Gold-Catalyzed Regio- and Stereoselective Addition of Carboxylic Acids to Iodoalkynes: Access to (Z)-β-Iodoenol Esters and 1,4-Disubstituted (Z)-Enynyl Esters

Article abstract of DOI:10.1021/acs.joc.6b02712

In the presence of catalytic amounts of the Au(I) cation [Au(PPh₃)]⁺, a large variety of (Z)-β-iodoenol esters (39 examples) could be synthesized under mild reaction conditions through the regio- and stereospecific intermolecular add

Full text of DOI:10.1021/acs.joc.6b02712

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Article
Gold-Catalyzed Regio- and Stereoselective Addition
of Carboxylic Acids to Iodoalkynes: Access to (Z)-#-
Iodoenol Esters and 1,4-Disubstituted (Z)-Enynyl Esters
Pedro J. González-Liste, Javier Francos, Sergio Emilio García-Garrido, and Victorio Cadierno
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.6b02712 • Publication Date (Web): 13 Jan 2017
Downloaded from http://pubs.acs.org on January 13, 2017
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The Journal of Organic Chemistry
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Gold-Catalyzed Regio- and Stereoselective Addition of Carboxylic
Acids to Iodoalkynes: Access to (Z)-β-Iodoenol Esters and 1,4-
Disubstituted (Z)-Enynyl Esters
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Pedro J. González-Liste,‡ Javier Francos,‡ Sergio E. García-Garrido* and Victorio Cadierno*
Laboratorio de Compuestos Organometálicos y Catálisis (Unidad Asociada al CSIC), Centro de Innovación en Quí-
mica Avanzada (ORFEO-CINQA), Departamento de Química Orgánica e Inorgánica, Instituto Universitario de
Química Organometálica “Enrique Moles”, Universidad de Oviedo, 33006 Oviedo, Spain.
ABSTRACT: In the presence of catalytic amounts of the Au(I) cation [Au(PPh3)]+, a large variety of (Z)-β-iodoenol esters
(39 examples) could be synthetized under mild reaction conditions through the regio- and stereospecific intermolecular
addition of carboxylic acids to iodoalkynes. Sonogashira coupling of representative (Z)-β-iodoenol esters with terminal
alkynes, alkynols and 1,3-enynes allowed also the access to different 1,4-disubstituted (Z)-enynyl esters in excellent yields.
(RC(=O)CH2X),14 while the addition of thiols,15 phenols,16
diphenyl phosphate,17 amines/amides15a,18 and sulfonic
acids19 has allowed the preparation of a large variety of 2-
INTRODUCTION
The intermolecular addition of carboxylic acids to al-
kynes represents one of the most efficient and atom-
economical approaches currently available for the prepa-
ration of enol esters,1 which are relevant compounds for
synthetic chemistry and polymerization processes.2 Since
the report by Shvo and Rotem in 1983 employing
Ru3(CO)12,3 the vast majority of catalytic systems em-
ployed so far are based on ruthenium complexes, due to
functionalized-1-haloalkenes
(NuCR=CHX),
via
regioselective nucleophilic attack of the heteroatom on
the electrophilic C-2 carbon of the haloalkyne.20 Metal
catalysts have certainly played
a key role in the
development of this chemistry.14a-f,15b,17,20b-d However, an
important gap in the field concerns the intermolecular
addition of carboxylic acids to access β-haloenol esters, a
process that, to the best of our knowledge, has not been
yet reported.21 In fact, despite the enormous synthetic
potential of these functionalized olefins,22 there are still
relatively few methods available for their preparation.23
their high efficiency and functional groups tolerance.4,5
A
number of catalysts involving other late transition metals
such as rhenium,6 rhodium,7 iridium,8 palladium,9 gold10
and silver11 have also proven useful to promote these hy-
drocarboxylation reactions.12 Although the use of unacti-
vated internal alkynes, which due to steric grounds re-
quire much higher activation energies, has resulted in
many cases problematic, effective systems for these chal-
lenging substrates have seen the light very recently.5a,h,10
In addition, for the particular case of terminal alkynes,
catalysts capable of controlling the regio- and stereoselec-
tivity of the addition process are known, thus allowing the
preferential formation of one of the three possible enol
ester isomers (Scheme 1).4
Scheme 2. General Approaches to β-Haloenol Esters
Currently Available
Scheme 1. The Catalytic Addition of Carboxylic Acids
to Terminal Alkynes
On the other hand, easily accessible haloalkynes RC≡CX
(X = Cl, Br, I) are a significant class of building blocks in
organic chemistry, and remarkable efforts have been
devoted
in
recent
years
to
their
selective
hydrofunctionalization.13 In this context, the hydration of
haloalkynes has proven to be a very simple and efficient
method
for
accessing
α-halomethyl
ketones
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Among the most general, we can mention (Scheme 2): gio- and stereoselectivity is not surprising giving that: (i)
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(i) the silver-catalyzed difunctionalization of terminal
alkynes reported by Jiang and co-workers, which allows
the stereoselective access to (Z)-haloenol acetates,23b (ii)
the cohalogenation of internal aromatic alkynes using a
combination of a carboxylic acid and N-iodosuccinimide
(NIS) described by Yanada´s group, which generates the
corresponding β-iodoenol esters as mixtures of E/Z ste-
reoisomers,23c and (iii) the haloacyloxylation processes
developed by Xia and Baell groups, which give a broad
access to β-haloenol esters from terminal and internal
aromatic alkynes with high E-selectivity.23e,f
the C-2 carbon of the haloalkyne is the more electrophilic
one,14-20 and (ii) the nucleophilic Nu-H additions to π-
alkyne-gold complexes usually proceed in an anti-fashion
(Scheme 4).26 Regarding this last point, blank experiments
conducted separately with [AuCl(PPh3)] and AgPF6 alone
did not lead to the formation of the desired β-iodoenol
acetates, thus confirming that the cationic species
[Au(PPh3)]+ is responsible for the catalytic activity ob-
served.27
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Scheme 4. Proposed Mechanism for the Gold-
Catalyzed Addition of Acetic Acid to Iodoalkynes
With all these precedents in mind, we considered that
the development of a catalytic system able to promote the
intermolecular hydrocarboxylation of haloalkynes with
carboxylic acids should be greatly appreciated. In this
context, very recently, we communicated the synthesis of
a small family of (Z)-β-iodoenol acetates through a
gold(I)-catalyzed regio- and stereospecific addition of
acetic acid to aliphatic iodoalkynes.24 In addition, we also
demonstrated the synthetic utility of these functionalized
iodoolefins for the preparation of valuable chiral homo-
benzylic acetates, through their Suzuki arylation and
subsequent rhodium-catalyzed asymmetric hydrogena-
tion.24 Herein, a full report on the scope of the gold(I)-
catalyzed hydrocarboxylation of iodoalkynes is presented,
as well as the synthesis of a diverse family of 1,4-
disubstituted (Z)-enynyl esters via Sonogashira coupling
reactions of the resulting (Z)-β-iodoenol esters (Scheme
3).
On the other hand, although the reactions collected in
Table 1 were systematically carried out on a 1 mmol scale,
we would like to stress that they can be scaled up without
major problems. As a representative example, a reaction
conducted with 1-iodooct-1-yne (1d) on a 10 mmol scale
(2.5 g) allowed the preparation of 2.72 g (92% yield) of
(Z)-1-iodooct-1-en-2-yl acetate (2d).
Table 1. Gold-Catalyzed Addition of Acetic Acid to
Different Iodoalkynesa
Scheme 3. The Synthesis of (Z)-β-Iodoenol and (Z)-
Enynyl Esters from Iodoalkynes Described Herein
Entry
1
Alkyne 1
Yield 2 (%)b
2a; 95
2b; 93
2c; 96
2d; 97
2e; 97
2f; 88
R = nPr (1a)
R = nBu (1b)
R = nPent (1c)
R = nHex (1d)
2
3
RESULTS AND DISCUSSION
4
In our preliminary communication,24 we reported the
preparation of the (Z)-β-iodoenol acetates 2a-f,h by
treatment of the corresponding aliphatic iodoalkyne 1a-
f,h with 1 equiv. of acetic acid in the presence of 5 mol%
of the gold(I) complex [AuCl(PPh3)] and the silver(I) salt
AgPF6.25 Compounds 2a-f,h were isolated in 76-90% per-
forming the reactions in toluene at r.t. for 5 h.24 As shown
now in Table 1, the yields could be slightly improved ex-
tending the reaction time to 18 h (88-97%; entries 1-6 and
8). Under these new conditions, other iodoalkynes 1g,i-o,
including aromatic examples, were cleanly converted into
the corresponding (Z)-β-iodoenol acetates 2g,i-o, with
isolated yields ranging from 72 to 91% (entries 7 and 9-15).
The reactions proceeded in all the cases with complete
regio- and stereoselectivity. Thus, aside from 2a-o, the
only species detected by NMR in the crudes were the
unreacted starting materials and, in some cases, traces of
the enol acetates RC(OAc)=CH2 resulting from the partial
carbon-iodide bond cleavage of the products. Such a re-
i
5
R = CH2CH2 Pr (1e)
R = cPr (1f)
6
7
R = cPent (1g)
2g; 72
2h; 94
2i; 76
8
R = Cy (1h)
9
R = Bn (1i)
10
11
R = CH2Bn (1j)
R = CH2CH2Bn (1k)
R = Ph (1l)
2j; 79
2k; 82
2l; 74
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13
14
15
R = 4-C6H4Me (1m)
R = 4-C6H4F (1n)
R = 4-C6H4Br (1o)
2m; 91
2n; 84
2o; 79
a Reaction conditions: iodoalkyne 1 (1 mmol), glacial acetic
acid (1 mmol), [AuCl(PPh3)] (0.05 mmol), AgPF6 (0.05
b
mmol), toluene (3 mL), r.t., 18 h. Isolated yield after chro-
matographic purification.
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Scheme 5. Catalytic Addition of Different Carboxylic Acids to 1-Iodooct-1-yne (1d)
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In order to assess in more detail the scope of the pro-
cess, the addition of a number of other carboxylic acids to
1-iodooct-1-yne (1d) was explored under identical experi-
mental conditions (Scheme 5). To our delight, the catalyt-
ic reaction proved to be broadly applicable, and the novel
(Z)-β-iodoenol esters 3a-p could be synthesized with
complete regio- and stereoselectivity in 56-93% yield,
starting from different aliphatic, aromatic, heteroaro-
matic, heterocyclic and α,β-unsaturated carboxylic acids.
However, we must note that, compared to acetic acid
(entry 4 in Table 1), yields were in general lower, due
probably to the higher steric demand of the acids em-
ployed. In the case of substituted benzoic acids, electronic
effects also influence the reaction, with the electron-
donating substituents leading in general to higher yields.
nature, cleanly underwent the addition process to gener-
ate the corresponding (Z)-β-iodoenol esters 4a,b,f,g,i-l in
68-85% yield (Scheme 6).
One of the main applications of haloalkenes is their use
in the construction of polysubstituted olefins through
transition-metal-catalyzed cross-coupling reactions. In
this context, we previously demonstrated the utility of the
aliphatic (Z)-β-iodoenol acetates 2a-f,h as starting mate-
rials for the preparation of a broad family of (Z)-1-alkyl-2-
arylvinyl acetates by Pd-catalyzed Suzuki coupling with
arylboronic acids, products that were subsequently hy-
drogenated in the presence of chiral Rh(I) catalysts to
generate enantiomerically enriched homobenzylic ace-
tates.24 To further demonstrate the synthetic utility of the
(Z)-β-iodoenol esters generated through our gold-
catalyzed hydrocarboxylation reactions, their Sonogashira
coupling with terminal alkynes was now explored as an
entry route to 1,4-disubstituted (Z)-enynyl esters. We
would like to remark here that (Z)-enynyl acetates have
recently found application as starting materials for the
preparation of polysubstituted furans via metal-catalyzed
or iodine-induced electrophilic cyclization.22a,c,23e,28
Scheme 6. Catalytic Addition of Benzoic Acid to Dif-
ferent Iodoalkynes
As shown in Scheme 7, employing (Z)-1-iodooct-1-en-2-
yl acetate/benzoate (2d/3e) and (Z)-2-iodo-1-phenylvinyl
acetate (2l) as model substrates, a large variety of 1,4-
disubstituted (Z)-enynyl esters 5a-j, 6a-j and 7a-i could
be easily synthesized in excellent yields (80-96%) under
classical Sonogashira conditions, using different terminal
alkynes, 1,3-enynes and propargylic alcohols as coupling
partners.29
Further evidences of the generality of the process were
gained in the reaction of benzoic acid with iodoalkynes
1a,b,f,g,i-l which, regardless of their aliphatic or aromatic
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Scheme 7. Synthesis of 1,4-Disubstituted (Z)-Enynyl Esters from the (Z)-β-Iodoenol Esters 2d, 2l and 3e
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In summary, we have developed a wide scope procedure
for the synthesis of (Z)-β-iodoenol esters through the
unprecedented catalytic hydrocarboxylation of readily
available iodoalkynes with carboxylic acids.30 The process,
which is catalyzed by the in situ generated gold(I) cation
[Au(PPh3)]+, proceeds with complete regio- and stereose-
lectivity under mild conditions, affording the desired
products in moderate to excellent yields. The usefulness
of the resulting (Z)-β-iodoenol esters, some of them pre-
viously employed by us as starting materials for the syn-
thesis of valuable chiral homobenzylic acetates,24 was
further demonstrated herein with the preparation of a
broad family of 1,4-disubstituted (Z)-enynyl esters via
Sonogashira coupling with different terminal alkynes.
with the exception of complexes [AuCl(PPh3)]32 and
[Pd(PPh3)4],33 and the iodoalkynes 1a-o,34 which were
prepared by following the methods reported in the litera-
ture. For column chromatography, silica gel of 230-400
mesh was employed. For NMR spectra, the chemical shift
values (δ) are given in parts per million and are referred
to the residual peak of the deuterated solvent employed
(1H and 13C) or to the CFCl3 standard (19F). HRMS data
were obtained on a QTOF mass spectrometer.
General Procedure for the Catalytic Addition of
Carboxylic Acids to Iodoalkynes. Under an argon at-
mosphere, the corresponding iodoalkyne 1 (1 mmol) and
carboxylic acid (1 mmol), [AuCl(PPh3)] (0.024 g; 0.05
mmol), AgPF6 (0.012 g; 0.05 mmol) and toluene (3.0 mL)
were introduced into a Teflon-capped sealed tube, and
the reaction mixture stirred at room temperature for 18 h
in the absence of light. The solvent was then removed in
vacuo and the resulting oily residue purified by flash col-
umn chromatography over silica gel using diethyl
ether/hexane (1:10) as eluent. Characterization data for
the isolated (Z)-β-iodoenol esters are as follows:
EXPERIMENTAL SECTION
All the manipulations were performed under argon at-
mosphere using vacuum-line and standard sealed-tube
techniques. Solvents were dried by standard methods and
distilled under argon before use.31 All reagents were ob-
tained from commercial suppliers and used as received,
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(Z)-1-Iodopent-1-en-2-yl acetate (2a): Yellow oil. Yield:
21.1 ppm. IR (film): ν = 1765 (s, C=O), 1629 (m, C=C) cm-1.
0.241 g (95%). 1H NMR (CDCl3, 300 MHz): δ = 5.83 (s, 1H),
2.35 (t, J = 7.2 Hz, 2H), 2.24 (s, 3H), 1.58-1.46 (m, 2H), 0.94
(t, J = 7.5 Hz, 3H) ppm. 13C{1H} NMR (CDCl3, 75 MHz): δ =
167.5, 157.8, 65.3, 36.4, 21.0, 19.7, 13.4 ppm. IR (film): ν =
1767 (s, C=O), 1639 (m, C=C) cm-1. HRMS (ESI): m/z
276.9694, [M+Na+] (calcd for C7H11O2INa: 276.9696).
HRMS (ESI): m/z 317.0003, [M+Na+] (calcd for
1
2
3
4
5
6
7
8
C10H15O2INa: 317.0009).
(Z)-1-Iodo-3-phenylprop-1-en-2-yl acetate (2i): Yellow oil.
Yield: 0.230 g (76%). 1H NMR (CDCl3, 300 MHz): δ = 7.38-
7.22 (m, 5H), 5.79 (s, 1H), 3.68 (s, 2H), 2.20 (s, 3H) ppm.
13C{1H} NMR (CDCl3, 75 MHz): δ = 167.5, 156.8, 135.5, 129.2,
128.7, 127.1, 67.6, 40.5, 21.0 ppm. IR (film): ν = 1759 (s,
C=O), 1638 (m, C=C) cm-1. HRMS (ESI): m/z 324.9694,
[M+Na+] (calcd for C11H11O2INa: 324.9696).
(Z)-1-Iodohex-1-en-2-yl acetate (2b): Yellow oil. Yield:
0.249 g (93%). 1H NMR (CDCl3, 300 MHz): δ = 5.82 (s, 1H),
2.36 (t, J = 7.5 Hz, 2H), 2.23 (s, 3H), 1.49-1.44 (m, 2H), 1.37-
1.32 (m, 2H), 0.90 (t, J = 7.2 Hz, 3H) ppm. 13C{1H} NMR
(CDCl3, 75 MHz): δ = 167.5, 158.0, 65.2, 34.2, 28.4, 22.0,
21.0, 13.7 ppm. IR (film): ν = 1762 (s, C=O), 1638 (m, C=C)
cm-1. HRMS (ESI): m/z 290.9848, [M+Na+] (calcd for
C8H13O2INa: 290.9852).
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(Z)-1-Iodo-4-phenylbut-1-en-2-yl acetate (2j): Yellow oil.
Yield: 0.250 g (79%). 1H NMR (CDCl3, 300 MHz): δ = 7.35-
7.30 (m, 2H), 7.26-7.19 (m, 3H), 5.85 (s, 1H), 2.86-2.81 (m,
2H), 2.74-2.69 (m, 2H), 2.23 (s, 3H) ppm. 13C{1H} NMR
(CDCl3, 75 MHz): δ = 167.6, 157.0, 140.2, 128.5, 128.3, 126.3,
66.3, 36.1, 32.8, 21.0 ppm. IR (film): ν = 1759 (s, C=O), 1638
(m, C=C) cm-1. HRMS (ESI): m/z 338.9849, [M+Na+] (calcd
for C12H13O2INa: 338.9852).
(Z)-1-Iodohept-1-en-2-yl acetate (2c): Yellow oil. Yield:
0.271 g (96%). 1H NMR (CDCl3, 300 MHz): δ = 5.82 (s, 1H),
2.36 (t, J = 7.5 Hz, 2H), 2.23 (s, 3H), 1.50-1.46 (m, 2H), 1.32-
1.27 (m, 4H), 0.89 (t, J = 6.9 Hz, 3H) ppm. 13C{1H} NMR
(CDCl3, 75 MHz): δ = 167.5, 158.0, 65.2, 34.4, 31.0, 26.0,
22.3, 21.0, 13.9 ppm. IR (film): ν = 1761 (s, C=O), 1637 (m,
C=C) cm-1. HRMS (ESI): m/z 305.0004, [M+Na+] (calcd for
C9H15O2INa: 305.0009).
(Z)-1-Iodo-5-phenylpent-1-en-2-yl acetate (2k):35 Yellow
1
oil. Yield: 0.271 g (82%). H NMR (CDCl3, 300 MHz): δ =
7.33-7.28 (m, 2H), 7.24-7.17 (m, 3H), 5.86 (s, 1H), 2.66 (t, J
= 7.8 Hz, 2H), 2.41 (t, J = 6.9 Hz, 2H), 2.25 (s, 3H), 1.88-1.78
(m, 2H) ppm. 13C{1H} NMR (CDCl3, 75 MHz): δ = 167.5,
157.5, 141.3, 128.4 (2C), 126.0, 65.7, 34.9, 33.9, 27.9, 21.0
ppm.
(Z)-1-Iodooct-1-en-2-yl acetate (2d): Yellow oil. Yield:
0.287 g (97%). 1H NMR (CDCl3, 300 MHz): δ = 5.82 (s, 1H),
2.36 (t, J = 8.2 Hz, 2H), 2.23 (s, 3H), 1.50-1.45 (m, 2H), 1.34-
1.28 (m, 6H), 0.89 (t, J = 6.9 Hz, 3H) ppm. 13C{1H} NMR
(CDCl3, 75 MHz): δ = 167.4, 158.0, 65.1, 34.4, 31.5, 28.6,
26.3, 22.5, 21.0, 14.0 ppm. IR (film): ν = 1763 (s, C=O), 1638
(m, C=C) cm-1. HRMS (ESI): m/z 319.0153, [M+Na+] (calcd
for C10H17O2INa: 319.0165).
(Z)-2-Iodo-1-phenylvinyl acetate (2l):23b Yellow oil. Yield:
1
0.213 g (74%). H NMR (CDCl3, 300 MHz): δ = 7.47-7.44
(m, 2H), 7.39-7.36 (m, 3H), 6.66 (s, 1H), 2.37 (s, 3H) ppm.
13C{1H} NMR (CDCl3, 75 MHz): δ = 167.3, 155.0, 133.6, 129.4,
128.8, 125.2, 68.5, 21.0 ppm.
(Z)-2-Iodo-1-(4-methylphenyl)vinyl acetate (2m):23b Yel-
low oil. Yield: 0.275 g (91%). 1H NMR (CDCl3, 300 MHz): δ
= 7.33 (d, J = 8.1 Hz, 2H), 7.17 (d, J = 8.1 Hz, 2H), 6.57 (s,
1H), 2.36 (s, 3H), 2.35 (s, 3H) ppm. 13C{1H} NMR (CDCl3, 75
MHz): δ = 167.4, 155.1, 139.6, 130.9, 129.5, 125.1, 67.2, 21.3,
21.0 ppm.
(Z)-1-Iodo-5-methylhex-1-en-2-yl acetate (2e): Yellow oil.
1
Yield: 0.274 g (97%). H NMR (CDCl3, 300 MHz): δ = 5.83
(s, 1H), 2.36 (t, J = 7.8 Hz, 2H), 2.24 (s, 3H), 1.57-1.50 (m,
1H), 1.41-1.34 (m, 2H), 0.90 (d, J = 6.6 Hz, 6H) ppm. 13C{1H}
NMR (CDCl3, 75 MHz): δ = 167.5, 158.2, 65.1, 35.2, 32.4,
27.4, 22.3, 21.0 ppm. IR (film): ν = 1766 (s, C=O), 1639 (m,
C=C) cm-1. HRMS (ESI): m/z 305.0005, [M+Na+] (calcd for
C9H15O2INa: 305.0009).
(Z)-1-(4-Fluorophenyl)-2-iodovinyl acetate (2n):22d Yellow
1
oil. Yield: 0.257 g (84%). H NMR (CDCl3, 300 MHz): δ =
7.45-7.40 (m, 2H), 7.08-7.02 (m, 2H), 6.58 (s, 1H), 2.36 (s,
3H) ppm. 13C{1H} NMR (CDCl3, 75 MHz): δ = 167.3, 163.2
(d, J = 250.0 Hz), 154.1, 130.0 (d, J = 3.3 Hz), 127.2 (d, J = 8.4
Hz), 115.8 (d, J = 22.1 Hz), 68.0, 21.0 ppm. 19F{1H} NMR
(CDCl3, 282 MHz): δ = -111.1 ppm.
(Z)-1-Cyclopropyl-2-iodovinyl acetate (2f): Yellow oil.
1
Yield: 0.222 g (88%). H NMR (CDCl3, 300 MHz): δ = 5.87
(d, J = 0.6 Hz, 1H), 2.21 (s, 3H), 1.74-1.68 (m, 1H), 0.76-0.73
(m, 2H), 0.68-0.65 (m, 2H) ppm. 13C{1H} NMR (CDCl3, 75
MHz): δ = 167.3, 158.1, 63.9, 21.0, 14.8, 5.5 ppm. IR (film): ν
= 1764 (s, C=O), 1628 (m, C=C) cm-1. HRMS (ESI): m/z
274.9534, [M+Na+] (calcd for C7H9O2INa: 274.9539).
(Z)-1-(4-Bromophenyl)-2-iodovinyl acetate (2o): Yellow
1
solid. Yield: 0.290 g (79%). Mp 76-79 °C. H NMR (CDCl3,
300 MHz): δ = 7.49 (d, J = 8.7 Hz, 2H), 7.30 (d, J = 8.7 Hz,
2H), 6.68 (s, 1H), 2.36 (s, 3H) ppm. 13C{1H} NMR (CDCl3,
75 MHz): δ = 167.3, 154.1, 132.6, 132.0, 126.7, 123.6, 69.3, 21.0
ppm. IR (KBr): ν = 1763 (s, C=O), 1604 (m, C=C) cm-1.
HRMS (ESI): m/z 388.8642, [M+Na+] (calcd for
C10H8O2BrINa: 388.8644).
(Z)-1-Cyclopentyl-2-iodovinyl acetate (2g): Colourless oil.
1
Yield: 0.202 g (72%). H NMR (CDCl3, 300 MHz): δ = 5.91
(d, J = 1.0 Hz, 1H), 2.83-2.72 (m, 1H), 2.23 (s, 3H), 1.86-1.84
(m, 2H), 1.69-1.53 (m, 6H) ppm. 13C{1H} NMR (CDCl3, 75
MHz): δ = 167.4, 160.5, 64.7, 45.2, 30.3, 24.7, 21.1 ppm. IR
(film): ν = 1765 (s, C=O), 1629 (m, C=C) cm-1. HRMS (ESI):
m/z 302.9850, [M+Na+] (calcd for C9H13O2INa: 302.9852).
(Z)-1-Iodooct-1-en-2-yl propionate (3a): Orange oil. Yield:
0.279 g (90%). 1H NMR (CDCl3, 300 MHz): δ = 5.81 (s, 1H),
2.52 (q, J = 7.8 Hz, 2H), 2.36 (t, J = 7.2 Hz, 2H), 1.49-1.41
(m, 2H), 1.36-1.28 (m, 6H), 1.25 (t, J = 7.8 Hz, 3H), 0.89 (t, J
= 6.3 Hz, 3H) ppm. 13C{1H} NMR (CDCl3, 75 MHz): δ =
170.9, 158.0, 64.9, 34.4, 31.5, 28.6, 27.7, 26.3, 22.5, 14.0, 9.1
(Z)-1-Cyclohexyl-2-iodovinyl acetate (2h): Yellow oil.
1
Yield: 0.276 g (94%). H NMR (CDCl3, 300 MHz): δ = 5.85
(s, 1H), 2.29-2.15 (m, 1H), 2.23 (s, 3H), 1.91-1.88 (m, 2H),
1.77-1.65 (m, 3H), 1.32-1.12 (m, 5H) ppm. 13C{1H} NMR
(CDCl3, 75 MHz): δ = 167.4, 161.8, 65.1, 43.5, 30.5, 25.9, 25.8,
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ppm. IR (film): ν = 1759 (s, C=O), 1638 (m, C=C) cm-1.
8.13 (d, J = 8.4 Hz, 2H), 7.54 (d, J = 8.4 Hz, 2H), 6.79 (dd, J
HRMS (ESI): m/z 333.0308, [M+Na+] (calcd for
= 17.7 and 10.8 Hz, 1H), 5.92 (d, J = 17.7 Hz, 1H), 5.94 (s,
1H), 5.44 (d, J = 10.8 Hz, 1H), 2.51 (t, J = 7.5 Hz, 2H), 1.57-
1.50 (m, 2H), 1.40-1.30 (m, 6H), 0.89 (t, J = 6.6 Hz, 3H)
ppm. 13C{1H} NMR (CDCl3, 75 MHz): δ = 163.0, 158.2, 142.7,
135.9, 130.6, 128.3, 126.3, 117.0, 65.2, 34.6, 31.5, 28.6, 26.4,
22.5, 14.1 ppm. IR (film): ν = 1736 (s, C=O), 1638 (m, C=C),
1607 (s, C=C) cm-1. HRMS (ESI): m/z 407.0474, [M+Na+]
(calcd for C17H21O2INa: 407.0478).
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C11H19O2INa: 333.0322).
(Z)-1-Iodooct-1-en-2-yl heptanoate (3b): Yellow oil. Yield:
0.278 g (76%). 1H NMR (CDCl3, 300 MHz): δ = 5.81 (s, 1H),
2.49 (t, J = 7.5 Hz, 2H), 2.37 (t, J = 7.8 Hz, 2H), 1.79-1.70
(m, 2H), 1.50-1.29 (m, 14H), 0.93-0.87 (m, 6H) ppm. 13C{1H}
NMR (CDCl3, 75 MHz): δ = 170.3, 158.0, 64.9, 34.5, 34.3,
31.5, 31.4, 28.8, 28.6, 26.3, 24.8, 22.5 (2C), 14.0 (2C) ppm. IR
(film): ν = 1760 (s, C=O), 1638 (m, C=C) cm-1. HRMS (ESI):
m/z 389.0933, [M+Na+] (calcd for C15H27O2INa: 389.0948).
9
(Z)-1-Iodooct-1-en-2-yl 4-fluorobenzoate (3i): Orange oil.
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11
12
13
14
15
16
17
18
19
20
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22
23
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25
26
27
28
29
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42
43
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1
Yield: 0.256 g (68%). H NMR (CDCl3, 300 MHz): δ = 8.21-
8.17 (m, 2H), 7.22-7.16 (m, 2H), 5.95 (s, 1H), 2.51 (t, J = 7.5
Hz, 2H), 1.57-1.52 (m, 2H), 1.37-1.30 (m, 6H), 0.89 (t, J = 6.3
Hz, 3H) ppm. 13C{1H} NMR (CDCl3, 75 MHz): δ = 166.2 (d, J
= 255.3 Hz), 162.2, 158.1, 132.8 (d, J = 9.4 Hz), 125.5, 115.8 (d,
J = 22.1 Hz), 65.3, 34.5, 31.5, 28.6, 26.4, 22.5, 14.0 ppm.
19F{1H} NMR (CDCl3, 282 MHz): δ = -104.2 ppm. IR (film):
ν = 1739 (s, C=O), 1639 (m, C=C) cm-1. HRMS (ESI): m/z
399.0221, [M+Na+] (calcd for C15H18O2FINa: 399.0228).
(Z)-1-Iodooct-1-en-2-yl 3-cyclopentylpropanoate (3c):
Colourless oil. Yield: 0.299 g (79%). H NMR (CDCl3, 400
1
MHz): δ = 5.79 (s, 1H), 2.49 (t, J = 7.6 Hz, 2H), 2.35 (t, J =
7.6 Hz, 2H), 1.86-1.74 (m, 5H), 1.55-1.44 (m, 6H), 1.34-1.27
(m, 6H), 1.16-1.11 (m, 2H), 0.88 (t, J = 6.4 Hz, 3H) ppm.
13C{1H} NMR (CDCl3, 100 MHz): δ = 170.4, 158.0, 64.8, 39.6,
34.4, 33.6, 32.4, 31.4, 31.0, 28.6, 26.3, 25.1, 22.5, 14.0 ppm. IR
(film): ν = 1760 (s, C=O), 1638 (m, C=C) cm-1. HRMS (ESI):
m/z 401.0945, [M+Na+] (calcd for C16H27O2INa: 401.0948).
(Z)-1-Iodooct-1-en-2-yl 2-chlorobenzoate (3j): Colourless
1
oil. Yield: 0.243 g (62%). H NMR (CDCl3, 300 MHz): δ =
(Z)-1-Iodooct-1-en-2-yl cyclohexanecarboxylate (3d): Or-
1
8.09 (dd, J = 7.8 and 1.0 Hz, 1H), 7.54-7.37 (m, 3H), 5.97 (s,
1H), 2.52 (t, J = 7.5 Hz, 2H), 1.61-1.55 (m, 2H), 1.41-1.31 (m,
ange oil. Yield: 0.277 g (76%). H NMR (CDCl3, 300 MHz):
δ = 5.79 (s, 1H), 2.53-2.43 (m, 1H), 2.36 (t, J = 7.8 Hz, 2H),
2.08-2.03 (m, 2H), 1.85-1.80 (m, 2H), 1.69-1.24 (m, 14H),
0.89 (t, J = 6.6 Hz, 3H) ppm. 13C{1H} NMR (CDCl3, 75
MHz): δ = 172.5, 157.9, 64.7, 43.2, 34.4, 31.5, 29.0, 28.5, 26.3,
25.7, 25.3, 22.5, 14.0 ppm. IR (film): ν = 1755 (s, C=O), 1638
(m, C=C) cm-1. HRMS (ESI): m/z 387.0782, [M+Na+] (calcd
for C15H25O2INa: 387.0791).
13
6H), 0.90 (t, J = 6.6 Hz, 3H) ppm. C{1H} NMR (CDCl3, 75
MHz): δ = 161.8, 158.0, 134.3, 133.2, 132.0, 131.3, 129.0, 126.7,
65.5, 34.5, 31.5, 28.6, 26.4, 22.5, 14.0 ppm. IR (film): ν =
1750 (s, C=O), 1639 (m, C=C) cm-1. HRMS (ESI): m/z
393.0112, [M+H+] (calcd for C15H19O2ClI: 393.0113).
(Z)-1-Iodooct-1-en-2-yl 3-chlorobenzoate (3k): Colourless
1
oil. Yield: 0.267 g (68%). H NMR (CDCl3, 300 MHz): δ =
(Z)-1-Iodooct-1-en-2-yl benzoate (3e): Yellow oil. Yield:
1
8.15-8.04 (m, 2H), 7.63-7.59 (m, 1H), 7.43 (dd, J = 7.8 and
7.8 Hz, 1H), 5.96 (s, 1H), 2.50 (t, J = 7.8 Hz, 2H), 1.57-1.52
(m, 2H), 1.38-1.31 (m, 6H), 0.89 (t, J = 6.6 Hz, 3H) ppm.
13C{1H} NMR (CDCl3, 75 MHz): δ = 162.0, 158.0, 134.8, 133.7,
131.0, 130.2, 129.9, 128.3, 65.5, 34.5, 31.5, 28.6, 26.4, 22.5, 14.0
ppm. IR (film): ν = 1741 (s, C=O), 1639 (m, C=C) cm-1.
HRMS (ESI): m/z 414.9936, [M+Na+] (calcd for
C15H18O2ClINa: 414.9932).
0.329 g (92%). H NMR (CDCl3, 300 MHz): δ = 8.19-8.16
(m, 2H), 7.67-7.62 (m, 1H), 7.54-7.49 (m, 2H), 5.95 (s, 1H),
2.52 (t, J = 7.2 Hz, 2H), 1.58-1.51 (m, 2H), 1.39-1.31 (m, 6H),
0.90 (t, J = 6.3 Hz, 3H) ppm. 13C{1H} NMR (CDCl3, 75
MHz): δ = 163.2, 158.2, 133.7, 130.2, 129.3, 128.6, 65.2, 34.6,
31.5, 28.6, 26.4, 22.5, 14.1 ppm. IR (film): ν = 1738 (s, C=O),
1639 (m, C=C) cm-1. HRMS (ESI): m/z 381.0307, [M+Na+]
(calcd for C15H19O2INa: 381.0322).
(Z)-1-Iodooct-1-en-2-yl 2-bromo-6-methoxybenzoate (3l):
(Z)-1-Iodooct-1-en-2-yl 4-methoxybenzoate (3f): Yellow
1
1
Orange oil. Yield: 0.299 g (64%). H NMR (CDCl3, 300
oil. Yield: 0.361 g (93%). H NMR (CDCl3, 300 MHz): δ =
MHz): δ = 7.60-7.57 (m, 2H), 6.96 (dd, J = 9.0 and 3.3 Hz,
1H), 5.96 (s, 1H), 3.86 (s, 3H), 2.52 (t, J = 7.2 Hz, 2H), 1.60-
1.55 (m, 2H), 1.39-1.27 (m, 6H), 0.89 (t, J = 6.6 Hz, 3H)
ppm. 13C{1H} NMR (CDCl3, 75 MHz): δ = 162.1, 158.6, 158.0,
135.3, 131.5, 119.5, 117.0, 112.4, 65.5, 55.7, 34.4, 31.5, 28.6, 26.4,
22.5, 14.1 ppm. IR (film): ν = 1755 (s, C=O), 1640 (m, C=C)
cm-1. HRMS (ESI): m/z 488.9526, [M+Na+] (calcd for
C16H20O3BrINa: 488.9533).
8.12 (d, J = 9.0 Hz, 2H), 6.99 (d, J = 9.0 Hz, 2H), 5.91 (s,
1H), 3.90 (s, 3H), 2.50 (t, J = 7.2 Hz, 2H), 1.57-1.52 (m, 2H),
1.37-1.26 (m, 6H), 0.89 (t, J = 6.6 Hz, 3H) ppm. 13C{1H}
NMR (CDCl3, 75 MHz): δ = 163.9, 162.9, 158.3, 132.3, 121.5,
113.8, 65.0, 55.5, 34.6, 31.5, 28.6, 26.4, 22.5, 14.0 ppm. IR
(film): ν = 1731 (s, C=O), 1606 (m, C=C) cm-1. HRMS (ESI):
m/z 411.0412, [M+Na+] (calcd for C16H21O3INa: 411.0428).
(Z)-1-Iodooct-1-en-2-yl 3-methylbenzoate (3g): Yellow oil.
Yield: 0.298 g (80%). 1H NMR (CDCl3, 300 MHz): δ = 7.99-
7.97 (m, 2H), 7.47-7.38 (m, 2H), 5.94 (s, 1H), 2.51 (t, J = 7.5
Hz, 2H), 2.46 (s, 3H), 1.58-1.53 (m, 2H), 1.39-1.31 (m, 6H),
0.90 (t, J = 6.6 Hz, 3H) ppm. 13C{1H} NMR (CDCl3, 75
MHz): δ = 163.3, 158.2, 138.4, 134.4, 130.7, 129.1, 128.5, 127.4,
65.1, 34.6, 31.5, 28.6, 26.4, 22.5, 21.3, 14.0 ppm. IR (film): ν =
1736 (s, C=O), 1639 (m, C=C) cm-1. HRMS (ESI): m/z
395.0479, [M+Na+] (calcd for C16H21O2INa: 395.0484).
(Z)-1-Iodooct-1-en-2-yl pentafluorobenzoate (3m): Yellow
1
oil. Yield: 0.251 g (56%). H NMR (CDCl3, 300 MHz): δ =
6.05 (t, J = 1.0 Hz, 1H), 2.49 (td, J = 7.6 and 1.0 Hz, 2H),
1.58-1.53 (m, 2H), 1.38-1.31 (m, 6H), 0.90 (t, J = 6.6 Hz, 3H)
13
ppm. C{1H} NMR (CDCl3, 75 MHz): δ = 157.6, 155.3, 144.7
(m), 143.0 (m), 137.8 (m), 107.4, 66.1, 34.4, 31.4, 28.5, 26.1,
22.5, 14.0 ppm. 19F{1H} NMR (CDCl3, 282 MHz): δ = -136.5
(m, 2F), -147.1 (m, 1F), -159.9 (m, 2F) ppm. IR (film): ν =
1757 (s, C=O), 1652 (m, C=C) cm-1. HRMS (ESI): m/z
470.9835, [M+Na+] (calcd for C15H14F5O2INa: 470.9851).
(Z)-1-Iodooct-1-en-2-yl 4-vinylbenzoate (3h): Colourless
1
oil. Yield: 0.242 g (63%). H NMR (CDCl3, 300 MHz): δ =
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The Journal of Organic Chemistry
J = 1.2 Hz, 1H), 2.99-2.89 (m, 1H), 1.93-1.90 (m, 2H), 1.72-
(Z)-1-Iodooct-1-en-2-yl thiophene-2-carboxylate (3n): Yel-
low oil. Yield: 0.298 g (82%). 1H NMR (CDCl3, 300 MHz): δ
= 7.94 (d, J = 3.9 Hz, 1H), 7.65 (d, J = 4.5 Hz, 1H), 7.16 (dd, J
= 4.5 and 3.9 Hz, 1H), 5.93 (s, 1H), 2.49 (t, J = 7.2 Hz, 2H),
1.56-1.49 (m, 2H), 1.36-1.29 (m, 6H), 0.88 (t, J = 6.6 Hz, 3H)
ppm. 13C{1H} NMR (CDCl3, 75 MHz): δ = 158.5, 157.8, 134.8,
133.7, 132.5, 128.1, 65.6, 34.6, 31.5, 28.6, 26.4, 22.5, 14.1 ppm.
IR (film): ν = 1731 (s, C=O), 1640 (m, C=C) cm-1. HRMS
(ESI): m/z 386.9875, [M+Na+] (calcd for C13H17O2INaS:
386.9886).
1.59 (m, 6H) ppm. 13C{1H} NMR (CDCl3, 75 MHz): δ = 163.1,
160.6, 133.6, 130.2, 129.3, 128.6, 64.8, 45.4, 30.5, 24.7 ppm.
IR (film): ν = 1737 (s, C=O), 1630 (m, C=C) cm-1. HRMS
(ESI): m/z 364.9996, [M+Na+] (calcd for C14H15O2INa:
365.0009).
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(Z)-1-Iodo-3-phenylprop-1-en-2-yl benzoate (4i): Orange
1
oil. Yield: 0.262 g (72%). H NMR (CDCl3, 300 MHz): δ =
8.14-8.11 (m, 2H), 7.67-7.62 (m, 1H), 7.53-7.48 (m, 2H),
7.35-7.27 (m, 5H), 5.89 (s, 1H), 3.82 (s, 2H) ppm. 13C{1H}
NMR (CDCl3, 75 MHz): δ = 163.3, 157.1, 135.7, 133.7, 130.2,
129.3, 129.0, 128.7, 128.6, 127.1, 67.7, 40.7 ppm. IR (film): ν =
1727 (s, C=O), 1601 (m, C=C) cm-1. HRMS (ESI): m/z
386.9842, [M+Na+] (calcd for C16H13O2INa: 386.9852).
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14
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17
18
19
20
21
22
23
24
25
26
27
28
29
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31
32
33
34
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36
37
38
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43
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(Z)-1-Iodooct-1-en-2-yl 2-oxo-2H-chromene-3-carboxylate
(3o): Yellow oil. Yield: 0.285 g (67%). 1H NMR (CDCl3, 400
MHz): δ = 8.71 (s, 1H), 7.70-7.65 (m, 2H), 7.38-7.34 (m,
2H), 5.92 (s, 1H), 2.48 (t, J = 7.6 Hz, 2H), 1.55-1.51 (m, 2H),
1.34-1.26 (m, 6H), 0.86 (t, J = 6.8 Hz, 3H) ppm. 13C{1H}
NMR (CDCl3, 100 MHz): δ = 159.0, 158.0, 156.2, 155.4, 149.8,
134.9, 129.9, 125.0, 117.7, 117.0, 116.9, 65.6, 34.4, 31.4, 28.6,
26.3, 22.5, 14.0 ppm. IR (film): ν = 1770 (br, C=O), 1609 (br,
C=C) cm-1. HRMS (ESI): m/z 449.0215, [M+Na+] (calcd for
C18H19O4INa: 449.0220).
(Z)-1-Iodo-4-phenylbut-1-en-2-yl benzoate (4j): Orange
1
oil. Yield: 0.284 g (75%). H NMR (CDCl3, 300 MHz): δ =
8.21-8.18 (m, 2H), 7.68-7.65 (m, 1H), 7.57-7.52 (m, 2H),
7.35-7.21 (m, 5H), 5.97 (s, 1H), 2.94-2.83 (m, 4H) ppm.
13C{1H} NMR (CDCl3, 75 MHz): δ = 163.3, 157.1, 140.2, 133.8,
130.3, 129.1, 128.6, 128.5, 128.4, 126.3, 66.3, 36.3, 32.9 ppm.
IR (film): ν = 1732 (s, C=O), 1602 (m, C=C) cm-1. HRMS
(ESI): m/z 400.9998, [M+Na+] (calcd for C17H15O2INa:
401.0009).
(Z)-1-Iodooct-1-en-2-yl (E)-cinnamate (3p): Yellow oil.
1
Yield: 0.299 g (78%). H NMR (CDCl3, 300 MHz): δ = 7.86
(d, J = 15.9 Hz, 1H), 7.62-7.59 (m, 2H), 7.46-7.43 (m, 3H),
6.57 (d, J = 15.9 Hz, 1H), 5.90 (s, 1H), 2.46 (t, J = 7.5 Hz,
2H), 1.56-1.51 (m, 2H), 1.38-1.29 (m, 6H), 0.90 (t, J = 6.6 Hz,
3H) ppm. 13C{1H} NMR (CDCl3, 75 MHz): δ = 163.3, 158.0,
146.9, 134.1, 130.8, 129.0, 128.3, 116.8, 65.1, 34.6, 31.5, 28.6,
26.4, 22.5, 14.1 ppm. IR (film): ν = 1733 (s, C=O), 1634 (m,
C=C) cm-1. HRMS (ESI): m/z 407.0463, [M+Na+] (calcd for
C17H21O2INa: 407.0478).
(Z)-1-Iodo-5-phenylpent-1-en-2-yl benzoate (4k): Orange
1
oil. Yield: 0.298 g (76%). H NMR (CDCl3, 300 MHz): δ =
8.21-8.18 (m, 2H), 7.67-7.65 (m, 1H), 7.56-7.51 (m, 2H),
7.34-7.19 (m, 5H), 5.99 (s, 1H), 2.71 (t, J = 7.5 Hz, 2H), 2.58
(t, J = 7.2 Hz, 2H), 1.97-1.87 (m, 2H) ppm. 13C{1H} NMR
(CDCl3, 75 MHz): δ = 163.2, 157.7, 141.4, 133.7, 130.2, 129.2,
128.6, 128.5 (2C), 126.0, 65.8, 35.0, 34.1, 28.1 ppm. IR (film):
ν = 1737 (s, C=O), 1601 (m, C=C) cm-1. HRMS (ESI): m/z
415.0150, [M+Na+] (calcd for C18H17O2INa: 415.0165).
(Z)-1-Iodopent-1-en-2-yl benzoate (4a): Yellow oil. Yield:
1
0.265 g (84%). H NMR (CDCl3, 300 MHz): δ = 8.19-8.16
(m, 2H), 7.68-7.62 (m, 1H), 7.54-7.49 (m, 2H), 5.95 (s, 1H),
2.50 (t, J = 7.5 Hz, 2H), 1.65-1.53 (m, 2H), 0.98 (t, J = 7.5
Hz, 3H) ppm. 13C{1H} NMR (CDCl3, 75 MHz): δ = 163.2,
157.9, 133.7, 130.2, 129.2, 128.6, 65.3, 36.5, 19.8, 13.5 ppm. IR
(film): ν = 1737 (s, C=O), 1639 (m, C=C) cm-1. HRMS (ESI):
m/z 338.9844, [M+Na+] (calcd for C12H13O2INa: 338.9852).
(Z)-2-Iodo-1-phenylvinyl benzoate (4l): Orange oil. Yield:
1
0.242 g (69%). H NMR (CDCl3, 300 MHz): δ = 8.32-8.29
(m, 2H), 7.73-7.68 (m, 1H), 7.61-7.52 (m, 4H), 7.39-7.37 (m,
13
3H), 6.79 (s, 1H) ppm. C{1H} NMR (CDCl3, 75 MHz): δ =
163.2, 155.2, 134.0, 133.7, 130.4, 129.5, 128.9, 128.8, 128.7,
125.2, 68.5 ppm. IR (film): ν = 1771 (s, C=O), 1604 (m, C=C)
cm-1. HRMS (ESI): m/z 372.9682, [M+Na+] (calcd for
C15H11O2INa: 372.9696).
(Z)-1-Iodohex-1-en-2-yl benzoate (4b): Yellow oil. Yield:
1
0.281 g (85%). H NMR (CDCl3, 300 MHz): δ = 8.20-8.16
(m, 2H), 7.68-7.62 (m, 1H), 7.54-7.49 (m, 2H), 5.95 (s, 1H),
2.52 (t, J = 6.9 Hz, 2H), 1.57-1.50 (m, 2H), 1.43-1.35 (m, 2H),
0.93 (t, J = 7.2 Hz, 3H) ppm. 13C{1H} NMR (CDCl3, 75
MHz): δ = 163.2, 158.2, 133.7, 130.2, 129.2, 128.6, 65.2, 34.3,
28.6, 22.1, 13.8 ppm. IR (film): ν = 1739 (s, C=O), 1639 (m,
C=C) cm-1. HRMS (ESI): m/z 352.9999, [M+Na+] (calcd for
C13H15O2INa: 353.0009).
General Procedure for the Preparation of the 1,4-
Disubstituted (Z)-Enynyl Esters. Under an argon at-
mosphere, [Pd(PPh3)4] (0.058 g; 0.05 mmol), CuI (0.019 g;
0.1 mmol), the corresponding (Z)-β-iodoenol ester (1
mmol) and 1,4-dioxane (3 mL) were introduced into a
Teflon-capped sealed tube, and the resulting suspension
stirred at room temperature for 10 min. Then, Et3N (0.420
mL; 3 mmol) and the appropriate terminal alkyne (1.3
mmol) were added, and the mixture stirred at room tem-
perature for 4 h in the absence of light. The volatiles were
then removed in vacuo and the resulting residue purified
by flash column chromatography over silica gel using
diethyl ether/hexane (1:10) as eluent. Characterization
data for the isolated (Z)-enynyl esters are as follows:
(Z)-1-Cyclopropyl-2-iodovinyl benzoate (4f): Orange oil.
1
Yield: 0.223 g (71%). H NMR (CDCl3, 300 MHz): δ = 8.17-
8.14 (m, 2H), 7.68-7.62 (m, 1H), 7.54-7.49 (m, 2H), 6.00 (d,
J = 1.0 Hz, 1H), 1.91-1.82 (m, 1H), 0.82-0.76 (m, 4H) ppm.
13C{1H} NMR (CDCl3, 75 MHz): δ = 163.1, 158.3, 133.7, 130.2,
129.1, 128.6, 63.9, 15.0, 5.7 ppm. IR (film): ν = 1738 (s, C=O),
1632 (m, C=C) cm-1. HRMS (ESI): m/z 336.9685, [M+Na+]
(calcd for C12H11O2INa: 336.9696).
(Z)-1-Phenyldec-3-en-1-yn-4-yl acetate (5a):22a Yellow oil.
Yield: 0.256 g (95%). 1H NMR (CDCl3, 300 MHz): δ = 7.43-
7.40 (m, 2H), 7.33-7.30 (m, 3H), 5.45 (s, 1H), 2.34 (t, J = 7.5
Hz, 2H), 2.26 (s, 3H), 1.53-1.41 (m, 2H), 1.39-1.28 (m, 6H),
(Z)-1-Cyclopentyl-2-iodovinyl benzoate (4g): Orange oil.
Yield: 0.233 g (68%). 1H NMR (CDCl3, 300 MHz): δ = 8.19-
8.16 (m, 2H), 7.67-7.62 (m, 1H), 7.54-7.49 (m, 2H), 6.04 (d,
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The Journal of Organic Chemistry
Page 8 of 12
0.91 (t, J = 6.9 Hz, 3H) ppm. 13C{1H} NMR (CDCl3, 75
MHz): δ = 167.9, 160.3, 131.4, 128.3, 128.2, 123.3, 97.7, 93.8,
83.2, 33.9, 31.5, 28.7, 26.2, 22.5, 20.8, 14.1 ppm.
(Z)-1-Cyclopropyldec-3-en-1-yn-4-yl acetate (5h): Yellow
oil. Yield: 0.215 g (92%). H NMR (CDCl3, 400 MHz): δ =
1
1
2
3
4
5
6
7
8
5.15 (s, 1H), 2.22 (t, J = 7.6 Hz, 2H), 2.20 (s, 3H), 1.47-1.40
(m, 2H), 1.36-1.27 (m, 7H), 0.88 (t, J = 6.8 Hz, 3H), 0.83-
0.78 (m, 2H), 0.70-0.66 (m, 2H) ppm. 13C{1H} NMR
(CDCl3, 100 MHz): δ = 168.0, 159.2, 98.1, 97.9, 69.3, 33.6,
31.5, 28.6, 26.2, 22.5, 20.8, 14.0, 8.7, 0.3 ppm. IR (film): ν =
2116 (w, C≡C), 1761 (s, C=O), 1653 (m, C=C) cm-1. HRMS
(ESI): m/z 257.1515, [M+Na+] (calcd for C15H22O2Na:
257.1517).
(Z)-1-(4-Fluorophenyl)dec-3-en-1-yn-4-yl acetate (5b):22a
1
Yellow oil. Yield: 0.277 g (96%). H NMR (CDCl3, 300
MHz): δ = 7.40-7.35 (m, 2H), 7.04-6.98 (m, 2H), 5.43 (s,
1H), 2.33 (t, J = 7.2 Hz, 2H), 2.25 (s, 3H), 1.51-1.49 (m, 2H),
1.36-1.28 (m, 6H), 0.91 (t, J = 6.6 Hz, 3H) ppm. 13C{1H}
NMR (CDCl3, 75 MHz): δ = 167.9, 162.4 (d, J = 249.5 Hz),
160.4, 133.2 (d, J = 8.3 Hz), 119.4 (d, J = 3.5 Hz), 115.5 (d, J =
22.2 Hz), 97.5, 92.7, 82.9, 33.8, 31.5, 28.7, 26.2, 22.5, 20.8,
14.0 ppm. 19F{1H} NMR (CDCl3, 282 MHz): δ = -111.1 ppm.
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(Z)-1-(Cyclohex-1-en-1-yl)dec-3-en-1-yn-4-yl acetate (5i):
1
Colourless oil. Yield: 0.249 g (91%). H NMR (CDCl3, 300
MHz): δ = 6.07 (br, 1H), 5.33 (s, 1H), 2.27 (t, J = 7.2 Hz,
2H), 2.22 (s, 3H), 2.12-2.10 (m, 4H), 1.65-1.59 (m, 4H), 1.48-
1.45 (m, 2H), 1.32-1.29 (m, 6H), 0.89 (t, J = 6.6 Hz, 3H)
ppm. 13C{1H} NMR (CDCl3, 75 MHz): δ = 168.0, 159.2, 134.8,
120.8, 97.9, 95.9, 80.6, 33.8, 31.5, 29.2, 28.7, 26.2, 25.7, 22.5,
22.3, 21.5, 20.8, 14.0 ppm. IR (film): ν = 2194 (w, C≡C), 1763
(s, C=O), 1653 (m, C=C), 1623 (w, C=C) cm-1. HRMS (ESI):
m/z 297.1823, [M+Na+] (calcd for C18H26O2Na: 297.1825).
(Z)-1-(4-Bromophenyl)dec-3-en-1-yn-4-yl acetate (5c):
Yellow oil. Yield: 0.293 g (84%). H NMR (CDCl3, 300
1
MHz): δ = 7.44 (d, J = 8.4 Hz, 2H), 7.26 (d, J = 8.5 Hz, 2H),
5.43 (s, 1H), 2.33 (t, J = 7.8 Hz, 2H), 2.25 (s, 3H), 1.59-1.49
(m, 2H), 1.38-1.31 (m, 6H), 0.91 (t, J = 6.6 Hz, 3H) ppm.
13C{1H} NMR (CDCl3, 75 MHz): δ = 167.8, 160.7, 132.8, 131.5,
122.4, 122.3, 97.5, 92.6, 84.4, 33.9, 31.5, 28.7, 26.2, 22.5, 20.8,
14.0 ppm. IR (film): ν = 2210 (w, C≡C), 1759 (s, C=O), 1653
(m, C=C) cm-1. HRMS (ESI): m/z 371.0607, [M+Na+] (calcd
for C18H21O2BrNa: 371.0617).
(Z)-2-Hydroxy-2-methyldodec-5-en-3-yn-6-yl acetate (5j):
1
Orange oil. Yield: 0.219 g (87%). H NMR (CDCl3, 300
MHz): δ = 5.18 (s, 1H), 2.68 (s, 1H), 2.22 (t, J = 6.9 Hz, 2H),
2.18 (s, 3H), 1.49 (s, 6H), 1.43-1.41 (m, 2H), 1.31-1.24 (m,
6H), 0.86 (t, J = 6.3 Hz, 3H) ppm. 13C{1H} NMR (CDCl3, 75
MHz): δ = 167.9, 160.2, 98.7, 97.1, 75.8, 65.3, 33.7, 31.5, 31.3,
28.6, 26.1, 22.5, 20.7, 14.0 ppm. IR (film): ν = 3434 (br,
OH), 2222 (w, C≡C), 1763 (s, C=O), 1655 (m, C=C) cm-1.
HRMS (ESI): m/z 275.1621, [M+Na+] (calcd for C15H24O3Na:
275.1618).
(Z)-1-(4-Methylphenyl)dec-3-en-1-yn-4-yl acetate (5d):
1
Yellow oil. Yield: 0.275 g (97%). H NMR (CDCl3, 300
MHz): δ = 7.31 (d, J = 8.1 Hz, 2H), 7.12 (d, J = 8.1 Hz, 2H),
5.44 (s, 1H), 2.36 (s, 3H), 2.33 (t, J = 8.1 Hz, 2H), 2.26 (s,
3H), 1.52-1.50 (m, 2H), 1.37-1.32 (m, 6H), 0.92 (t, J = 7.2 Hz,
13
3H) ppm. C{1H} NMR (CDCl3, 75 MHz): δ = 168.0, 160.0,
138.3, 131.3, 129.0, 120.3, 97.8, 94.0, 82.6, 33.8, 31.5, 28.7,
26.3, 22.5, 21.5, 20.8, 14.0 ppm. IR (film): ν = 2201 (w, C≡C),
1761 (s, C=O), 1652 (m, C=C) cm-1. HRMS (ESI): m/z
307.1659, [M+Na+] (calcd for C19H24O2Na: 307.1669).
(Z)-1-Phenyldec-3-en-1-yn-4-yl benzoate (6a): Yellow oil.
Yield: 0.319 g (96%). 1H NMR (CDCl3, 300 MHz): δ = 8.25-
8.22 (m, 2H), 7.65-7.50 (m, 3H), 7.22-7.18 (m, 5H), 5.58 (s,
1H), 2.52 (t, J = 6.9 Hz, 2H), 1.63-1.60 (m, 2H), 1.43-1.32 (m,
(Z)-1-(4-Methoxyphenyl)dec-3-en-1-yn-4-yl acetate (5e):22a
1
Yellow oil. Yield: 0.282 g (94%). H NMR (CDCl3, 300
13
6H), 0.94 (t, J = 6.6 Hz, 3H) ppm. C{1H} NMR (CDCl3, 75
MHz): δ = 7.34 (d, J = 8.7 Hz, 2H), 6.84 (d, J = 8.7 Hz, 2H),
5.43 (s, 1H), 3.81 (s, 3H), 2.32 (t, J = 7.5 Hz, 2H), 2.25 (s,
3H), 1.54-1.49 (m, 2H), 1.38-1.31 (m, 6H), 0.91 (t, J = 6.6 Hz,
3H) ppm. 13C{1H} NMR (CDCl3, 75 MHz): δ = 168.0, 159.6,
159.5, 132.8, 115.5, 113.9, 97.8, 93.8, 81.9, 55.2, 33.8, 31.5, 28.7,
26.3, 22.5, 20.8, 14.0 ppm.
MHz): δ = 163.9, 160.8, 133.5, 131.3, 130.2, 129.6, 128.6, 128.1,
128.0, 123.3, 97.9, 94.1, 83.5, 34.0, 31.6, 28.8, 26.4, 22.6, 14.1
ppm. IR (film): ν = 2198 (w, C≡C), 1733 (s, C=O), 1646 (m,
C=C) cm-1. HRMS (ESI): m/z 355.1661, [M+Na+] (calcd for
C23H24O2Na: 355.1669).
(Z)-1-(4-Fluorophenyl)dec-3-en-1-yn-4-yl benzoate (6b):
(Z)-1-(Trimethylsilyl)dec-3-en-1-yn-4-yl acetate (5f): Col-
1
1
Yellow oil. Yield: 0.318 g (91%). H NMR (CDCl3, 300
ourless oil. Yield: 0.232 g (87%). H NMR (CDCl3, 400
MHz): δ = 8.21-8.18 (m, 2H), 7.68-7.63 (m, 1H), 7.54-7.49
(m, 2H), 7.14-7.09 (m, 2H), 6.90-6.85 (m, 2H), 5.52 (s, 1H),
2.48 (t, J = 7.2 Hz, 2H), 1.60-1.58 (m, 2H), 1.38-1.29 (m,
6H), 0.91 (t, J = 6.3 Hz, 3H) ppm. 13C{1H} NMR (CDCl3, 100
MHz): δ = 163.8, 162.2 (d, J = 249.2 Hz), 160.9, 133.5, 133.0
(d, J = 8.4 Hz), 130.1, 129.5, 128.5, 119.3, 115.4 (d, J = 22.0
Hz), 97.6, 92.7, 83.1, 34.0, 31.5, 28.7, 26.3, 22.5, 14.0 ppm.
19F{1H} NMR (CDCl3, 282 MHz): δ = -111.3 ppm. IR (film): ν
= 2204 (w, C≡C), 1739 (s, C=O), 1646 (m, C=C) cm-1. HRMS
(ESI): m/z 373.1578, [M+Na+] (calcd for C23H23O2FNa:
373.1574).
MHz): δ = 5.23 (s, 1H), 2.25 (t, J = 7.6 Hz, 2H), 2.20 (s, 3H),
1.49-1.44 (m, 2H), 1.34-1.28 (m, 6H), 0.88 (t, J = 6.4 Hz,
3H), -0.18 (s, 9H) ppm. 13C{1H} NMR (CDCl3, 100 MHz): δ =
167.7, 161.6, 99.3, 98.7, 97.7, 33.8, 31.5, 28.6, 26.1, 22.5, 20.7,
14.0, -0.1 ppm. IR (film): ν = 2136 (m, C≡C), 1766 (s, C=O),
1649 (m, C=C) cm-1. HRMS (ESI): m/z 289.1593, [M+Na+]
(calcd for C15H26O2NaSi: 289.1594).
(Z)-Tetradec-7-en-9-yn-7-yl acetate (5g): Yellow oil.
1
Yield: 0.210 g (84%). H NMR (CDCl3, 300 MHz): δ = 5.20
(s, 1H), 2.35-2.30 (m, 2H), 2.25 (t, J = 7.2 Hz, 2H), 2.21 (s,
3H), 1.49-1.44 (m, 6H), 1.32-1.29 (m, 6H), 0.95-0.87 (m,
13
6H) ppm. C{1H} NMR (CDCl3, 75 MHz): δ = 168.0, 158.9,
(Z)-1-(4-Bromophenyl)dec-3-en-1-yn-4-yl benzoate (6c):
1
Yellow oil. Yield: 0.362 g (88%). H NMR (CDCl3, 300
98.0, 94.9, 74.1, 33.6, 31.5, 30.8, 28.6, 26.2, 22.5, 21.8, 20.7,
19.1, 14.0, 13.5 ppm. IR (film): ν = 2220 (w, C≡C), 1763 (s,
C=O), 1653 (m, C=C) cm-1. HRMS (ESI): m/z 273.1825,
[M+Na+] (calcd for C16H26O2Na: 273.1825).
MHz): δ = 8.21-8.19 (m, 2H), 7.68-7.63 (m, 1H), 7.55-7.50
(m, 2H), 7.31 (d, J = 8.4 Hz, 2H), 6.99 (d, J = 8.5 Hz, 2H),
5.53 (s, 1H), 2.49 (t, J = 7.2 Hz, 2H), 1.67-1.56 (m, 2H), 1.46-
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The Journal of Organic Chemistry
1.30 (m, 6H), 0.92 (t, J = 6.6 Hz, 3H) ppm. 13C{1H} NMR
2114 (w, C≡C), 1755 (s, C=O), 1663 (m, C=C) cm-1. HRMS
(ESI): m/z 319.1677, [M+Na+] (calcd for C20H24O2Na:
1
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4
5
6
7
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(CDCl3, 75 MHz): δ = 163.8, 161.4, 133.6, 132.6, 131.4, 130.1,
129.4, 128.6, 122.3, 122.2, 97.6, 93.0, 84.7, 34.1, 31.5, 28.7,
26.3, 22.5, 14.1 ppm. IR (film): ν = 2206 (w, C≡C), 1737 (s,
C=O), 1643 (m, C=C) cm-1. HRMS (ESI): m/z 433.0774,
[M+Na+] (calcd for C23H23O2BrNa: 433.0773).
319.1674).
(Z)-1-(Cyclohex-1-en-1-yl)dec-3-en-1-yn-4-yl benzoate (6i):
1
Yellow oil. Yield: 0.299 g (89%). H NMR (CDCl3, 400
MHz): δ = 8.16-8.14 (m, 2H), 7.63-7.59 (m, 1H), 7.50-7.47
(m, 2H), 5.84 (m, 1H), 5.42 (s, 1H), 2.42 (t, J = 7.6 Hz, 2H),
1.97 (br, 2H), 1.89 (br, 2H), 1.60-1.48 (m, 6H), 1.40-1.28 (m,
6H), 0.88 (t, J = 6.8 Hz, 3H) ppm. 13C{1H} NMR (CDCl3, 100
MHz): δ = 163.8, 159.6, 134.6, 133.3, 130.1, 129.7, 128.4, 120.7,
98.0, 96.1, 80.7, 33.9, 31.5, 28.8, 28.7, 26.4, 25.6, 22.5, 22.2,
21.4, 14.0 ppm. IR (film): ν = 2193 (w, C≡C), 1738 (s, C=O),
1653 (m, C=C), 1623 (w, C=C) cm-1. HRMS (ESI): m/z
359.1983, [M+Na+] (calcd for C23H28O2Na: 359.1981).
(Z)-1-(4-Methylphenyl)dec-3-en-1-yn-4-yl benzoate (6d):
1
Yellow oil. Yield: 0.304 g (88%). H NMR (CDCl3, 400
MHz): δ = 8.20-8.18 (m, 2H), 7.65-7.61 (m, 1H), 7.52-7.28
(m, 2H), 7.04 (d, J = 8.0 Hz, 2H), 6.97 (d, J = 8.0 Hz, 2H),
5.52 (s, 1H), 2.47 (t, J = 7.2 Hz, 2H), 2.28 (s, 3H), 1.58-1.56
(m, 2H), 1.39-1.30 (m, 6H), 0.89 (t, J = 6.8 Hz, 3H) ppm.
13C{1H} NMR (CDCl3, 100 MHz): δ = 163.9, 160.4, 138.1,
133.4, 131.1, 130.1, 129.6, 128.9, 128.5, 120.2, 97.9, 94.3, 82.7,
33.9, 31.5, 28.7, 26.4, 22.5, 21.4, 14.0 ppm. IR (film): ν =
2204 (w, C≡C), 1736 (s, C=O), 1648 (m, C=C) cm-1. HRMS
(ESI): m/z 369.1820, [M+Na+] (calcd for C24H26O2Na:
369.1825).
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(Z)-2-Hydroxy-2-methyldodec-5-en-3-yn-6-yl
benzoate
(6j): Orange oil. Yield: 0.264 g (84%). 1H NMR (CDCl3, 300
MHz): δ = 8.17-8.14 (m, 2H), 7.66-7.61 (m, 1H), 7.53-7.48
(m, 2H), 5.33 (s, 1H), 2.42 (t, J = 7.2 Hz, 2H), 1.74 (br, 1H),
1.58-1.52 (m, 2H), 1.20-1.31 (m, 6H), 1.32 (s, 6H), 0.90 (t, J =
6.6 Hz, 3H) ppm. 13C{1H} NMR (CDCl3, 75 MHz): δ = 163.7,
160.8, 133.5, 130.0, 129.4, 128.5, 98.9, 97.3, 75.9, 65.3, 33.8,
31.5, 31.1, 28.7, 26.2, 22.5, 14.0 ppm. IR (film): ν = 3423 (br,
OH), 2222 (w, C≡C), 1736 (s, C=O), 1650 (m, C=C) cm-1.
HRMS (ESI): m/z 337.1768, [M+Na+] (calcd for
C20H26O3Na: 337.1774).
(Z)-1-(4-Methoxyphenyl)dec-3-en-1-yn-4-yl benzoate (6e):
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Yellow oil. Yield: 0.337 g (93%). H NMR (CDCl3, 300
MHz): δ = 8.22-8.19 (m, 2H), 7.65-7.62 (m, 1H), 7.54-7.49
(m, 2H), 7.10 (d, J = 8.7 Hz, 2H), 6.72 (d, J = 8.7 Hz, 2H),
5.53 (s, 1H), 3.76 (s, 3H), 2.45 (t, J = 7.5 Hz, 2H), 1.60-1.57
(m, 2H), 1.40-1.29 (m, 6H), 0.91 (t, J = 6.6 Hz, 3H) ppm.
13C{1H} NMR (CDCl3, 75 MHz): δ = 163.9, 160.0, 159.4, 133.4,
132.7, 130.1, 129.6, 128.5, 115.5, 113.8, 98.0, 94.1, 82.1, 55.2,
33.9, 31.6, 28.7, 26.4, 22.5, 14.0 ppm. IR (film): ν = 2203 (w,
C≡C), 1735 (s, C=O), 1648 (m, C=C) cm-1. HRMS (ESI): m/z
385.1768, [M+Na+] (calcd for C24H26O3Na: 385.1774).
(Z)-1,4-Diphenylbut-1-en-3-yn-1-yl acetate (7a):22a White
1
solid. Mp 106-109 °C. Yield: 0.236 g (90%). H NMR
(CDCl3, 300 MHz): δ = 7.55-7.52 (m, 2H), 7.50-7.46 (m,
2H), 7.43-7.35 (m, 6H), 6.21 (s, 1H), 2.42 (s, 3H) ppm.
13C{1H} NMR (CDCl3, 75 MHz): δ = 167.9, 155.7, 133.4, 131.5,
129.7, 128.8, 128.5, 128.4, 124.6, 123.2, 97.9, 97.1, 84.1, 20.7
ppm.
(Z)-1-(Trimethylsilyl)dec-3-en-1-yn-4-yl benzoate (6f):
1
Yellow oil. Yield: 0.308 g (94%). H NMR (CDCl3, 300
MHz): δ = 8.17-8.14 (m, 2H), 7.64-7.59 (m, 1H), 7.51-7.46
(m, 2H), 5.33 (s, 1H), 2.42 (t, J = 7.5 Hz, 2H), 1.55-1.53 (m,
2H), 1.35-1.28 (m, 6H), 0.89 (t, J = 6.6 Hz, 3H), -0.02 (s,
9H) ppm. 13C{1H} NMR (CDCl3, 75 MHz): δ = 163.6, 162.3,
133.4, 130.1, 129.6, 128.4, 99.6, 98.8, 97.8, 33.9, 31.5, 28.7,
26.2, 22.5, 14.0, -0.4 ppm. IR (film): ν = 2125 (m, C≡C), 1757
(s, C=O), 1672 (m, C=C) cm-1. HRMS (ESI): m/z 351.1742,
[M+Na+] (calcd for C20H28O2NaSi: 351.1751).
(Z)-4-(4-Fluorophenyl)-1-phenylbut-1-en-3-yn-1-yl acetate
1
(7b):22a Yellow solid. Mp 85-88 °C. Yield: 0.255 g (91%). H
NMR (CDCl3, 300 MHz): δ = 7.54-7.39 (m, 7H), 7.08-7.02
(m, 2H), 6.18 (s, 1H), 2.41 (s, 3H) ppm. 13C{1H} NMR
(CDCl3, 100 MHz): δ = 167.8, 162.6 (d, J = 250.1 Hz), 155.7,
133.3 (d, J = 8.2 Hz), 129.7, 128.7, 124.6, 119.3, 115.7 (d, J =
22.1 Hz), 97.7, 95.9, 83.8, 20.7 ppm. 19F{1H} NMR (CDCl3,
282 MHz): δ = -110.4 ppm.
(Z)-Tetradec-7-en-9-yn-7-yl benzoate (6g): Yellow oil.
Yield: 0.278 g (89%). 1H NMR (CDCl3, 400 MHz): δ = 8.15-
8.13 (m, 2H), 7.62-7.58 (m, 1H), 7.50-7.46 (m, 2H), 5.29 (s,
1H), 2.37 (t, J = 7.6 Hz, 2H), 2.19-2.15 (m, 2H), 1.56-1.49 (m,
2H), 1.35-1.19 (m, 10H), 0.87 (t, J = 6.8 Hz, 3H), 0.68 (t, J =
7.2 Hz, 3H) ppm. 13C{1H} NMR (CDCl3, 100 MHz): δ =
163.8, 159.3, 133.2, 130.1, 129.7, 128.4, 98.2, 95.2, 74.2, 33.7,
31.5, 30.6, 28.7, 26.3, 22.5, 21.7, 19.1, 14.0, 13.4 ppm. IR
(Z)-4-(4-Methylphenyl)-1-phenylbut-1-en-3-yn-1-yl acetate
(7c):22a Yellow solid. Mp 102-104 °C. Yield: 0.235 g (85%).
1H NMR (CDCl3, 300 MHz): δ = 7.54-7.51 (m, 2H), 7.42-7.35
(m, 5H), 7.16 (d, J = 8.1 Hz, 2H), 6.20 (s, 1H), 2.41 (s, 3H),
2.39 (s, 3H) ppm. 13C{1H} NMR (CDCl3, 75 MHz): δ = 168.0,
155.4, 138.7, 133.5, 131.4, 129.6, 129.2, 128.7, 124.5, 120.1, 98.0,
97.3, 83.5, 21.5, 20.7 ppm.
(film): ν = 2220 (w, C≡C), 1738 (s, C=O), 1653 (m, C=C) cm-
(Z)-4-(4-Methoxyphenyl)-1-phenylbut-1-en-3-yn-1-yl ace-
1
.
HRMS (ESI): m/z 335.1982, [M+Na+] (calcd for
tate (7d):22a Yellow solid. Mp 130-132 °C. Yield: 0.257 g
C21H28O2Na: 335.1981).
1
(88%). H NMR (CDCl3, 300 MHz): δ = 7.53-7.50 (m, 2H),
(Z)-1-Cyclopropyldec-3-en-1-yn-4-yl benzoate (6h): Yel-
low oil. Yield: 0.237 g (80%). 1H NMR (CDCl3, 400 MHz): δ
= 8.16-8.14 (m, 2H), 7.65-7.62 (m, 1H), 7.53-7.49 (m, 2H),
5.27 (s, 1H), 2.39 (t, J = 7.6 Hz, 2H), 1.57-1.50 (m, 2H), 1.38-
1.21 (m, 7H), 0.89 (t, J = 6.8 Hz, 3H), 0.67-0.63 (m, 2H),
7.42-7.37 (m, 5H), 6.88 (d, J = 8.7 Hz, 2H), 6.19 (s, 1H), 3.85
(s, 3H), 2.41 (s, 3H) ppm. 13C{1H} NMR (CDCl3, 75 MHz): δ
= 168.0, 159.9, 155.1, 133.5, 133.0, 129.5, 128.8, 124.5, 115.3,
114.1, 98.1, 97.4, 83.0, 55.3, 20.7 ppm.
(Z)-1-Phenyloct-1-en-3-yn-1-yl acetate (7e): Yellow oil.
Yield: 0.213 g (88%). 1H NMR (CDCl3, 300 MHz): δ = 7.47-
7.44 (m, 2H), 7.38-7.34 (m, 3H), 5.97 (t, J = 2.1 Hz, 1H),
2.42 (td, J = 6.9 and 2.1 Hz, 2H), 2.35 (s, 3H), 1.57-1.46 (m,
13
0.47-0.43 (m, 2H) ppm. C{1H} NMR (CDCl3, 100 MHz): δ
= 163.8, 159.6, 133.3, 130.0, 129.7, 128.4, 98.4, 98.0, 69.4,
33.7, 31.5, 28.7, 26.4, 22.5, 14.0, 8.5, 0.2 ppm. IR (film): ν =
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The Journal of Organic Chemistry
Page 10 of 12
4H), 0.96 (t, J = 7.2 Hz, 3H) ppm. 13C{1H} NMR (CDCl3, 75
MHz): δ = 168.0, 154.8, 133.6, 129.3, 128.7, 124.4, 98.7, 98.5,
75.0, 30.8, 21.9, 20.7, 19.5, 13.6 ppm. IR (film): ν = 2217 (m,
C≡C), 1770 (s, C=O), 1625 (m, C=C) cm-1. HRMS (ESI): m/z
265.1200, [M+Na+] (calcd for C16H18O2Na: 265.1199).
(Z)-1-Phenyldec-1-en-3-yn-1-yl acetate (7f):22a Yellow oil.
Yield: 0.238 g (88%). 1H NMR (CDCl3, 300 MHz): δ = 7.47-
7.44 (m, 2H), 7.38-7.34 (m, 3H), 5.96 (t, J = 2.4 Hz, 1H),
2.40 (td, J = 6.9 and 2.4 Hz, 2H), 2.35 (s, 3H), 1.60-1.31 (m,
8H), 0.92 (t, J = 6.6 Hz, 3H) ppm. 13C{1H} NMR (CDCl3, 75
MHz): δ = 168.0, 154.7, 133.6, 129.3, 128.7, 124.3, 98.8, 98.5,
75.0, 31.4, 28.7, 28.6, 22.6, 20.7, 19.8, 14.1 ppm.
We thank the Spanish Ministry of Economy and Competi-
1
2
3
4
5
6
7
8
tiveness (MINECO; Projects CTQ2013-40591-P, CTQ2016-
75986-P and CTQ2014-51912-REDC) and the Regional Gov-
ernment of Asturias (Project GRUPIN14-006) for financial
support. J.F. thanks MINECO and ESF for the award of a Juan
de la Cierva contract.
REFERENCES
1. The intramolecular version of this reaction also presents a
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60
(Z)-1,6-Diphenylhex-1-en-3-yn-1-yl acetate (7g): Colour-
less oil. Yield: 0.253 g (87%). 1H NMR (CDCl3, 300 MHz): δ
= 7.49-7.45 (m, 2H), 7.42-7.33 (m, 5H), 7.30-7.24 (m, 3H),
5.98 (t, J = 2.4 Hz, 1H), 2.92 (t, J = 7.5 Hz, 2H) 2.73 (td, J =
7.2 and 2.4 Hz, 2H), 2.28 (s, 3H) ppm. 13C{1H} NMR
(CDCl3, 75 MHz): δ = 168.1, 155.0, 140.5, 133.5, 129.4, 128.7,
128.5, 128.4, 126.4, 124.4, 98.3, 97.7, 75.6, 35.1, 22.0, 20.7
ppm. IR (film): ν = 2214 (w, C≡C), 1765 (s, C=O), 1694 (m,
C=C) cm-1. HRMS (ESI): m/z 313.1198, [M+Na+] (calcd for
C20H18O2Na: 313.1199).
(Z)-4-(Cyclohex-1-en-1-yl)-1-phenylbut-1-en-3-yn-1-yl ace-
tate (7h):22a White solid. Mp 87-90 °C. Yield: 0.232 g
1
2. See, for example: (a) Kleman, P.; González-Liste, P. J.; Gar-
cía-Garrido, S. E.; Cadierno, V.; Pizzano, A. Chem. Eur. J. 2013, 19,
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Destarac, M. ACS Macro Lett. 2015, 4, 89-93. (d) Foarta, F.; Lan-
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(87%). H NMR (CDCl3): δ = 7.49-7.46 (m, 2H), 7.39-7.35
(m, 3H), 6.17 (br, 1H), 6.10 (s, 1H), 2.37 (s, 3H), 2.18-2.15 (m,
4H), 1.70-1.62 (m, 4H) ppm. 13C{1H} NMR (CDCl3): δ =
167.9, 154.7, 135.7, 133.5, 129.4, 128.7, 124.4, 120.8, 99.4, 98.2,
81.6, 29.1, 25.8, 22.3, 21.4, 20.7 ppm.
(Z)-5-Hydroxy-1,5-diphenylpent-1-en-3-yn-1-yl
acetate
(7i): Orange oil. Yield: 0.242 g (83%). 1H NMR (CDCl3, 300
MHz): δ = 7.59 (d, J = 6.9 Hz, 2H), 7.50-7.36 (m, 8H), 6.04
(d, J = 1.5 Hz, 1H), 5.66 (d, J = 1.5 Hz, 1H), 2.67 (br, 1H), 2.21
(s, 3H) ppm. 13C{1H} NMR (CDCl3, 75 MHz): δ = 168.1,
156.6, 140.6, 133.2, 129.8, 128.8, 128.7, 128.4, 126.7, 124.7,
97.1, 96.6, 81.1, 65.1, 20.6 ppm. IR (film): ν = 3413 (br, OH),
2214 (w, C≡C), 1766 (s, C=O), 1625 (w, C=C) cm-1. HRMS
(ESI): m/z 315.099426, [M+Na+] (calcd for C19H16O3Na:
315.0992).
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ASSOCIATED CONTENT
Supporting Information. Copies of the NMR spectra of all
the (Z)-β-iodoenol and (Z)-enynyl esters synthesized in this
work. Synthesis, characterization data and NMR spectra of
compounds 10 and 11. This material is available free of charge
via the Internet at http://pubs.acs.org.
AUTHOR INFORMATION
Corresponding Author
* E-mail: garciagsergio@uniovi.es (S.E.G.-G.)
* E-mail: vcm@uniovi.es (V.C.)
Author Contributions
8. (a) Nakagawa, H.; Okimoto, Y.; Sakaguchi, S.; Ishii, Y. Tet-
rahedron Lett. 2003, 44, 103-106. (b) Merola, J. S.; Ladipo, F. T.
Polyhedron 2014, 70, 125-132.
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‡ These authors contributed equally.
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENT
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Smith, D. L.; Goundry, W. R. F.; Lam, H. W. Chem. Commun.
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25. The use of the [AuCl(PPh3)]/AgPF6 combination to pro-
mote the catalytic addition of carboxylic acids to non-
halogenated alkynes was previously described by Kim and co-
workers. See ref. 10b.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
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29
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33
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37
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26. See, for example: (a) Hashmi, A. S. K.; Hutchings, G. J. An-
gew. Chem. Int. Ed. 2006, 45, 7896-7936. (b) Hashmi, A. S. K.
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F. D. Nature 2007, 446, 395-403. (e) Gorin, D. J.; Sherry, B. D.;
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27. Additional experiments demonstrated the need of using
silver(I) salts containing non-coordinating anions, since identi-
cal reactions performed with AgOAc, AgOTs or AgOTf led to the
recovery of the starting iodoalkynes unchanged (both AgPF6 and
AgSbF6 can be used without major differences in yields). On the
other hand, we also noted that: (i) As previously observed by
Kim and co-workers (ref. 10b), the catalytic system
[AuCl(PPh3)]/AgPF6 was very sensitive to the solvent employed,
the yields decreasing drastically in DCM, DCE or MeOH. (ii) An
increase of the temperature (60 °C) results, as expected, in faster
conversions, but the side products RC(OAc)=CH2 are formed in
larger quantities. (iii) The reactions also proceed with a lower Au
loading (i.e. 2 mol%), but much longer times (48 h) are in this
case needed to obtain the (Z)-β-iodoenol acetates 2 in similar
yields.
15. (a) Xu, H.; Gu, S.; Chen, W.; Li, D.; Dou, J. J. Org. Chem.
2011, 76, 2448-2458. (b) Rajesh, N.; Prajapati, D. RSC Adv. 2014,
4, 32108-32112. (c) Liu, G.; Kong, L.; Shen, J.; Zhu, G. Org. Biomol.
Chem. 2014, 12, 2310-2321.
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29. The preparation of enynes 5a,b,e and 7a-d,f,h was previ-
ously described by Jiang and co-workers employing (Z)-β-
bromoenol acetates as starting materials. See ref. 22a.
30. The present hydrocarboxylation process is not restricted to
iodoalkynes, bromo- and cloroalkynes can also participate in the
reaction. Thus, employing identical experimental conditions, we
were able to synthesize (Z)-1-bromooct-1-en-2-yl acetate (10) and
(Z)-2-chloro-1-(4-methylphenyl)vinyl acetate (11) in 73 and 69%
yield by reacting 1-bromooct-1-yne (8) or 1-(chloroethynyl)-4-
methylbenzene (9), respectively, with acetic acid. Details are
given in the Supporting Information.
31. Armarego, W. L. F.; Chai, C. L. L., Purification of Laborato-
ry Chemicals (5th ed.); Butterworth-Heinemann: Oxford, 2003.
32. Mézailles, N.; Ricard, L.; Gagosz, F. Org. Lett. 2005, 7, 4133-
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33. Coulson, D. R.; Satek, L. C.; Grim, S. O. Inorg. Synth. 1972,
13, 121-124.
20. Hydrohalogenation reactions to afford 1,2-dihaloalkenes
have also been described: (a) Chen, Z.; Jiang, H.; Li, Y.; Qi, C.
Chem. Commun. 2010, 46, 8049-8051. (b) Zhu, G.; Chen, D.;
Wang, Y.; Zheng, R. Chem. Commun. 2012, 48, 5796-5798. (c) Li,
Y.; Liu, X.; Ma, D.; Liu, B.; Jiang, H. Adv. Synth. Catal. 2012, 354,
2683-2688. (d) Gómez-Herrera, A.; Nahra, F.; Brill, M.; Nolan, S.
P.; Cazin, C. S. J. ChemCatChem 2016, 8, 3381-3388.
21. Intramolecular examples of this reaction to give haloenol
lactones, promoted by mercury salts and gold catalysts, are
known. See, for example: (a) Krafft, G. A.; Katzenellenbogen, J.
A. J. Am. Chem. Soc. 1981, 103, 5459-5466; (b) Dai, W.; Katzenel-
lenbogen, J. A. J. Org. Chem. 1991, 56, 6893-6896. (c) Harkat, H.;
Weibel, J.-M.; Pale, P. Tetrahedron Lett. 2006, 47, 6273-6276. (d)
Harkat, H.; Dembelé, A. Y.; Weibel, J.-M.; Blanc, A.; Pale, P.
Tetrahedron 2009, 65, 1871-1879.
22. See, for example: (a) Chen, Z.; Huang, G.; Jiang, H.; Huang,
H.; Pan, X. J. Org. Chem. 2011, 76, 1134-1139. (b) Chen, X.; Chen,
D.; Lu, Z.; Kong, L.; Zhu, G. J. Org. Chem. 2011, 76, 6338-6343. (c)
Okamoto, N.; Yanada, R. J. Org. Chem. 2012, 77, 3944-3951. (d)
Chen, Z.; Ye, D.; Xu, G.; Ye, M.; Liu, L. Org. Biomol. Chem. 2013,
11, 6699-6702.
34. (a) Luithle, J. E. A.; Pietruszka, J. Eur. J. Org. Chem. 2000,
2557-2562. (b) Reddy, K. R.; Venkateshwar, M.; Maheswari, C. U.;
Kumar, P. S. Tetrahedron Lett. 2010, 51, 2170-2173. (c) Usanov, D.
L.; Yamamoto, H. J. Am. Chem. Soc. 2011, 133, 1286-1289.
35. Ochiai, M.; Tsuchimoto, Y.; Hayashi, T. Tetrahedron Lett.
2003, 44, 5381-5384.
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