Z-Selective hydroamidation of terminal alkynes with secondary amides and imides catalyzed by a Ru/Yb-system

Article abstract of DOI:10.1016/j.jorganchem.2010.08.034

A catalyst system formed in situ from bis(2-methallyl)cycloocta-1,5-diene- ruthenium(II) [(cod)Ru(met)₂], 1,4-bis(dicyclohexylphosphino)butane (dcypb) and ytterbium(III) triflate hydrate (Yb(OTf)₃) was found to catalyze the addition of nitrogen nucleophiles to terminal alkynes under mild conditions to stereoselectively form the Z-enamide or Z-enimide products. Various secondary amides and imides could be added across the triple bond of a range of aliphatic and aromatic alkynes. The new bimetallic catalyst system sets new standards with regard to scope and selectivity for the synthesis of Z-configured anti-Markovnikov enamides.

Full text of DOI:10.1016/j.jorganchem.2010.08.034

Journal of Organometallic Chemistry 696 (2011) 170e178
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Journal of Organometallic Chemistry
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Z-Selective hydroamidation of terminal alkynes with secondary amides
and imides catalyzed by a Ru/Yb-system
*
Annette E. Buba, Matthias Arndt, Lukas J. Gooßen
Fachbereich Chemie, Technische Universität Kaiserslautern, Erwin-Schrödinger-Straße, Building 54, D-67663 Kaiserslautern, Germany
a r t i c l e i n f o
a b s t r a c t
Article history:
A catalyst system formed in situ from bis(2-methallyl)cycloocta-1,5-diene-ruthenium(II) [(cod)Ru(met)2],
1,4-bis(dicyclohexylphosphino)butane (dcypb) and ytterbium(III) triflate hydrate (Yb(OTf)3) was found to
catalyze the addition of nitrogen nucleophiles to terminal alkynes under mild conditions to stereo-
selectively form the Z-enamide or Z-enimide products. Various secondary amides and imides could be
added across the triple bond of a range of aliphatic and aromatic alkynes. The new bimetallic catalyst
system sets new standards with regard to scope and selectivity for the synthesis of Z-configured anti-
Markovnikov enamides.
Received 21 July 2010
Received in revised form
12 August 2010
Accepted 24 August 2010
Keywords:
Ó 2010 Elsevier B.V. All rights reserved.
Addition reaction
Bimetallic catalysis
Z-Enamide
Hydroamidation
Lewis acid
Ruthenium
1. Introduction
In the context of our research on the use of carboxylic acid
derivatives as substrates in catalysis [21], and based on related
The enamide substructure is abundant in natural products [1]
and synthetic drugs with sedative [2], cytotoxic [3], or anti-
inflammatory [4] properties. Examples for biologically active
enamides with Z-configuration are lansiumamides A and B [5],
cyclopeptide alkaloids like mucronines or abyssenines [6], asper-
gillamide A [3], igzamide [7], as well as botryllamide [8,9]. Fig. 1
Enamides are versatile synthetic intermediates that can serve as
substrates for heterocycle syntheses [10,11], cross-coupling reac-
tions [12], Heck olefinations [13], enantioselective additions [14], or
asymmetric hydrogenations [15]. Established enamide syntheses,
such as the condensation of carbonyl derivatives with amides [16],
require harsh conditions and yield mixtures of E- and Z-enamides.
Alternative syntheses of enamides are often based on sensitive
precursors, e.g. alkoxyallenes [17].
work on the addition of nucleophiles to multiple bonds [22], we
developed Ru-catalysts that allow the atom-economic addition of
NeH-bonds to terminal alkynes under mild conditions (Scheme 1).
The scope of the initial protocol, in which ruthenium phos-
phines complexes in combination with auxiliary bases were
employed as catalysts, included secondary amides, ureas, lactams,
and oxazolidinones [23,24]. The stereoselectivity of the addition
reaction was determined by the choice of ligands and bases. In the
presence of monodentate ligands and strongly coordinating bases
such as 4-dimethylaminopyridine, E-products were obtained in
high selectivity. The stereoselectivity could be reversed using
chelating ligands and small amounts of water instead of the base.
However, the scope and the Z-selectivity of this second protocol
were only moderate. Improved catalyst systems allowed the
extension of this reaction concept to imides [25], thioamides [26],
and finally primary amides [27].
In this last protocol, the auxiliary bases were replaced by Lewis
acid co-catalysts. As a result, the NeH acidity rather than the
nucleophilicity of the NeH component determined the reaction
outcome. This way, primary amides could chemoselectively be
coupled in the presence of secondary amides to give the Z-config-
ured enamides in up to 22:1 stereoselectivity. These experiments
seemed to suggest that secondary amides are very slow to react
The selective synthesis of the thermodynamically disfavored Z-
enamide is much harder and has less literature precedent. Prepa-
rations via Curtius rearrangement [18], Peterson elimination
[5c,19], or cross-coupling reactions [20] transfer the selectivity
problem to the availability of the starting materials.
* Corresponding author. Tel.: þ49 631 205 2046; fax: þ49 631 205 3921.
E-mail address: goossen@chemie.uni-kl.de (L.J. Gooßen).
0022-328X/$ e see front matter Ó 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2010.08.034

A.E. Buba et al. / Journal of Organometallic Chemistry 696 (2011) 170e178
171
Fig. 1. Z-Enamide structure in bioactive molecules.
with such bimetallic catalyst systems. However, we now found that
under modified reaction conditions, Yb/Ru-catalysts can also
promote the addition of secondary amides and imides to terminal
alkynes in high yields and excellent selectivities for the Z-config-
ured anti-Markovnikov products.
effective (entries 14e18). Without added ligand, no conversion
was observed (entry 13). Variation of the Lewis acidic co-catalyst
did not improve the yield or the stereoselectivity, and Yb(OTf)3
remained the most effective additive (entries 19e21). A shorter
reaction time of 6 h resulted in lower yields (entry 22), and 60 ꢀC
reaction temperature was confirmed to be optimal. Decreasing as
well as increasing the temperature led to worse yields and
selectivities (entries 23e25). Heating a mixture of enamide
isomers in the presence of the ruthenium catalyst did not influ-
ence the isomeric ratio, indicating that an interconversion
between the product isomers, e.g., via reversible amide addition
does not take place [28].
After optimizing the catalyst system, we tested the generality of
the new Z-selective hydroamidation protocol (Table 2). Several
reactions had to be carried out in DMF because of an insufficient
solubility of some amides in chlorobenzene. We were pleased to
find that besides lactams (1aec), several carbamates (1dee) and
linear amides (1gek) selectively reacted with hex-1-yne (2a) in
moderate to high yields to the desired Z-enamides. Even chiral
auxiliaries can be used as coupling partners (1e). Limitations were
observed for linear amides with aliphatic substituents on the
nitrogen, possibly based on stereoelectronic effects (1g, 1i). Various
alkynes were successfully converted into Z-enamides, among them
are the aliphatic derivatives hept-1-yne (2b), oct-1-yne (2c), and 3-
cyclohexyl-prop-1-yne (2d). Alkynes with chloride (2g) or aromatic
substituents (2hel) were tolerated, yielding the Z-enamides in
good to excellent Z/E-selectivities. With (trimethylsilyl)acetylene
(2e) or propargyl chloride (2f), none of the desired product could be
obtained. Instead, side products, e.g. from oligomerization reac-
tions, were observed.
2. Results and discussion
In our search for an effective catalyst for the desired hydro-
amidation of secondary amides, we chose the reaction of pyrro-
lidin-2-one (1a) with hex-1-yne (2a) as a model system to
investigate several catalyst systems under various conditions
(Table 1). Initially, a combination of (cod)Ru(met)2, dcypb, and Yb
(OTf)3 in DMF and 6 equiv of water was employed, which has been
the most effective system for the hydroamidation of primary
amides (entry 1). Here, the model substrates were converted in
66% yield and a stereoselectivity of 3:1 in favor of the thermo-
dynamically unfavored Z-enamide 3aa. Lowering the catalyst
loading to 2 mol% (cod)Ru(met)2 and 3 mol% dcypb led to higher
yields with a marginal upgrade of the selectivity, due to less
isomerization and polymerization side reactions also catalyzed by
ruthenium (entry 2). Without water as the co-solvent, decreased
selectivities were obtained (entry 3). A further reduction to 1 mol
% of Ru-source and 1.5 mol% phosphine resulted in lower yields
and did not enhance the selectivity in favor of the Z-enamide
(entry 4). Variation of the solvent revealed that nonpolar aromatic
solvents such as toluene or chlorobenzene were most effective
concerning the selectivity. Moreover, chlorobenzene led to an
improved ratio of 9:1 in favor of the Z-product (entries 5e10).
Although DMF gave a higher total yield, we subsequently focused
on chlorobenzene due to the higher selectivity of the catalyst
system obtained in this solvent. A smaller amount of 2.25 mol% of
dcypb showed further improvement. Under these conditions, 72%
yield could be obtained with a satisfactory Z/E-selectivity of 9:1
(entry 12). Among the ligands investigated, dcypb gave the
highest Z-selectivity. Bidentate ligands with smaller bite angles or
aromatic groups, as well as monodentate phosphines, were less
We also tested this catalyst system in the addition of imides to
terminal alkynes and were pleased to find that imides including
succinimide, 1,5,5-trimethylhydantoin and phthalimide (1len)
could be converted to Z-enimides with the same catalyst system in
excellent yields and selectivities greater than 20:1. Besides hex-1-
yne (2a), various aliphatic alkynes reacted with succinimide
yielding selectively the corresponding Z-enimides.
Scheme 1. Ruthenium-catalyzed hydroamidation of terminal alkynes.

172
A.E. Buba et al. / Journal of Organometallic Chemistry 696 (2011) 170e178
Table 1
Optimization of the catalyst and conditions.a
O
O
(cod)Ru(met)2
O
ligand, Lewis acid
nBu
+
+
N
nBu
NH
N
solvent,
nBu
60 °C, 16 h
1a
2a
3aa
4aa
Entry
(cod)Ru(met)2 [mol%]
Ligand [mol%]
Lewis acid [mol%]
Solvent
Yield [%] (ratio (3aa:4aa))
1
2
3
4
5
6
7
8
5
2
2
1
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
6 dcypb
3
3
1.5
3
3
3
3
3
4 Yb(OTf)3
4 Yb(OTf)3
4 Yb(OTf)3
4 Yb(OTf)3
4 Yb(OTf)3
4 Yb(OTf)3
4 Yb(OTf)3
4 Yb(OTf)3
4 Yb(OTf)3
4 Yb(OTf)3
4 Yb(OTf)3
4 Yb(OTf)3
4 Yb(OTf)3
4 Yb(OTf)3
4 Yb(OTf)3
4 Yb(OTf)3
4 Yb(OTf)3
4 Yb(OTf)3
4 Sc(OTf)3
4 Mg(OTf)2
4 AgOTf
DMF/6 equiv H2O
DMF/6 equiv H2O
DMF
DMF
Toluene
Chlorbenzene
THF
Quinoline
Acetonitrile
Water
Chlorobenzene
Chlorobenzene
Chlorobenzene
Chlorobenzene
Chlorobenzene
Chlorobenzene
Chlorobenzene
Chlorobenzene
Chlorobenzene
Chlorobenzene
Chlorobenzene
Chlorobenzene
Chlorobenzene
Chlorobenzene
Chlorobenzene
66 (3:1)
86 (4:1)
86 (3:1)
81 (3:1)
70 (7:1)
70 (9:1)
53 (7:1)
52 (2:1)
0
9
10
11
12
13
14
15
16
17
18
19
20
21
22b
23c
24d
25e
3
0
2 dcypb
2.25 dcypb
0 dcypb
2.25 dcype
2.25 dcypm
2.25 dppb
4.5 PCy3
4.5 P(nBu)3
2.25 dcypb
2.25 dcypb
2.25 dcypb
2.25 dcypb
2.25 dcypb
2.25 dcypb
2.25 dcypb
69 (8:1)
72 (9:1)
0
53 (5:1)
7
66 (1.5:1)
0
77 (1:1)
68 (8:1)
60 (9:1)
0
4 Yb(OTf)3
4 Yb(OTf)3
4 Yb(OTf)3
4 Yb(OTf)3
57 (9:1)
66 (6:1)
48 (8:1)
27 (6:1)
a
Reaction conditions: pyrrolidin-2-one (1.00 mmol), hex-1-yne (2.00 mmol), (cod)Ru(met)2, ligand, Lewis acid, solvent (3 mL), GC yields determined using n-tetradecane as
internal standard. Product ratio determined by GC. dcype ¼ 1,2-di(cyclohexylphosphino)ethane, dcypm ¼ 1,2-di(cyclohexylphosphino)methane, dppb ¼ di(phenylphosphino)
butane, PCy3 ¼ tricyclohexylphosphine, P(nBu)3 ¼ tri-n-butylphosphine.
b
6 h reaction time.
c
40 ꢀC temperature.
d
80 ꢀC temperature.
100 ꢀC temperature.
e
3. Conclusion
spectra were obtained on Bruker AMX 400 systems using benzene-
d6 or chloroform-d1 as solvent, with proton and carbon resonances
at 400 MHz and 101 MHz, respectively. Mass spectral data were
acquired on a GCeMS Saturn 2100 T (Varian). IR spectra were
measured using a Perkin Elmer FT-IR system. Elemental analyses
were carried out using a vario Micro tube (Elementar Analy-
setechnik/Hanau). GC/HRMS spectra were obtained on a GCT
Premier (WATERS).
In summary, a Ru-phosphine catalyst in combination with the
Lewis acid Yb(OTf)3 has been found to promote the regio- and
stereoselective addition of secondary amides and imides under
selective formation of the Z-configured anti-Markovnikov products.
The bimetallic catalyst system is superior to preceding mono-
metallic catalysts in terms of scope and stereoselectivity. The new
protocol provides an atom-economic entry to the thermodynami-
cally disfavored Z-isomers of various synthetically important
enamides and enimides.
4.1. Synthesis of Z-configured enamides and enimides
4. Experimental
4.1.1. General procedure
An oven-dried vessel was charged with N-nucleophile
1
All reactions were performed in oven-dried glassware contain-
ing a Teflon-coated stirring bar and dry septum under a nitrogen
atmosphere. Solvents were purified by standard procedures prior
to use. All reactions were monitored by GC using n-tetradecane as
an internal standard. Response factors of the products with regard
to n-tetradecane were obtained experimentally by analyzing
known quantities of the substances. GC analyses were carried out
using an HP-5 capillary column (phenyl methyl siloxane
30 m ꢁ 320 ꢁ 0.25, 100/2.3-30-300/3) and a time program begin-
ning with 2 min at 60 ꢀC followed by 30 ꢀC/min ramp to 300 ꢀC,
then 3 min at this temperature. Column chromatography was
(1.00 mmol), bis(2-methallyl)-cycloocta-1,5-diene-ruthenium(II)
(6.39 mg,
0.02 mmol),
1,4-bis(dicyclohexylphosphino)butane
(10.1 mg, 22.5
mmol) and ytterbium(III) triflate hydrate (24.8 mg,
0.04 mmol). After flushing the vessel with alternating vacuum and
nitrogen purge cycles, dry chlorobenzene (3 mL) or dry DMF (3 mL)
and the alkyne 2 (2.00 mmol) were added via syringe and the
resulting mixture was stirred at 60 ꢀC for 16 h. Then, it was allowed
to cool to room temperature and the reaction mixture was purified
without any work-up by column chromatography (silica gel, ethyl
acetate/hexane) to yield the Z-product. The identity and purity of
the products were confirmed by 1H and 13C NMR spectroscopy,
mass spectroscopy, elemental analysis, infrared spectroscopy and, if
a solid product was obtained, the melting points were determined.
performed using
a Combi Flash Companion chromatography
system (Isco-Systems) and RediSep prepacked columns (12 g). NMR

A.E. Buba et al. / Journal of Organometallic Chemistry 696 (2011) 170e178
173
Table 2
Substrate scope of the enamide and enimide synthesis.a
Product
Yield [%] (ratio 3:4)
Product
Yield [%] (ratio 3:4)
Product
Yield [%] (ratio 3:4)
O
O
O
N
nBu
N
N
nBu
72 (11:1)
43 (>20:1)
32 (>20:1)
nBu
3ca
3aa
3ba
O
O
O
O
O
N
N
O
N
nBu
88 (17:1)b
92 (>20:1)b
86 (10:1)b
nBu
nBu
Ph
3da
3ea
3fa
O
O
O
H
N
H
N
N
16 (>20:1)b,c
85 (3:1)b
5 (>20:1)b,c
Ph nBu
nBu
nBu
3ga
3ia
3ha
O
N
O
O
nBu
N
N
84 (>20:1)b
45 (1:1)b
74 (8:1)
Ph nBu
nPent
3ka
3ab
OEt
3ja
O
O
O
N
N
N
72 (9:1)
74 (12:1)
0c
nHex
Si
(CH2)Cy
(CH2)3Cl
3ad
3ac
3ae
O
O
O
N
N
N
0c
87 (4:1)b
75 (9:1)
3ah
3af
Cl
3ag
Ph
O
N
O
O
N
N
3aj
74 (>20:1)
73 (>20:1)
83 (>20:1)
Ph
3ak
3ai
(CH2)2CH3
O
O
O
N
N
N
86 (4:1)b
89 (>20:1)b
96 (>20:1)b
O
nBu
nBu
N
O
O
3ma
3al
3la
(continued on next page)

174
A.E. Buba et al. / Journal of Organometallic Chemistry 696 (2011) 170e178
Table 2 (continued )
Product
Yield [%] (ratio 3:4)
Product
Yield [%] (ratio 3:4)
Product
Yield [%] (ratio 3:4)
O
O
O
N
N
N
76 (>20:1)b
99 (>20:1)b
80 (>20:1)b
nBu
nHex
(CH2)Cy
O
O
O
3ld
3lc
3na
O
N
O
N
71 (>20:1)b
95 (>20:1)b
(CH2)3Cl
O
O
3lh
Ph
3lg
a
Reaction conditions: amide (1.00 mmol), alkyne (2.00 mmol), (cod)Ru(met)2 (0.02 mmol), 1,4-bis(dicyclohexylphosphino)butane (22.5
hydrate (0.04 mmol), chlorobenzene (3 mL), 60 ꢀC, 16 h, isolated yields. Product ratio determined by 1H NMR.
m
mol), ytterbium(III) triflate
b
DMF as solvent.
c
GC yields determined using n-tetradecane as internal standard. Product ratio determined by GC.
4.1.2. N-((Z)-Hex-1-enyl)pyrrolidin-2-one (3aa)
4.1.5. N-((Z)-Hex-1-enyl)oxazolidin-2-one (3da)
Compound 3aa was synthesized following the general proce-
dure using pyrrolidin-2-one (1a) (85.1 mg, 1.00 mmol) and hex-1-
Compound (3da) was synthesized following the general
procedure using oxazolidin-2-one (1d) (87.1 mg, 1.00 mmol) and
yne (2a) (234
mL, 2.00 mmol) in chlorobenzene and purified by
hex-1-yne (2a) (234 mL, 2.00 mmol) in DMF and purified by column
column chromatography (30:70 ethyl acetate/hexane), yielding the
product as a colorless oil (119 mg, 71%) with a (Z/E)-selectivity of
chromatography (30:70 ethyl acetate/hexane), yielding the product
as a colorless oil (149 mg, 88%) with a (Z/E)-selectivity of 17:1. 1H
11:1. 1H NMR (benzene-d6, 400 MHz):
d
¼ 6.73 (d, 3J ¼ 10.2 Hz, 1H),
NMR (benzene-d6, 400 MHz)
d
¼ 6.41 (d, 3J ¼ 9.8 Hz, 1H), 4.45e4.53
4.54e4.61 (m, 1H), 3.08 (t, 3J ¼ 7.0 Hz, 2H), 1.97e2.06 (m, 2H), 1.90
(m, 1H), 4.33 (t, 3J ¼ 8.0 Hz, 2H), 3.90 (t, 3J ¼ 8.0 Hz, 2H), 2.11 (q,
(t, 3J ¼ 8.2 Hz, 2H), 1.15e1.30 (m, 6H), 0.86 (t, 3J ¼ 6.8 Hz, 3H) ppm.
3J ¼ 6.8 Hz, 2H), 1.23e1.35 (m, 4H), 0.84 (t, 3J ¼ 7.0 Hz, 3H) ppm. 13
C
13C NMR (benzene-d6, 101 MHz):
d
¼ 173.4, 122.8, 113.3, 47.8, 33.1,
NMR (benzene-d6, 101 MHz)
d
¼ 156.5, 123.2, 112.9, 61.5, 44.9, 32.9,
29.9, 27.1, 22.6, 18.3, 14.1 ppm. MS (EI, 70 eV), m/z (%): 167 (Mþ, 9),
124 (100), 96 (63), 94 (10), 86 (46), 79 (22), 41 (36). IR (NaCl) 1662,
1702, 2872, 2927, 2957 cmꢂ1. GC/HRMS-EI m/z [Mþ] calcd. for
C10H17NO 167.1310; found: 167.1316.
26.3, 22.6, 14.1 ppm. MS (EI, 70 eV), m/z (%): 169 (Mþ, 4), 126 (86),
82 (13), 80 (15), 67 (9), 55 (12), 42 (100). IR (NaCl) 1668, 1752, 2872,
2927, 2958 cmꢂ1. Anal. Calcd. for C9H15NO2 (169.2): C, 63.88; H,
8.93; N, 8.28. Found: C, 63.71; H, 8.98; N, 8.26.
4.1.3. N-((Z)-Hex-1-enyl)piperidin-2-one (3ba)
Compound (3ba) was synthesized following the general proce-
dure using piperidin-2-one (1b) (101 mg, 1.00 mmol) and hex-1-
4.1.6. (4S,5R)-3-((Z)-Hex-1-enyl)-5-methyl-4-phenyloxazolidin-2-
one (3ea)
Compound (3ea) was synthesized following the general proce-
dure using (1e) (4S,5R)-5-methyl-4-phenyloxazolidin-2-one
yne (2a) (234 mL, 2.00 mmol) in chlorobenzene and purified by
column chromatography (30:70 ethyl acetate/hexane), yielding the
(177 mg, 1.00 mmol) and hex-1-yne (2a) (234 mL, 2.00 mmol) in
product as a colorless oil (78 mg, 43%) with a (Z/E)-selectivity of
DMF and purified by column chromatography (30:70 ethyl acetate/
hexane), yielding the product as a colorless solid (239 mg, 92%)
with a (Z/E)-selectivity of >20:1. Mp: 44.6 ꢀC. 1H NMR (benzene-d6,
>20:1. 1H NMR (benzene-d6, 400 MHz)
d
¼ 7.85 (d, 3J ¼ 7.9 Hz, 1H),
4.67e4.77 (m, 1H), 2.75 (t, 3J ¼ 5.5 Hz, 2H), 2.16 (t, 3J ¼ 5.9 Hz, 2H),
2.01 (q, 3J ¼ 6.9 Hz, 2H), 1.22e1.38 (m, 4H), 1.02e1.15 (m, 4H), 0.87
MHz 400 MHz)
d
¼ 7.02e7.09 (m, 3H), 6.97e7.01 (m, 2H), 6.04 (d,
(t, 3J ¼ 6.7 Hz, 3H) ppm. 13C NMR (benzene-d6, 101 MHz)
d
¼ 166.8,
3J ¼ 8.8 Hz, 1H), 5.67 (d, 3J ¼ 7.6 Hz, 1H), 5.10 (q, 1H), 4.33e4.42 (m,
1H), 2.07e2.16 (m, 2H), 1.30e1.45 (m, 4H), 0.90 (t, 3J ¼ 7.0 Hz, 3H),
0.76 (d, 3J ¼ 6.6 Hz, 3H) ppm. 13C NMR (benzene-d6, 101 MHz)
109.7, 44.8, 33.0, 30.5, 22.6, 22.5, 20.6, 14.1 ppm. MS (EI, 70 eV), m/z
(%): 181 (Mþ, 20), 152 (19), 138 (100), 110 (49), 100 (44), 82 (36), 67
(25). IR (NaCl) 1650, 2871, 2927, 3035, 3073 cmꢂ1. GC/HRMS-EI m/z
[Mþ] calcd. for C11H19NO 181.1467; found: 181.1474.
d
¼ 155.6, 135.4,128.6, 126.2, 121.9,119.9.6, 78.1, 56.6, 31.9, 27.1, 22.7,
14.2 ppm. MS (EI, 70 eV), m/z (%): 261 [MHþ] (14), 218 (18), 217
(100), 215 (13), 173 (23),118 (14), 98 (16). IR (NaCl) 1668,1731, 2868,
2957, 3038 cmꢂ1. Anal. Calcd. for C16H21NO2 (259.4): C, 74.10; H,
8.16; N, 5.40. Found: C, 74.02; H, 8.28; N, 5.46.
4.1.4. N-((Z)-Hex-1-enyl)azepan-2-one (3ca)
Compound (3ca) was synthesized following the general
procedure using azepan-2-one (1c) (113 mg, 1.00 mmol) and hex-
1-yne (2a) (234
m
L, 2.00 mmol) in chlorobenzene and purified by
4.1.7. N-((Z)-Hex-1-enyl)indolidin-2-one (3fa)
column chromatography (30:70 ethyl acetate/hexane), yielding
the product as a colorless oil (63.2 mg, 32%) with a (Z/E)-selec-
Compound (3fa) was synthesized following the general proce-
dure using oxindol (1f) (137 mg, 1.00 mmol) and hex-1-yne (2a)
(234 mL, 2.00 mmol) in DMF and purified by column chromatog-
tivity of >20:1. 1H NMR (benzene-d6, 400 MHz)
d
¼ 7.60 (d,
3J ¼ 7.5 Hz, 1H), 4.72e4.82 (m, 1H), 2.98e3.04 (m, 2H), 2.28e2.35
(m, 2H), 1.99 (q, 3J ¼ 6.9 Hz, 2H), 1.23e1.35 (m, 6H), 1.14e1.21 (m,
4H), 0.85 (t, 3J ¼ 6.8 Hz, 3H) ppm. 13C NMR (benzene-d6, 101 MHz)
raphy (50:50 ethyl acetate/hexane), yielding the product as
a colorless oil (185 mg, 86%) with a (Z/E)-selectivity of 10:1. 1H NMR
(CDCl3-d1, 400 MHz)
d
¼ 7.23e7.31 (m, 2H), 7.07 (q, 3J ¼ 7.7 Hz, 1H),
d
¼ 172.7, 109.2, 44.5, 37, 32.8, 30.2, 29.2, 27.3, 23.4, 22.3, 13.9 ppm.
6.74 (d, 3J ¼ 7.5 Hz, 1H), 6.04 (d, 3J ¼ 8.1 Hz, 1H), 5.79 (q, 3J ¼ 7.5 Hz,
1H), 3.59 (s, 2H), 2.02e2.09 (m, 2H), 1.22e1.31 (m, 2H), 1.17 (m, 2H),
MS (EI, 70 eV), m/z (%): 195 (Mþ, 22), 152 (60), 138 (100), 124 (25),
96 (40), 67 (34), 41 (49). IR (NaCl) 1650, 1761, 2856, 2926,
3070 cmꢂ1. GC/HRMS-EI m/z [Mþ] calcd. for C12H21NO 195.1623;
found: 195.1623.
0.76 (t, 3J ¼ 7.2 Hz, 3H) ppm. 13C NMR (CDCl3-d1,101 MHz)
¼ 174.0,
d
144.6, 133.6, 127.9, 124.5, 122.6, 118.9, 109.4, 35.8, 30.9, 27.7, 22.3,
13.9 ppm. MS (EI, 70 eV), m/z (%): 215 (Mþ, 100), 172 (30), 144 (84),

A.E. Buba et al. / Journal of Organometallic Chemistry 696 (2011) 170e178
175
133 (22), 130 (17), 117 (13). IR (NaCl) 1659, 1727, 2870, 2926, 3034,
3053 cmꢂ1. Anal. Calcd. for C14H17NO (215.3): C, 78.10; H, 7.96; N,
6.51. Found: C, 77.70; H, 8.12; N, 6.92.
selectivity of 8:1. 1H NMR (benzene-d6, 400 MHz)
d
¼ 6.76 (d,
3J ¼ 9.8 Hz, 1H), 4.54e4.63 (m, 1H), 3.06 (t, 3J ¼ 7.0 Hz, 2H),
1.19e1.34 (m, 6H), 1.11e1.19 (m, 2H), 0.89 (t, 3J ¼ 6.8 Hz, 3H) ppm.
13C NMR (benzene-d6, 101 MHz)
d
¼ 173.2, 122.8, 113.4, 47.8, 31.8,
4.1.8. N-((Z)-Hex-1-enyl)-N-phenyl-formamide (3ha)
Compound (3ha) was synthesized following the general
procedure using formanilide (1h) (121 mg, 1.00 mmol) and hex-
1-yne (2a) (234 mL, 2.00 mmol) in DMF and purified by column
chromatography (30:70 ethyl acetate/hexane), yielding the
30.6, 29.9, 27.4, 22.9, 18.2, 14.2 ppm. MS (EI, 70 eV), m/z (%) ¼ 181
(Mþ, 7), 138 (15), 124 (100), 98 (28), 96 (58), 86 (56), 81 (23). IR
(NaCl) 1662, 1703, 2857, 2871, 2926, 2956 cmꢂ1. Anal. Calcd. for
C11H19NO (181.3): C, 72.88; H, 10.56; N, 7.73. Found: C, 72.30; H,
10.43, N, 7.59.
product as a colorless oil (173 mg, 85%) with a (Z/E)-selectivity of
3:1. 1H NMR (benzene-d6, 400 MHz)
d
¼ 8.17 (s, 1H), 7.50 (d,
4.1.12. N-((Z)-Oct-1-enyl)pyrrolidin-2-one (3ac)
Compound (3ac) was synthesized following the general
procedure using pyrrolidin-2-one (1a) (85.1 mg, 1.00 mmol) and
3J ¼ 7.8 Hz, 1H), 7.12 (t, 3J ¼ 7.6 Hz, 1H), 6.95 (t, 3J ¼ 7.4 Hz, 1H),
6.87 (t, 3J ¼ 7.2 Hz, 1H), 6.73 (d, 3J ¼ 7.4 Hz, 1H), 6.55 (d,
3J ¼ 9.0 Hz, 1H), 4.98 (q, 3J ¼ 7.8 Hz, 1H), 1.48e1.57 (m, 2H),
0.97e1.03 (m, 4H), 0.64e0.75 (m, 3H) ppm. 13C NMR (benzene-
oct-1-yne (2c) (298 mL, 2.00 mmol) in chlorobenzene and puri-
fied by column chromatography (30:70 ethyl acetate/hexane),
yielding the product as a colorless oil (140 mg, 72%) with a (Z/E)-
d6, 101 MHz)
d
¼ 161.3, 141.5, 129.5, 128.9, 126.7, 123.9, 123.8, 31.7,
31.0, 27.5, 26.3, 22.5, 13.9 ppm. MS (EI, 70 eV), m/z (%) ¼ 203 (Mþ,
30), 160 (54), 132 (100), 130 (31), 121 (32), 117 (64), 77 (55). IR
(NaCl) 1554, 1690, 2871, 2927, 2956, 3039 cmꢂ1. Anal. Calcd. for
C13H17NO (203.3): C, 76.81, H, 8.43, N, 6.89. Found: C, 76.38; H,
8.38; N, 6.83. GC/HRMS-EI m/z [Mþ] calcd. for C13H17NO
203.1310; found: 203.1313.
selectivity of 9:1. 1H NMR (benzene-d6, 400 MHz)
d
¼ 6.75 (d,
3J ¼ 9.8 Hz, 1H), 4.60 (q, 3J ¼ 8.0 Hz, 1H), 3.09 (t, 3J ¼ 7.0 Hz, 2H),
1.99e2.09 (m, 2H), 1.90 (t, 3J ¼ 8.2 Hz, 2H), 1.12e1.36 (m, 10H),
0.90 (t, 3J ¼ 6.5 Hz, 3H) ppm. 13C NMR (benzene-d6, 101 MHz)
d
¼ 173.3, 122.8, 113.5, 47.9, 32.1, 30.9, 29.9, 29.3, 27.4, 23.0, 18.3,
14.3 ppm. MS (EI, 70 eV), m/z (%) ¼ 195 (Mþ, 9), 138 (30), 98 (100),
96 (41), 86 (73), 81 (22), 67 (35). IR (NaCl) 1661, 1704, 2854, 2924,
2955 cmꢂ1. GC/HRMS-EI m/z [Mþ] calcd. for C12H21NO 195.1623;
found: 195.1625.
4.1.9. N-(4-Ethoxyphenyl)-N-((Z)-hex-1-enyl)acetamide (3ja)
Compound (3ja) was synthesized following the general proce-
dure using N-(4-ethoxyphenyl)acetamide (1j) (179 mg, 1.00 mmol)
and hex-1-yne (2a) (234
mL, 2.00 mmol) in DMF and purified by
4.1.13. N-((Z)-2-Cyclohexylvinyl)pyrrolidin-2-one (3ad)
column chromatography (30:70 ethyl acetate/hexane), yielding the
product as a colorless oil (219 mg, 84%) with a (Z/E)-selectivity of
Compound (3ad) was synthesized following the general
procedure using pyrrolidin-2-one (1a) (85.1 mg, 1.00 mmol) and 3-
cyclohexyl-prop-1-yne (2d) (290 mL, 2.00 mmol) in chlorobenzene
>20:1. 1H NMR (benzene-d6, 400 MHz)
d
¼ 6.73 (d, 3J ¼ 8.6 Hz, 2H),
6.64 (d, 3J ¼ 8.6 Hz, 2H), 5.54e5.64 (m, 1H), 5.28e5.37 (m, 1H), 4.31
(d, 3J ¼ 6.7 Hz, 2H), 3.52 (q, 3J ¼ 7.0 Hz, 2H), 1.83 (q, 3J ¼ 7.3 Hz, 2H),
1.78 (s, 3H), 1.16e1.26 (m, 2H), 1.09 (t, 3J ¼ 7.0 Hz, 3H), 0.75 (t,
and purified by column chromatography (30:70 ethyl acetate/
hexane), yielding the product as a colorless oil (154 mg, 74%) with
a (Z/E)-selectivity of 12:1. 1H NMR (benzene-d6, 400 MHz)
d
¼ 6.78
3J ¼ 7.2 Hz, 3H) ppm. 13C NMR (benzene-d6, 101 MHz)
d
¼ 169.1,
(d, 3J ¼ 9.8 Hz, 1H), 4.58 (q, 3J ¼ 7.8 Hz, 1H), 3.12 (t, 3J ¼ 7.0 Hz, 2H),
1.93e1.99 (m, 2H), 1.88e1.93 (m, 2H), 1.67 (d, 3J ¼ 12.5 Hz, 5H),
1.19e1.28 (m, 3H), 1.08e1.18 (m, 3H), 0.76e0.88 (m, 2H) ppm. 13C
158.5, 136.3, 134.3, 129.7, 125.9, 115.1, 63.5, 51.5, 34.6, 22.6, 14.7,
13.7 ppm. MS (EI, 70 eV), m/z (%) ¼ 261 (Mþ, 55), 219 (43),176 (100),
137 (50), 109 (25). IR (NaCl) 1651, 2872, 2928, 2958, 3041 cmꢂ1
.
NMR (benzene-d6, 101 MHz)
d
¼ 173.6, 123.7, 112.0, 48.3, 39.5, 35.3,
Anal. Calcd. for C16H23NO2 (261.4): C, 73.53, H, 8.87, N, 5.36. Found:
C, 73.02; H, 9.12; N, 5.30. GC/HRMS-EI m/z [Mþ] calcd. for
C16H23NO2 261.17289; found: 261.1718.
33.7, 33.5, 30.1, 27.1, 26.9, 18.5 ppm. MS (EI, 70 eV), m/z (%) ¼ 207
(Mþ, 7),124 (100), 96 (36), 86 (22), 79 (15), 68 (11), 41 (20). IR (NaCl)
1662, 1702, 2850, 2922 cmꢂ1. GC/HRMS-EI m/z [Mþ] calcd. for
C13H21NO 207.1623; found: 207.1628.
4.1.10. N-((Z)-Hex-1-enyl)-N-phenyl-butanamide (3ka)
Compound (3ka) was synthesized following the general
procedure using N-phenyl-butanamide (1k) (163 mg, 1.00 mmol)
and hex-1-yne (2a) (234 mL, 2.00 mmol) in DMF and purified by
4.1.14. N-((Z)-5-Chloropent-1-enyl)pyrrolidin-2-one (3ag)
Compound (3ag) was synthesized following the general
procedure using pyrrolidin-2-one (1a) (85.1 mg, 1.00 mmol) and
column chromatography (30:70 ethyl acetate/hexane), yielding the
5-chloro-pent-1-yne (2g) (214 mL, 2.00 mmol) in DMF and puri-
product as a colorless oil (111 mg, 45%) with a (Z/E)-selectivity of
fied by column chromatography (30:70 ethyl acetate/hexane),
yielding the product as a colorless oil (164 mg, 87%) with a (Z/E)-
1:1. 1H NMR (benzene-d6, 400 MHz)
d
¼ 6.99e7.09 (m, 3H),
6.89e6.98 (m, 1H), 6.85 (d, 3J ¼ 6.7 Hz, 1H), 5.23e5.34 (m, 1H), 4.31
(d, 3J ¼ 5.5 Hz, 1H), 2.02e2.11 (m, 1H), 1.99 (t, 3J ¼ 7.2 Hz, 1H), 1.80
(q, 3J ¼ 7.3 Hz, 1H), 1.64e1.76 (m, 2H), 1.44e1.56 (m, 1H), 1.13e1.25
(m, 1H), 1.01 (d, 3J ¼ 2.7 Hz, 2H), 0.76e0.86 (m, 3H), 0.67e0.76 (m,
selectivity of 4:1. 1H NMR (benzene-d6, 400 MHz)
d
¼ 6.69 (d,
3J ¼ 9.8 Hz, 1H), 4.33 (q, 3J ¼ 7.8 Hz, 1H), 3.15 (t, 3J ¼ 5.7 Hz, 2H),
3.07 (t, 3J ¼ 7.2 Hz, 2H), 2.05 (q, 3J ¼ 7.3 Hz, 2H), 1.89 (t, 3J ¼ 7.6 Hz,
2H), 1.40e1.50 (m, 2H), 1.15e1.25 (m, 2H) ppm. 13C NMR
3H) ppm. 13C NMR (benzene-d6, 101 MHz)
d
¼ 171.5, 143.5, 134.3,
(benzene-d6, 101 MHz)
d
¼ 173.7, 124.2, 111.3, 48.0, 44.6, 33.5,
129.4, 127.4, 126.1, 51.5, 36.5, 34.5, 26.4, 22.6, 19.2, 18.9, 13.9,
13.7 ppm. MS (EI, 70 eV), m/z (%) ¼ 245 (Mþ, 9), 175 (32), 132 (100),
117 (13), 93 (15), 77 (25), 43 (23). IR (NaCl) 1595, 1659, 2872, 2929,
2959, 3037 cmꢂ1. GC/HRMS-EI m/z [Mþ] calcd. for C16H23NO
245.1780; found: 245.1776.
30.1, 24.6, 18.4 ppm. MS (EI, 70 eV), m/z (%) ¼ 187 (Mþ, 22), 152
(15), 124 (100), 96 (53), 69 (16), 41 (22). IR (NaCl) 1701,
2958 cmꢂ1. GC/HRMS-EI m/z [Mþ] calcd. for C9H14ClNO 187.0764
and 189.0734; found: 187.0770 and 189.0752.
4.1.15. N-((Z)-4-Phenylbut-1-enyl)pyrrolidin-2-one (3ah)
4.1.11. N-((Z)-Hept-1-enyl)pyrrolidin-2-one (3ab)
Compound (3ab) was synthesized following the general
procedure using pyrrolidin-2-one (1a) (85.1 mg, 1.00 mmol) and
Compound (3ah) was synthesized following the general
procedure using pyrrolidin-2-one (1a) (85.1 mg, 1.00 mmol) and 4-
phenyl-but-1-yne (2h) (281 mL, 2.00 mmol) in chlorobenzene and
hept-1-yne (2b) (269
fied by column chromatography (30:70 ethyl acetate/hexane),
yielding the product as a colorless oil (134 mg, 74%) with a (Z/E)-
m
L, 2.00 mmol) in chlorobenzene and puri-
purified by column chromatography (30:70 ethyl acetate/hexane),
yielding the product as a colorless oil (161 mg, 75%) with a (Z/E)-
selectivity of 9:1. 1H NMR (benzene-d6, 400 MHz)
d
¼ 7.14e7.23 (m,

176
A.E. Buba et al. / Journal of Organometallic Chemistry 696 (2011) 170e178
2H), 7.04e7.12 (m, 3H), 6.69 (d, 3J ¼ 10.2 Hz, 1H), 4.60 (q, 3J ¼ 7.4 Hz,
1H), 2.92 (t, 3J ¼ 7.0 Hz, 2H), 2.51 (t, 3J ¼ 7.6 Hz, 2H), 2.31 (q,
1.88 (t, 3J ¼ 8.0 Hz, 2H), 1.02e1.11 (m, 2H) ppm. 13C NMR (benzene-
d6, 101 MHz)
d
¼ 174.3, 157.6, 131.4, 128.5, 124.8, 119.9, 110.2, 107.9,
3J ¼ 7.7 Hz, 2H), 1.87 (t, 3J ¼ 8.0 Hz, 2H), 1.09e1.19 (m, 2H) ppm. 13
C
55.0, 47.5, 30.1, 18.5 ppm. MS (EI, 70 eV), m/z (%) ¼ 218 (MHþ, 100),
132 (22), 131 (11), 91 (11), 89 (10), 86 (20). IR (NaCl) 1647, 1701,
2836, 2960, 3073 cmꢂ1. GC/HRMS-EI m/z [Mþ] calcd. for C13H15NO2
201.1154; found: 201.1153.
NMR (benzene-d6, 101 MHz)
d
¼ 173.4, 141.9, 128.8, 128.6, 126.3,
123.1, 112.5, 47.7, 36.9, 29.9, 29.5, 18.18 ppm. MS (EI, 70 eV), m/z
(%) ¼ 215 (Mþ,1),124 (100), 96 (39), 91 (13), 79 (12), 69 (12), 41 (16).
IR (NaCl) 1698, 2923, 3025, 3059, 3083 cmꢂ1. GC/HRMS-EI m/z [Mþ]
calcd. for C14H17NO 215.1310; found: 215.1305.
4.1.20. N-((Z)-Hex-1-enyl)succinimide (3la)
Compound (3la) was synthesized following the general proce-
dure using succinimide (1l) (99.1 mg, 1.00 mmol) and hex-1-yne
4.1.16. N-((Z)-2-Phenylvinyl)pyrrolidin-2-one (3ai)
Compound (3ai) was synthesized following the general proce-
dure using pyrrolidin-2-one (1a) (85.1 mg, 1.00 mmol) and phe-
(2a) (231 mL, 2.00 mmol) in DMF and purified by column chroma-
tography (30:70 ethyl acetate/hexane), yielding the product as
nylacetylene (2i) (220
mL, 2.00 mmol) in chlorobenzene and
a colorless oil (162 mg, 89%) with a (Z/E)-selectivity of >20:1. 1H
purified by column chromatography (30:70 ethyl acetate/hexane),
yielding the product as a yellowish oil (139 mg, 74%) with a (Z/E)-
selectivity of >20:1. [CAS: 6908e67e4]. 1H NMR (benzene-d6,
NMR (benzene-d6, 400 MHz)
d
¼ 5.86 (d, 3J ¼ 8.8 Hz, 1H), 5.42 (q,
3J ¼ 8.6, 7.5 Hz, 1H), 1.97 (qd, 3J ¼ 7.3, 1.6 Hz, 2H), 1.91 (s, 4H),
1.20e1.31 (m, 4H), 0.81 (t, 3J ¼ 7.1 Hz, 3H) ppm. 13C NMR (benzene-
400 MHz)
d
¼ 7.06e7.14 (m, 3H), 6.99e7.14 (m, 3H), 5.73 (d,
d6, 101 MHz)
d
¼ 174.6, 137.0, 113.1, 32.0, 28.8, 27.4, 22.2, 13.7 ppm.
3J ¼ 9.8 Hz, 1H), 2.69 (t, 3J ¼ 7.0 Hz, 2H), 1.87 (t, 3J ¼ 8.0 Hz, 2H),
MS (EI, 70 eV), m/z (%) ¼ 182 (MHþ, 13), 138 (67), 100 (75), 82 (100),
56 (44). IR (NaCl) 1710, 2871, 2931, 2957, 3039 cmꢂ1. Anal. Calcd. for
C10H15NO2 (181.2): C, 66.27; H, 8.34; N, 7.73. Found: C, 66.19; H,
8.59; N, 7.89.
0.97e1.08 (m, 2H) ppm. 13C NMR (benzene-d6, 101 MHz)
137.2, 129.7, 126.9, 124.8, 111.8, 47.9, 30.1, 18.6 ppm. MS (EI, 70 eV),
m/z (%) ¼ 187 (Mþ, 100), 159 (11), 132 (52), 130 (52), 117 (26), 115
(24), 77 (20).
d
¼ 174.5,
4.1.21. N-((Z)-Hex-1-enyl)-1,5,5-trimethylhydantoin (3ma)
Compound (3ma) was synthesized following the general
procedure using 1,5,5-trimethylhydantoin (1m) (142 mg,
4.1.17. N-((Z)-4-Propylstyryl)pyrrolidin-2-one (3aj)
Compound (3aj) was synthesized following the general
procedure using pyrrolidin-2-one (1a) (85.1 mg, 1.00 mmol) and
1.00 mmol) and hex-1-yne (2a) (234 mL, 2.00 mmol) in DMF and
1-ethynyl-4-propylbenzene (2j) (317
m
L, 2.00 mmol) in chloro-
purified by column chromatography (30:70 ethyl acetate/hexane),
yielding the product as a yellowish oil (215 mg, 96%) with a (Z/E)-
benzene and purified by column chromatography (30:70 ethyl
acetate/hexane), yielding the product as a yellowish oil (167 mg,
73%) with a (Z/E)-selectivity of >20:1. 1H NMR (benzene-d6,
selectivity of >20:1. 1H NMR (CDCl3-d1, 400 MHz)
d
¼ 5.85 (d,
3J ¼ 8.3 Hz, 1H), 5.60 (q, 3J ¼ 7.3 Hz, 1H), 2.85 (s, 3H), 1.89e1.98 (m,
2H), 1.36 (s, 6H), 1.28e1.34 (m, 2H), 1.21e1.28 (m, 2H), 0.81 (t,
400 MHz)
d
¼ 6.97e7.08 (m, 5H), 5.78 (d, 3J ¼ 9.8 Hz, 1H), 2.79 (t,
3J ¼ 7.0 Hz, 2H), 2.43 (t, 3J ¼ 7.6 Hz, 2H), 1.89 (t, 3J ¼ 8.0 Hz, 2H),
3J ¼ 7.1 Hz, 3H) ppm. 13C NMR (CDCl3-d1, 101 MHz)
¼ 174.8, 154.2,
d
1.46e1.58 (m, 2H), 1.01e1.11 (m, 2H), 0.84 (t, 3J ¼ 7.2 Hz, 3H) ppm.
132.8, 116.3, 61.2, 30.7, 27.5, 24.5, 22.3, 22.2, 13.8 ppm. MS (EI,
13C NMR (benzene-d6, 101 MHz)
d
¼ 174.3, 141.1, 134.5, 131.3, 129.6,
70 eV), m/z (%) ¼ 225 (MHþ, 100), 224 (10), 181 (11), 96 (13), 72 (15),
124.4, 111.9, 47.7, 37.9, 30.0, 24.8, 18.3, 13.7 ppm. MS (EI, 70 eV), m/
z (%) ¼ 229 (Mþ, 68), 201 (17), 200 (100), 131 (42), 130 (16), 115
(25). IR (NaCl) 1647, 1707, 2871, 2929, 2958 cmꢂ1. Anal. Calcd. for
C15H19NO (229.3): C, 78.56; H, 8.35, N, 6.11. Found: C, 77.98; H,
8.00; N, 6.29.
56 (26). IR (NaCl) 1662, 1719, 1777, 2871, 2930, 2956, 3044 cmꢂ1
.
Anal. Calcd. for C12H20N2O2 (224.3): C, 64.26; H, 8.99; N, 12.49.
Found: C, 63.69, H, 9.08, N, 12.25.
4.1.22. N-((Z)-Hex-1-enyl)phthalimide (3na)
Compound (3na) was synthesized following the general
procedure using phthalimide (1n) (147 mg, 1.00 mmol) and hex-1-
4.1.18. N-((Z)-2-Methylstyryl)pyrrolidin-2-one (3ak)
Compound (3ak) was synthesized following the general
procedure using pyrrolidin-2-one (1a) (85.1 mg, 1.00 mmol) and 2-
yne (2a) (234 mL, 2.00 mmol) in DMF and purified by column
chromatography (30:70 ethyl acetate/hexane), yielding the product
ethynyltoluene (2k) (260
mL, 2.00 mmol) in chlorobenzene and
as a yellowish oil (175 mg, 76%) with a (Z/E)-selectivity of >20:1. 1H
purified by column chromatography (30:70 ethyl acetate/hexane),
yielding the product as a yellowish oil (186 mg, 83%) with a (Z/E)-
NMR (CDCl3-d1, 400 MHz)
d
¼ 7.74, 7.84 (m, 2H), 7.61e7.71 (m, 2H),
6.00 (d, 3J ¼ 8.3 Hz, 1H), 5.67 (q, 3J ¼ 7.3 Hz, 1H), 1.93e2.05 (m, 2H),
selectivity of >20:1. 1H NMR (benzene-d6, 400 MHz)
d
¼ 7.24 (d,
1.28e1.39 (m, 2H), 1.17e1.27 (m, 2H), 0.77 (t, 3J ¼ 7.2 Hz, 3H) ppm.
3J ¼ 10.2 Hz, 1H), 7.05e7.16 (m, 4H), 5.69 (d, 3J ¼ 10.2 Hz, 1H), 2.70
13C NMR (CDCl3-d1, 101 MHz)
d
¼ 166.4, 132.5, 132.0, 123.2, 116.9,
(t, 3J ¼ 7.0 Hz, 2H), 2.19 (s, 3H), 1.95 (t, 3J ¼ 8.0 Hz, 2H), 1.03e1.14 (m,
31.3, 28.5, 22.6, 14.0 ppm. MS (EI, 70 eV), m/z (%) ¼ 230 (MHþ, 100),
229 (18), 187 (13), 186 (77), 130 (24). IR (NaCl) 1663, 1718, 1764,
1785, 2858, 2956, 3041 cmꢂ1. Anal. Calcd. for C14H15NO2 (229.3): C,
73.34, H, 6.59; N, 6.11. Found: C, 72.88; H, 6.62; N, 5.80.
2H) ppm. 13C NMR (benzene-d6, 101 MHz)
d
¼ 174.1, 136.7, 136.5,
130.4, 129.5, 127.3, 125.2, 124.7, 110.0, 47.5, 30.0, 20.2, 18.3 ppm. MS
(EI, 70 eV), m/z (%) ¼ 201 (Mþ, 100), 144 (18), 131 (19), 130 (20), 116
(35), 115 (35). IR (NaCl) 1648, 1706, 2895, 2979, 3019, 3065 cmꢂ1
.
Anal. Calcd. for C13H15NO (201.3): C, 77.58; H, 7.51; N, 6.96. Found:
C, 77.12; H, 7.47; N, 6.92.
4.1.23. N-((Z)-Oct-1-enyl)succinimide (3lc)
Compound (3lc) was synthesized following the general proce-
dure using succinimide (1l) (99.1 mg, 1.00 mmol) and oct-1-yne
4.1.19. N-((Z)-2-Methoxystyryl)pyrrolidin-2-one (3al)
(2c) (298 mL, 2.00 mmol) in DMF and purified by column chroma-
Compound (3al) was synthesized following the general proce-
dure using pyrrolidin-2-one (1a) (85.1 mg, 1.00 mmol) and ethy-
tography (30:70 ethyl acetate/hexane), yielding the product as
a colorless oil (208 mg, 99%) with a (Z/E)-selectivity of >20:1. 1H
nylanisole (2l) (259
mL, 2.00 mmol) in DMF and purified by column
NMR (benzene-d6, 400 MHz)
d
¼ 5.86 (d, 3J ¼ 8.6 Hz, 1H), 5.43 (q,
chromatography (30:70 ethyl acetate/hexane), yielding the product
3J ¼ 8.6, 7.3 Hz, 1H), 1.98 (qd, 3J ¼ 7.4, 1.6 Hz, 2H), 1.91 (s, 4H),
1.27e1.34 (m, 2H), 1.13e1.25 (m, 6H), 0.82 (t, 3J ¼ 6.8 Hz, 3H) ppm.
as a yellowish oil (186 mg, 86%) with a (Z/E)-selectivity of 4:1. 1H
NMR (benzene-d6, 400 MHz)
d
¼ 7.17 (d, 3J ¼ 9.8 Hz, 1H), 7.07e7.12
13C NMR (benzene-d6, 101 MHz)
29.4, 29.1, 28.7, 28.2, 22.9, 14.2 ppm. MS (EI, 70 eV), m/z (%) ¼ 210
d
¼ 175.0, 174.9, 131.8, 117.7, 32.0,
(m, 1H), 6.98e7.03 (m, 1H), 6.79e6.85 (m, 1H), 6.57 (d, 3J ¼ 8.2 Hz,
1H), 5.95 (d, 3J ¼ 9.8 Hz, 1H), 3.38 (s, 3H), 2.81 (t, 3J ¼ 7.0 Hz, 2H),
(MHþ, 100), 138 (43), 110 (65), 82 (29), 81 (30), 56 (42), 55 (30). IR

A.E. Buba et al. / Journal of Organometallic Chemistry 696 (2011) 170e178
[5] (a) J.-H. Lin, Phytochemistry 28 (1989) 621e622;
177
(NaCl) 1664, 1710, 2856, 2928, 3039 cmꢂ1
. Anal. Calcd. for
(b) I. Stefanuti, S.A. Smith, R.J.K. Taylor, Tetrahedron Lett. 41 (2000)
3735e3738;
(c) A. Fürstner, C. Brehm, Y. Cancho-Grande, Org. Lett. 3 (2001) 3955e3957.
[6] (a) H.-W. Fehlhaber, J. Uhlendorf, S.T. David, R. Tschesche, Liebigs Ann. Chem.
759 (1972) 195e207;
C12H19NO2 (209.3): C, 68.87; H, 9.15; N, 6.69. Found: C, 68.99; H,
9.32; N, 6.67.
4.1.24. N-((Z)-2-Cyclohexylvinyl)succinimide (3ld)
Compound (3ld) was synthesized following the general proce-
dure using succinimide (1l) (99.1 mg, 1.00 mmol) and 3-cyclohexyl-
prop-1-yne (2d) (290 mL, 2.00 mmol) in DMF and purified by
column chromatography (30:70 ethyl acetate/hexane), yielding the
(b) R. Tschesche, S.T. David, R. Zerbes, M. von Radloff, E.U. Kaußmann,
G. Eckhardt, Liebigs Ann. Chem. (1974) 1915e1928;
(c) C. Auvin, F. Lezenven, A. Blond, I. Augeven-Bour, L. J-Pousette, B. Bodo, J.
Nat. Prod. 59 (1996) 676e678.
[7] E. Dumdei, R.J. Andersen, J. Nat. Prod. 56 (1993) 792e794.
[8] (a) M.R. Rao, D.J. Faulkner, J. Nat. Prod. 67 (2004) 1064e1066;
(b) M.J. McKay, A.R. Carroll, R.J. Quinn, J. Nat. Prod. 68 (2005) 1776e1778;
(c) C.J. Heinrich, R.W. Robey, K. Takada, H.R. Bokesch, S.E. Bates, S. Shukla,
product as a colorless solid (176 mg, 80%) with a (Z/E)-selectivity of
>20:1. Mp: 106.3 ꢀC. 1H NMR (benzene-d6, 400 MHz)
d
¼ 5.93 (d,
S.V. Ambudkar, J.B. McMahon, K.R. Gustafson, ACS Chem. Biol.
637e647;
(d) K. Takada, N. Imamura, K.R. Gustafson, C.J. Heinrich, Bioorg. Med. Chem.
Lett. 20 (2010) 1330e1333;
4 (2009)
3J ¼ 8.6 Hz, 1H), 5.47 (q, 3J ¼ 7.4 Hz, 1H), 1.97 (t, 3J ¼ 6.5 Hz, 2H), 1.75
(m, 4H), 1.51e1.70 (m, 5H) 1.20e1.29 (m, 1H), 0.97e1.19 (m, 3H),
0.77e0.90 (m, 2H) ppm. 13C NMR (benzene-d6, 101 MHz)
d
¼ 174.7,
(e) L.A. McDonald, J.C. Swersey, C.M. Ireland, A.R. Carroll, J.C. Coll, B.F. Bowden,
C.R. Fairchild, L. Cornell, Tetrahedron 51 (1995) 5237e5244.
[9] L.J. Gooßen, M. Blanchot, M. Arndt, K.S.M. Salih, Synlett (2010) 1685e1687.
[10] (a) A.R. Katritzky, B. Rachwal, S. Rachwal, J. Org. Chem. 60 (1995) 3993e4001;
(b) C.A. Zezza, M.B. Smith, J. Org. Chem. 53 (1988) 1161e1167;
(c) L.E. Overman, L.A. Clizbe, J. Am. Chem. Soc. 98 (1976) 2352e2354;
(d) P.J. Stevenson, I. Graham, ARKIVOC 7 (2003) 139e144.
[11] C. Gaulon, R. Dhal, T. Chapin, V. Maisonneuve, G. Dujardin, J. Org. Chem. 69
(2004) 4192e4202.
[12] G.J. Roff, R.C. Lloyd, N.J. Turner, J. Am. Chem. Soc. 126 (2004) 4098e4099.
[13] C.E. Wilians, C.A. Mulder, J.G. de Vries, H.M. de Vries, J. Organomet. Chem. 687
(2003) 494e497.
[14] R. Matsubara, Y. Nakamura, S. Kobayashi, Angew. Chem. 116 (2004) 1711e1713;
Angew. Chem. Int. Ed. 43(2004) 1679e1681.
130.7, 118.4, 37.7, 36.3, 33.4, 28.1, 26.6 ppm. MS (EI, 70 eV), m/z
(%) ¼ 222 [MHþ] (38), 139 (26), 122 (100), 83 (25), 80 (27), 56 (27),
55 (49). IR (NaCl) 1659, 1704, 1765, 2847, 2928, 3029 cmꢂ1. Anal.
Calcd. for C13H19NO2 (221.3): C, 70.56, H, 8.65; N, 6.33. Found: C,
70.01; H, 8.99; N, 6.39.
4.1.25. N-((Z)-5-Chloropent-1-enyl)succinimide (3lg)
Compound (3lg) was synthesized following the general proce-
dure using succinimide (1l) (99.1 mg, 1.00 mmol) and 5-chloro-
pent-1-yne (2g) (214 mL, 2.00 mmol) in DMF and purified by
column chromatography (30:70 ethyl acetate/hexane), yielding the
[15] (a) T. Sell, A. Meiswinkel, G. Mehler, M.T. Reetz, Tetrahedron Lett. 43 (2002)
7941e7943;
product as a colorless oil (143 mg, 71%) with a (Z/E)-selectivity of
>20:1. 1H NMR (benzene-d6, 400 MHz)
d
¼ 5.85 (d, 3J ¼ 8.6 Hz, 1H),
(b) M. van den Berg, A.J. Minnaard, R.M. Haak, M. Leeman, E.P. Schudde,
A. Meetsma, B.L. Feringa, H.M. de Vries, E.P. Maljaars, C.E. Wilians, D. Hyett,
A.F. Boogers, J.W. Hendricks, J.G. de Vries, Adv. Synth. Catal. 345 (2003)
308e323.
5.21 (q, 3J ¼ 7.7 Hz, 1H), 3.15 (t, 3J ¼ 6.4 Hz, 2H), 1.96e2.06 (m, 2H),
1.84e1.90 (m, 4H), 1.51 (qd, 3J ¼ 6.9, 6.7 Hz, 2H) ppm. 13C NMR
[16] W. Adam, S.G. Bosio, N.J. Turro, J. Org. Chem. 69 (2004) 1704e1715.
[17] (a) M. Brasholz, H.-U. Reißig, R. Zimmer, Acc. Chem. Res. 42 (2009) 45e56;
(b) O. Fögel, J. Dash, I. Brüdgam, H. Hartl, H.-U. Reißig, Chem. Eur. J. 10 (2004)
4283e4290.
(benzene-d6, 101 MHz)
d
¼ 175.0, 129.9, 118.9, 44.5, 31.3, 28.2,
25.6 ppm. MS (EI, 70 eV), m/z (%) ¼ 202 (MHþ, 67), 166 (79), 138
(100), 100 (52), 82 (71), 56 (75), 55 (59). IR (NaCl) 1708, 1777,
2942 cmꢂ1. Anal. Calcd. for C9H12ClNO2 (201.7): C, 53.61; H, 6.00; N,
6.95. Found: C, 53.44; H, 5.98; N, 6.94.
[18] (a) R. Brettle, A.J. Mosedale, J. Chem. Soc. Perkin Trans. 1 (1988) 2185e2195;
(b) K. Kuramochi, H. Watanabe, T. Kitahara, Synlett (2000) 397e399.
[19] D. Ager, Synthesis (1984) 384e398.
[20] (a) L. Jiang, G.E. Job, A. Klapars, S.L. Buchwald, Org. Lett. 5 (2003) 3667e3669;
(b) D.J. Wallace, D.J. Klauber, C.-Y. Chen, R.P. Volante, Org. Lett. 5 (2003)
4749e4752;
4.1.26. N-((Z)-2-Phenylbut-1-enyl)succinimide (3lh)
Compound (3lh) was synthesized following the general
procedure using succinimide (1l) (99.1 mg, 1.00 mmol) and 4-
(c) C. Han, R. Shen, S. Su, J.A. Porco Jr., Org. Lett. 6 (2004) 27e30;
(d) X. Pan, Q. Cai, D. Ma, Org. Lett. 6 (2004) 1809e1812;
(e) J.L. Brice, J.E. Meerdink, S.S. Stahl, Org. Lett. 6 (2004) 1845e1848;
phenyl-but-1-yne (2h) (281 mL, 2.00 mmol) and purified by
(f) A. Klapars, K.R. Campos, C. Chen, R.P. Volante, Org. Lett.
1185e1188;
7 (2005)
column chromatography (30:70 ethyl acetate/hexane), yielding
the product as a colorless oil (218 mg, 95%) with a (Z/E)-selectivity
of >20:1. Mp: 63.6 ꢀC. 1H NMR (benzene-d6, 400 MHz)
(g) Y. Bolshan, R.A. Batey, Angew. Chem. 120 (2008) 2139e2142;
Angew. Chem., Int. Ed. 47 (2008) 1e5.
d
¼ 7.07e7.28 (m, 5H), 5.93 (d, 3J ¼ 8.6 Hz, 1H), 5.45e5.55 (m, 1H),
[21] (a) L.J. Gooßen, N. Rodríguez, K. Gooßen, Angew. Chem. Int. Ed. 47 (2008)
3100e3120;
2.62e2.71 (m, 2H), 2.28e2.38 (m, 2H), 1.91 (s, 4H) ppm. 13C NMR
(b) L.J. Gooßen, A. Dohring, Adv. Synth. Catal. 345 (2003) 943e947;
(c) L.J. Gooßen, J. Paetzold, L. Winkel, Synlett (2002) 1721e1723;
(d) L.J. Gooßen, L. Winkel, A. Döhring, Ghosh, J. Paetzold, Synlett (2002)
1237e1240.
(benzene-d6, 101 MHz)
d
¼ 174.9, 141.8, 130.3, 128.7, 128.6, 126.2,
118.1, 35.0, 30.7, 28.2 ppm. MS (EI, 70 eV), m/z (%) ¼ 230 (MHþ, 5),
138 (100), 130 (84), 110 (24), 91 (40), 65 (24), 56 (59), 55 (27). IR
(NaCl) 1702, 1764, 2858, 2922, 3024, 3059, 3084 cmꢂ1. Anal. Calcd.
for C14H15NO2 (229.3): C, 73.34; H, 6.59; N, 6.11. Found: C, 73.35; H,
6.49; N, 5.64.
[22] (a) T.-A. Mitsudo, Y. Hori, Y. Watanabe, J. Org. Chem. 50 (1985) 1566e1568;
(b) H. Doucet, N. Derrien, Z. Kabouche, C. Bruneau, P.H. Dixneuf, J. Organomet.
Chem. 551 (1997) 151e157;
(c) L.J. Gooßen, J. Paetzold, D. Koley, Chem. Commun. (2003) 706e707;
(d) F. Pohlki, S. Doye, Chem. Soc. Rev. 32 (2003) 104e114;
(e) R. Severin, S. Doye, Chem. Soc. Rev. 36 (2007) 1407e1420;
(f) F. Alonso, I.P. Beletskaya, M. Yus, Chem. Rev. 104 (2004) 3079e3159;
(g) C. Bruneau, P.H. Dixneuf, Angew. Chem. 118 (2006) 2232e2260;
Angew. Chem. Int. Ed. 45 (2006) 2176e2203.
Acknowledgements
[23] L.J. Gooßen, J.E. Rauhaus, G. Deng, Angew. Chem. 117 (2005) 4110e4113;
Angew. Chem. Int. Ed. 44 (2005) 4042e4045.
[24] L.J. Gooßen, M. Arndt, M. Blanchot, F. Rudolphi, F. Menges, G. Niedner-
Schatteburg, Adv. Synth. Catal. 350 (2008) 2701e2707.
[25] L.J. Gooßen, M. Blanchot, C. Brinkmann, K. Gooßen, R. Karch, A. Rivas-Nass, J.
Org. Chem. 71 (2006) 9506e9509.
We thank the Deutsche Forschungsgemeinschaft and NanoKat
for financial support and the Landesgraduiertenförderung Rhein-
land-Pfalz for a scholarship to M.A.
References
[26] L.J. Gooßen, M. Blanchot, K.S.M. Salih, R. Karch, A. Rivas-Nass, Org. Lett. 10
(2008) 4497e4499.
[27] (a) L.J. Gooßen, K.S.M. Salih, M. Blanchot, Angew. Chem. 120 (2008)
8620e8623;
[1] L. Yet, Chem. Rev. 103 (2003) 4283e4306.
[2] Y.N. Han, G.-Y. Kim, H.K. Han, B.H. Han, Arch. Pharm. Res. 16 (1993) 289e294.
[3] S.G. Toske, P.R. Jensen, C.A. Kaufman, W. Fenical, Tetrahedron 54 (1998)
13459e13466.
[4] D. Davyt, W. Entz, R. Fernandez, R. Mariezcurrena, A.W. Mombru, J. Saldana,
L. Dominguez, J. Coll, E. Manta, J. Nat. Prod. 61 (1998) 1560e1563.
Angew. Chem. Int. Ed. 47 (2008) 8492e8495;
(b) L.J. Gooßen, M. Blanchot, K.S.M. Salih, K. Gooßen, Synthesis (2009)
2283e2288.
[28] M. Toumi, F. Couty, G. Evano, J. Org. Chem. 73 (2008) 1270e1281.

178
A.E. Buba et al. / Journal of Organometallic Chemistry 696 (2011) 170e178
Annette Buba was born in 1986 in Ratibor, Poland. In
Prof. Dr. Lukas J. Gooßen, born 1969 in Bielefeld/
Germany, studied chemistry at Universität Bielefeld/
University of Michigan, conducted his diploma work
with K.P.C. Vollhardt, UC Berkeley and his PhD
research with W.A. Herrmann, TU München. After
2005, she started to study chemistry at Universität
des Saarlandes. After one year she continued her
study at the TU Kaiserslautern. In october 2009, she
joined the group of L.J. Gooßen for her diploma
research on the Z-selective Hydroamidation of alkynes.
a
postdoctoral stay with K.B. Sharpless, Scripps
Research Institute and a position as a head of labo-
ratory at Bayer AG, he started his academic career at
MPI für Kohlenforschung in the group of M.T. Reetz
(2000e2003). In 2004, he moved to RWTH Aachen as
a Heisenberg fellow, and in 2005, he was appointed
professor at TU Kaiserslautern.
Matthias Arndt was born in 1983 in Koblenz,
Germany. In 2003, he started to study chemistry at
the TU Kaiserslautern. In 2007 he attended to the
Sokrates/Erasmus exchange program and studied at
the University of Glasgow for 3 months. In 2008 he
joined the group of L.J. Gooßen, finished his diploma
work in the same year and started with his PhD
research on the Mechanistic Investigation of Hydro-
amidation Reactions.