, 3H), 6.85
(s, 1H), 4.44 – 4.42 (m, 1H), 3.81 (ddd, J = 13.9, 8.8, 7.2
Hz, 1H), 3.00 (ddd, J = 13.9, 8.6, 5.3 Hz, 1H), 2.00 – 1.90
(m, 1H), 1.85 – 1.76 (m, 1H), 1.66 – 1.50 (m, 2H), 1.37 –
1.31 (m, 2H), 0.96 (dt, J = 11.5, 7.4 Hz, 6H).13C NMR
(100 MHz, CDCl3) δ = 166.63, 136.37, 132.65, 128.59,
127.62, 127.32, 124.92, 67.69, 42.96, 29.54, 27.35, 20.00,
13.70, 7.67. HRMS (ESI): [M+H+] calcd. for
C16H21NNaOSe+, 346.0681; found, 346.0700.
(Z)-3-Butyl-5-(cyclohex-1-en-1-ylmethylene)-4,4-
dimethyl-1,3-selenazolidin-2-one (2m)
50.9 mg, 78% yield, yellow oil. 1H NMR (400 MHz,
CDCl3) δ = 6.27 (s, 1H), 5.71 (s, 1H), 3.22 – 3.18 (m, 2H),
2.14 – 2.11 (m, 4H), 1.66 – 1.62 (m, 2H), 1.60 – 1.54 (m,
4H), 1.46 (s, 6H), 1.35 – 1.29 (m, 2H), 0.92 (t, J = 7.3 Hz,
3H). 13C NMR (126 MHz, CDCl3) δ = 166.76, 135.53,
135.30, 128.88, 125.31, 68.82, 43.05, 31.59, 28.05, 27.84,
25.63, 22.59, 21.88, 20.36, 13.74. HRMS (ESI): [M+Na+]
calcd. for C16H25NNaOSe+, 350.0994; found, 350.1003.
(Z)-5-Benzylidene-3-butyl-4-phenethyl-1,3-
selenazolidin-2-one (2s)
76.5 mg, 96% yield, yellow oil. 1H NMR (400 MHz,
CDCl3) δ = 7.38 (t, J = 7.6 Hz, 2H), 7.30 – 7.25 (m, 5H),
7.22 – 7.16 (m, 3H), 6.92 (s, 1H), 4.48 (d, J = 4.2 Hz, 1H),
3.85 – 3.77 (m, 1H), 2.99 (ddd, J = 13.8, 8.3, 5.5 Hz, 1H),
2.80 – 2.67 (m, 2H), 2.27 – 2.18 (m, 1H), 2.11 – 2.03 (m,
1H), 1.61 – 1.51 (m, 2H), 1.32 (dt, J = 14.8, 7.3 Hz, 2H),
0.92 (t, J = 7.3 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ =
166.49, 140.76, 136.22, 132.68, 128.62, 128.49, 128.18,
127.67, 127.46, 126.10, 125.29, 66.40, 42.96, 35.83, 29.52,
29.48, 19.93, 13.64. HRMS (ESI): [M+Na+] calcd. for
C22H25NNaOSe+, 422.0994; found, 422.1009.
(Z)-5-Benzylidene-4,4-dimethyl-1,3-selenazolidin-2-one
(2n)
45.8 mg, 86% yield, pale yellow solid, mp 123.4-125.7 °C.
1H NMR (400 MHz, CDCl3) δ = 7.40 (t, J = 7.6 Hz, 2H),
7.38 – 7.28 (m, 3H), 6.87 (s, 1H), 1.64 (s, 6H).13C NMR
(100 MHz, CDCl3) δ = 168.70, 141.54, 136.77, 128.59,
127.53, 127.33, 122.76, 64.59, 29.99. HRMS (ESI):
[M+Na+] calcd. for C12H13NNaOSe+, 290.0055; found,
290.0069.
(Z)-5-Benzylidene-3-butyl-4-cyclohexyl-1,3-
selenazolidin-2-one (2t)
73.0 mg, 97% yield, yellow oil. 1H NMR (400 MHz,
CDCl3) δ = 7.38 (t, J = 7.6 Hz, 2H), 7.26 (t, J = 8.1 Hz,
3H), 6.80 (s, 1H), 4.23 (d, J = 2.2 Hz, 1H), 3.82 (ddd, J =
14.1, 8.8, 7.0 Hz, 1H), 3.06 (ddd, J = 14.0, 8.8, 5.3 Hz, 1H),
1.80 (d, J = 8.6 Hz, 4H), 1.68 – 1.52 (m, 4H), 1.42 – 1.28
(m, 4H), 1.15 (dt, J = 26.1, 11.1 Hz, 3H), 0.94 (t, J = 7.3
Hz, 3H). 13C NMR (100 MHz, CDCl3) δ = 167.26, 136.23,
130.98, 128.55, 127.78, 127.41, 126.90, 72.20, 43.70,
42.25, 29.60, 29.29, 26.80, 26.46, 26.36, 26.16, 20.02,
13.72. HRMS (ESI): [M+Na+] calcd. for C20H27NNaOSe+,
400.1150; found, 400.1170.
(Z)-5-Benzylidene-3-butyl-4-phenyl-1,3-selenazolidin-2-
one (2o)
37.0 mg, 50% yield, pale yellow solid, mp 93.5-96.9 °C.
1H NMR (400 MHz, CDCl3) δ = 7.38 (dt, J = 10.3, 4.5 Hz,
5H), 7.32 (t, J = 7.6 Hz, 2H), 7.25 – 7.15 (m, 3H), 6.73 (s,
1H), 5.43 (s, 1H), 3.77 – 3.69 (m, 1H), 2.70 (ddd, J = 13.8,
8.0, 5.7 Hz, 1H), 1.50 – 1.48 (m, 2H), 1.29 – 1.26 (m, 2H),
0.88 (t, J = 7.3 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ =
166.63, 139.69, 136.40, 133.03, 129.16, 128.78, 128.55,
127.61, 127.38, 126.92, 126.65, 71.28, 43.53, 29.23, 19.94,
13.65. HRMS (ESI): [M+Na+] calcd. for C20H21NNaOSe+,
394.0681; found, 394.0671.
3-Benzyl-5-methylene-1,3-selenazolidin-2-one (2u)
42.9 mg, 85% yield, yellow oil. 1H NMR (400 MHz,
CDCl3) δ = 7.38 – 7.26 (m, 5H), 5.55 (s, 1H), 5.24 (s, 1H),
4.55 (s, 2H), 4.13 (s, 2H). 13C NMR (126 MHz, CDCl3) δ
= 167.29, 135.48, 134.77, 128.84, 128.07, 127.95, 110.91,
55.89, 48.57. HRMS (ESI): [M+H+] calcd. for
C11H12NOSe+, 254.0079; found, 254.0076.
(Z)-5-Benzylidene-3-butyl-4-(4-methoxyphenyl)-1,3-
selenazolidin-2-one (2p)
46.5 mg, 58% yield, yellow oil. 1H NMR (400 MHz,
CDCl3) δ = 7.34 – 7.30 (m, 4H), 7.22 – 7.16 (m, 3H), 6.93
(d, J = 8.6 Hz, 2H), 6.69 (s, 1H), 5.40 (s, 1H), 3.82 (s, 3H),
3.71 (dt, J = 14.0, 7.8 Hz, 1H), 2.71 (ddd, J = 13.8, 8.2, 5.6
Hz, 1H), 1.49 – 1.46 (m, 2H), 1.29 – 1.26 (m, 3H), 0.88 (t,
J = 7.3 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ = 166.42,
159.92, 136.48, 133.49, 131.70, 128.55, 128.27, 127.61,
127.33, 126.47, 114.50, 70.84, 55.32, 43.47, 29.21, 19.96,
13.68. HRMS (ESI): [M+Na+] calcd. for C21H23NNaO2Se+,
424.0786; found, 424.0780.
Acknowledgements
The authors are grateful for the financial support from NSFC
(21472174, 21772177), Zhejiang Natural Science Fund for
Young Scholars (LQ18B020008) and Zhejiang Natural Science
Fund for Distinguished Young Scholars (LR16B020002).
(Z)-5-Benzylidene-3-butyl-4-(4-fluorophenyl)-1,3-
selenazolidin-2-one (2q)
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8
This article is protected by copyright. All rights reserved.

10.1002/adsc.201800109
Advanced Synthesis & Catalysis
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FULL PAPER
Base-Promoted Carbonylative Cyclization of
Propargylic Amines with Selenium under CO gas-
free conditions
Adv. Synth. Catal. Year, Volume, Page – Page
Hai Wang, Jun Ying, Ming Lai, Xinxin Qi, Jin-Bao
Peng, and Xiao-Feng Wu*
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