Alkynylation of aldehydes and ketones using the Bu4NOH/H 2O/DMSO catalytic composition: A wide-scope methodology

Article abstract of DOI:10.1002/ejoc.201402275

The Favorsky reaction of a wide range of aldehydes and ketones with alkynes has been implemented under mild conditions (5-20 C). Using a Bu ₄NOH/H₂O/DMSO catalytic system, propargylic alcohols are formed cleanly in 39-93% (mostly 72-93%) yields and with ca. 100% selectivity. The method is suitable for aliphatic, aromatic, and heteroaromatic aldehydes and ketones, and for aliphatic, aromatic, and functionalized acetylenes. Thus, this represents the most general and efficient protocol to achieve the Favorsky reaction. Copyright

Full text of DOI:10.1002/ejoc.201402275

Job/Unit: O42275
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Date: 03-06-14 19:09:19
Pages: 9
FULL PAPER
DOI: 10.1002/ejoc.201402275
Alkynylation of Aldehydes and Ketones Using the Bu4NOH/H2O/DMSO
Catalytic Composition: A Wide-Scope Methodology
Elena Yu. Schmidt,[a] Natalia A. Cherimichkina,[a] Ivan A. Bidusenko,[a]
Nadezhda I. Protzuk,[a] and Boris A. Trofimov*[a]
Keywords: Synthetic methods / C–C bond formation / Alkynes / Aldehydes / Ketones
The Favorsky reaction of a wide range of aldehydes and
ketones with alkynes has been implemented under mild con-
ditions (5–20 °C). Using a Bu4NOH/H2O/DMSO catalytic sys-
tem, propargylic alcohols are formed cleanly in 39–93%
(mostly 72–93%) yields and with ca. 100% selectivity. The
method is suitable for aliphatic, aromatic, and heteroaromatic
aldehydes and ketones, and for aliphatic, aromatic, and func-
tionalized acetylenes. Thus, this represents the most general
and efficient protocol to achieve the Favorsky reaction.
alkynes. Another disadvantage of this protocol was that
aromatic aldehydes with phenylacetylene formed chalcones
instead of the target secondary ynols.[14]
Introduction
The alkynylation of carbonyl compounds to generate
propargylic alcohols (the Favorsky reaction) is among the
most important carbon–carbon bond-forming reactions.[1]
Propargylic alcohols are versatile synthetic intermediates
for both fine[2] and large-scale[3] organic synthesis. Recent
advances in the enantioselective synthesis of propargylic
alcohols[4] have stimulated interest in this class of acetylenic
compounds. It is no wonder that effort continues to be in-
vested in finding inexpensive procedures for the synthesis
of propargylic alcohols.
Later, a version of phase-transfer catalysis (Bu4NBr/
NaOHaq and fluorobenzene as an organic phase) for the
ethynylation of aldehydes and ketones with substituted
acetylenes was disclosed, but the reactions of aromatic alde-
hydes and ketones with phenylacetylene gave low yields
(30–35%).[15] Recently, alkylaromatic ketones were success-
fully alkynylated with arylacetylenes using a very high (10-
fold) molar excess of KOH and 10 mol-% of Bu4NCl in
THF.[16]
It
was
reported
that
Bu4NF[17]
or
Catalysis by transition-metal complexes (e.g., Ti,[5] Cr,[6]
Cu,[7] Zn,[8] Ru,[9] Rh,[10] Pd,[11] Ag,[12] or In[13]) is success-
fully used for the synthesis of propargylic alcohols. But
there are some recognized shortcomings of this approach.
These include the toxicity and high cost of some catalysts,
and the difficulty of getting rid of traces of metals, which
is particularly problematic for the synthesis of pharmaceuti-
cals.
Several approaches are being investigated in attempts to
circumvent these drawbacks. For example, a common or-
ganic base, triton B, or a basic Dowex resin have been used
for the alkynylation of some carbonyl compounds, but aro-
matic aldehydes and ketones gave low yields with these cata-
lysts.[14] Also, this reaction worked only for monosubsti-
tuted acetylenes; the most important parent compound,
acetylene itself, was not even mentioned among the tested
P(PhCH2NCH2CH2)3N[18] catalyzed the addition of silyl-
acetylenes to carbonyl compounds to deliver, after hydroly-
sis/desilylation, the corresponding propargylic alcohols in
satisfactory-to-good yields.
Several
strong-base-catalyzed
syntheses
(KOH/
DMSO,[1b] CsOH·H2O/THF,[19] tBuOK[20]) have been re-
ported, but they allow only aliphatic propargylic alcohols
to be prepared efficiently. For instance, only aliphatic
ketones were converted into the corresponding tertiary yn-
ols using tBuOK;[20a] attempted alkynylation of aldehydes
led to a complex mixture of products. The superbasic sys-
tem CsOH·H2O/THF gave a solution to this problem when
it was used with a syringe pump technique, but the alk-
ynylation of aromatic carbonyl compounds could not be
achieved with this system.[19] Quantitative yields of prop-
argylic alcohols were obtained by using tBu-P4 base in
DMSO, but the substrates investigated were limited to
phenylacetylene, pivalaldehyde, and acetone only.[21] Sol-
vent-free ball-milling conditions for the alkynylation of aro-
matic ketones with substituted acetylenes based on the use
of 18-crown-6 and solid KOH have also been published.[22]
Unfortunately, stoichiometric amounts of crown ether were
necessary to drive the reactions to completion.
[a] A. E. Favorsky Irkutsk Institute of Chemistry Siberian Branch,
Russian Academy of Sciences,
1 Favorsky Str., 664033 Irkutsk, Russia
E-mail: boris_trofimov@irioch.irk.ru
http://www.irkinstchem.ru/
Supporting information for this article is available on the
WWW under http://dx.doi.org/10.1002/ejoc.201402275.
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FULL PAPER
It should be emphasized that all the protocols described
above relate to the synthesis of propargylic alcohols con-
taining an internal triple bond through the reaction of sub-
stituted acetylenes with carbonyl compounds. Surprisingly,
there have been far fewer reports on the synthesis of prop-
argylic alcohols with a terminal triple bond, i.e., using un-
substituted acetylene. However, the latter class of proparg-
ylic alcohols is especially valuable, because the -CϵCH
moiety is capable of such important reactions as addition
to carbonyl compounds, aminomethylation (Mannich reac-
tion), oxidative homocoupling, silylation, diverse met-
alation, and Pd-catalyzed cross-couplings and their varia-
tions (Sonogashira reaction).
In 2013, an efficient and attractively simple method for
the ethynylation of aromatic and heteroaromatic aldehydes
and ketones with unsubstituted acetylene (ethyne) at atmo-
spheric pressure in the presence of a superbase catalyst (i.e.,
KOH/H2O/DMSO[23] or KOH/EtOH/H2O/DMSO[24]) was
disclosed. These findings appear to be a promising step
towards the synthesis of secondary and tertiary propargylic
alcohols with a terminal ethynyl group, starting from free
acetylene, an industrially available feedstock. This sounds
particularly attractive, because calcium carbide (a multi-
million-tons industrial source of acetylene)[25] has proved to
be a renewable raw material, due to the development of its
synthesis from biochar[26] or lignocellulose.[27] This new
trend has been recognized in the most recent publication on
the direct utilization of calcium carbide for the preparation
of aliphatic propargylic alcohols.[28] It was claimed that
both secondary and tertiary aliphatic propargylic alcohols
could be prepared from calcium carbide (2.5 equiv.),
Cs2CO3 (0.5 equiv. with respect to the carbonyl compound)
in aqueous DMSO at 60 °C for 8 h, though under these
conditions at least tertiary propargylic alcohols are known
to undergo retro-Favorsky decomposition. Also, despite the
superficial appeal of this method, the recovery of the target
acetylenic alcohols from a large amount of a solid mixture
containing Ca(OH)2, CaC2, and Cs2CO3 represents an ob-
vious challenge.
Scheme 1. Bu4NOH/H2O/DMSO-catalyzed alkynylation of alde-
hydes and ketones with alkynes.
The catalytic system includes commercially available Bu4-
NOH (40% aqueous solution) and DMSO. Initially, the
aqueous Bu4NOH was partially dried over molecular sieves
(4 Å type) in DMSO solution for 1 h. The water content in
the catalytic system prepared in this way was ca. 10%.
As a model reaction for the initial testing of the activity
of the Bu4NOH/H2O/DMSO catalytic system (Table 1), we
chose the reaction of acetophenone (1g) with unsubstituted
acetylene (2a). Reactions were carried out in a flow reactor
at atmospheric pressure, at 5Ϯ2 °C, in aqueous DMSO.
The molar ratio of ketone 1g to Bu4NOH was 1:0.25–2.00.
Acetylene was passed (at a rate of ca. 15 mL/min) through
the stirred catalytic solution, while the ketone was gradually
added. After certain time intervals, the reaction mixture was
diluted with ice-water (1:1) and extracted with Et2O. The
extract was washed with water, and, after evaporation of
extractant, the crude product was purified by column
chromatography. As seen from Table 1, with 0.25 and
0.50 equiv. of Bu4NOH relative to ketone 1g, the yields of
target propargylic alcohol 3g were 53 and 65%, respectively
(Table 1, entries 1 and 2). When ketone 1g and the base
were used in an equimolar ratio, the yield of target com-
pound 3g became 91% (Table 1, entry 3). But when the
aqueous Bu4NOH was not pre-dried over molecular sieves,
the yield of alcohol 3g was 43%, and the conversion (50%)
of the starting ketone was incomplete (Table 1, entry 4). A
further increase of the concentration of Bu4NOH up to
2 equiv. relative to ketone 1g resulted in a decrease in the
Table 1. Alkynylation of acetophenone (1g) with acetylene (2a)
using the Bu4NOH/H2O/DMSO system: effect of various reaction
parameters on the yield of propargyl alcohol 3g.[a]
Virtually none of the above methods is universally appli-
cable to both aliphatic and aromatic carbonyl compounds,
as well as monosubstituted acetylenes, and, especially,
acetylene itself.
Results and Discussion
In this paper, we report a general efficient metal-free
method for the alkynylation of aldehydes and ketones (in-
cluding both aliphatic and aromatic examples), using the
original organic catalytic system Bu4NOH/H2O/DMSO.
The method proved to be equally efficient for free acetylene
and phenylacetylene, the most widespread and practically
useful alkynes (Scheme 1). It appears that this catalytic sys-
tem is also applicable to diverse less popular alkynes, such
as 1-octyne, 1-ethynylcyclohexane, 3,3-dimethyl-1-butyne,
and 3-butoxy-1-propyne. This indicates that the method has
a general character.
Entry
Bu4NOH [equiv.]
Time [h]
Yield of 3g [%][b]
1
2
3
4
5
6
0.25
0.50
1
1
2
1
1
1
1
1
2
53
65
91
43[c]
70
1
87
[a] Reaction conditions: acetophenone (1g; 2 g, 17 mmol), DMSO
(50 mL), atmospheric pressure of acetylene (2a), flow reactor,
5Ϯ2 °C. [b] Isolated yield after purification (column chromatog-
raphy, basic Al2O3, hexane/ethyl acetate as eluent). [c] Without pre-
drying over molecular sieves.
2
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Alkynylation of Aldehydes and Ketones
product yield to 70% (Table 1, entry 5). The close-to-opti-
We went on to investigate the substrate scope of this cata-
mal reaction time was determined to be 1 h. The yield of lytic system with a series of ketones 1a–1i and alkynes 2a–
alcohol 3g was found to be slightly lower after a reaction 2f (Table 2).
time of 2 h than after 1 h (87 vs. 91%, Table 1, entries 6 and
Under the conditions described above, alkynylation of
3), and this probably results from a slight decomposition of the ketones with unsubstituted acetylene (2a) proceeded
the product. The reaction was highly selective: the forma- smoothly under atmospheric pressure to give the desired
tion even of trace amounts of acetylenic diol was not ob- tertiary propargylic alcohols (i.e., 3a–3i) in good-to-high
served (GLC, NMR spectroscopy).
isolated yields (72–93%). In most cases, the conversion of
Table 2. Alkynylation of ketones with alkynes using the Bu4NOH/H2O/DMSO catalytic system.[a]
[a] Reaction conditions: ketone 1a–1i (17 mmol), Bu4NOH (17 mmol), DMSO (50 mL). [b] Isolated yield after purification (column
chromatography, basic Al2O3, hexane/ethyl acetate as eluent). [c] Atmospheric pressure of acetylene (2a), flow reactor, 5Ϯ2 °C, 1 h.
[d] Alkyne 2b–2d (51 mmol), 20Ϯ2 °C, 72 h. [e] Incomplete conversion of ketone, no by-products were detected in the crude product
(NMR spectroscopy). [f] Alkyne 2e, 2f (51 mmol), 5Ϯ2 °C, 3 h.
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B. A. Trofimov et al.
FULL PAPER
1
the starting ketones was complete. H NMR spectroscopic Table 3. Alkynylation of aldehydes with alkynes using the
Bu4NOH/H2O/DMSO system.[a]
analysis of the reaction mixtures showed no formation of
products other than the target propargylic alcohols, which
implies that the ethynylation reaction has a 100% selec-
tivity. However, the yields given in Table 2 are less than
quantitative, which is due to losses during chromatographic
isolation. As seen in Table 2, the reaction tolerates ketones
with diverse structures bearing aliphatic (1a–1e), alicyclic
(1f), and aromatic (1g–1i) substituents, including condensed
aromatic (1h) and heteroaromatic (1i) groups.
With phenylacetylene (2e), high yields (69–87%) of the
corresponding propargylic alcohols (i.e., 3m–3q) were also
obtained (Table 2). But we found from a series of experi-
ments that to achieve this, a threefold molar excess of phen-
ylacetylene and a longer reaction time (3 h) were needed.
Under these conditions, the conversion of the ketones was
also close to 100%.
Aliphatic acetylenes 2b–2d are, as expected, less reactive
in the alkynylation reaction described here, requiring a
higher temperature (20Ϯ2 °C) and longer reaction time
(72 h). It should also be noted that, unlike the experiments
with parent acetylene (2a) and phenylacetylene (2e), the
yields of alcohols 3j–3l (39, 74, and 39%, respectively)
shown in Table 2 are not optimized. The coverage of alkyl-
acetylenes by this methodology is particularly synthetically
valuable, since such acetylenes usually undergo rapid proto-
tropic shift of the triple bond along the alkyl chain under
the action of strong metal-derived bases like KOH/
DMSO.[1b] Analysis of the reaction mixtures shows that in
the presence of the Bu4NOH/H2O/DMSO catalytic system,
this isomerization is entirely suppressed, which is obviously
due to a high protonation rate (high concentration of
water).
[a] Reaction conditions: aldehyde
4
(17 mmol), Bu4NOH
(17 mmol), DMSO (50 mL), 5Ϯ2 °C, 5 min. [b] Isolated yield after
purification (column chromatography, basic Al2O3, hexane/ethyl
acetate as eluent). [c] Atmospheric pressure of acetylene (2a), flow
reactor. [d] Alkyne 2e (51 mmol).
matic ones, proceeds with various complications[19,23,28] that
result in lower yield[14,15] and selectivity[14,23] as compared
with the alkynylation of ketones. For example, aromatic al-
dehydes, when alkynylated with phenylacetylene, deliver
chalcone derivatives[15] (owing to the prototropic rearrange-
ment of the target secondary propargylic alcohols), along
with other aldehyde condensation products.
Apparently, the suppression of the prototropic shifts and
the autocondensation processes in the reaction of aldehydes
with alkynes mediated by the catalytic system disclosed in
this paper may relate to the lower basicity of a reaction
mixture that contains more water (≈ 10%) than is com-
This effect is particularly striking for 3-butoxy-1-propyne
(2f), a propargylic ether, which, in the presence of KOH and
DMSO, isomerizes instantly into the corresponding allenic
ether at room temperature.[1b] The catalytic system de-
scribed here does not promote such an isomerization at all,
and the selectivity of the major alkynylation process is sus-
tained.
For aldehydes 4, both aliphatic and aromatic, this alk- monly the case for the alkynylation of carbonyl compounds.
ynylation method has been shown to be as efficient as it is
It should be emphasized that the real yields of proparg-
for ketones (Table 3).
ylic alcohols 3a–3r and 5a–5g (as estimated by NMR spec-
With aldehydes, the reaction time is considerably shorter troscopy or GLC) are actually higher (almost quantitative)
(5 min). This is due to the greater electrophilicity of the than those obtained after purification by column
aldehyde functionality. The almost equal potency of the chromatography (Tables 2 and 3). This is due to inevitable
catalytic system for both aldehydes and ketones represents losses during extraction and chromatography, since the
a very important advantage over other known systems. In products may, to some extent, be soluble in water, and be
fact, as a rule, the alkynylation of aldehydes, especially aro- retained on the chromatographic stationary phase.
4
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Alkynylation of Aldehydes and Ketones
equipped with an inverse-gradient 5 mm probe, in CDCl3, C6D6,
or (CD3)2CO, using hexamethyldisiloxane (HMDS) as an internal
standard. All 2D NMR spectra were recorded using standard gra-
dient Bruker pulse programs. IR spectra were obtained with a
Bruker Vertex 70 spectrometer. Elemental analysis was carried out
with a ThermoFinnigan 1112 elemental analyzer.
The mechanism of the alkynylation in the presence of
the catalytic system described here should normally involve
deprotonation of the alkyne by the hydroxide anion. Subse-
quent nucleophilic addition of the resulting acetylide ion
A to the carbonyl group would then generate the oxygen-
centered anion of the propargylic alcohol, accompanied by
the bulky tetrabutylammonium cation (intermediate B,
Scheme 2). In the loose (due to bulky butyl substituents)
ion pair in B, the alkoxide anion is more accessible for pro-
tons in the reaction medium than in the common contact
ion pairs of alkali metal cations. This facilitates the release
of the free propargylic alcohol. Since both the acetylene–
allene isomerization and the retro-Favorsky reaction of
propargylic alcohols are initiated by deprotonation, the
lower concentration of alkoxides (intermediate B) explains
the observed suppression of these side-reactions, i.e., the
higher selectivity of the alkynylation.
General Procedure for the Synthesis of Propargylic Alcohols: To
11 mL of commercial 40% aqueous solution of Bu4NOH (4.41 g,
17 mmol) in DMSO (30 mL), was added 23.4 g of molecular sieves
(4 Å). The mixture was allowed to stand for 1 h. Then the sieves
were removed by filtration, and DMSO (20 mL) was added. The
content of water in the reaction mixture was ≈ 10%. Acetylene 2a
was bubbled (30 min) through the cooled (5Ϯ2 °C) catalyst solu-
tion, or alkyne 2b–2f (51 mmol) was added to the solution. Then a
solution of a carbonyl compound (17 mmol) in DMSO (5 mL) was
added over 15 min. After the reaction had finished, the reaction
mixture was diluted with cool (5–10 °C) H2O (50 mL), and ex-
tracted with Et2O (4ϫ 10 mL). The organic extract was washed
with H2O (3ϫ 5 mL), and dried (MgSO4). The Et2O was removed,
and the crude residue was purified by column chromatography
(SiO2, hexane/ethyl acetate, 5:1).
2-Methylbut-3-yn-2-ol (3a): Colorless oil. IR (film): ν = 3370, 3301,
˜
2986, 2936, 2874, 2515, 2117, 1458, 1377, 1366, 1215, 1168, 962,
889, 651, 558 cm–1. 1H NMR (CDCl3): δ = 2.56 (s, 1 H, OH), 2.42
(s, 1 H, 4-H), 1.52 (s, 6 H, Me) ppm. 13C NMR (CDCl3): δ = 89.2
(C-3), 70.5 (C-4), 65.4 (C-2), 31.7 (2 C, Me) ppm. C5H8O (84.12):
calcd. C 71.39, H 9.59; found C 71.60, H 9.59.
3-Methylpent-1-yn-3-ol (3b): Colorless oil. IR (film): ν = 3390,
˜
3310, 2961, 2936, 2875, 2110, 1468, 1457, 1371, 1287, 1253, 1162,
1134, 1084, 1052, 1032, 1021, 953, 925, 904, 859, 747, 651,
1
630 cm–1. H NMR (CDCl3): δ = 2.48 (s, 1 H, OH), 2.42 (s, 1 H,
1-H), 1.76–1.62 (m, 2 H, 4-H), 1.47 (s, 3 H, 3-Me), 1.03 (t, 3J =
7.5 Hz, 3 H, 5-H) ppm. 13C NMR (CDCl3): δ = 88.0 (C-2), 71.6
(C-1), 68.9 (C-3), 36.7 (C-4), 29.2 (3-Me), 9.3 (C-5) ppm. C6H10O
(98.14): calcd. C 73.43, H 10.27; found C 73.25, H 10.31.
Scheme 2. Proposed reaction mechanism for the formation of prop-
argylic alcohols.
3-Methylhex-1-yn-3-ol (3c): Colorless oil. IR (film): ν = 3410, 2963,
˜
2931, 2874, 2109, 1493, 1448, 1378, 1366, 1318, 1304, 1261, 1211,
1179, 1158, 1073, 1026, 983, 968, 926, 902, 867, 747, 697, 661 cm–1.
1H NMR (CDCl3): δ = 2.41 (s, 1 H, 1-H), 1.99 (s, 1 H, OH), 1.66–
Conclusions
3
1.61, 1.55–1.49 (m, 4 H, 4,5-H), 1.48 (s, 3 H, 3-Me), 0.95 (t, J =
In conclusion, an original wide-scope method for the alk-
ynylation of aldehydes and ketones with alkynes using an
organic catalytic system Bu4NOH/H2O/DMSO has been
developed. The procedure tolerates aliphatic, alicyclic, aro-
matic, and heteroaromatic aldehydes and ketones, as well
as aliphatic, aromatic, and functionalized alkynes. Second-
ary and tertiary propargylic alcohols may be synthesized in
good-to-high yields and with ca. 100% selectivity. As this
method is simple, inexpensive, and environmentally benign,
it may attract the attention of wide circles of experts from
both academia and the chemical industry.
7.2 Hz, 3 H, 6-H) ppm. 13C NMR (CDCl3): δ = 88.3 (C-2), 71.6
(C-1), 72.3 (C-3), 46.2 (C-4), 30.1 (3-CH3), 18.3 (C-5), 14.6 (C-6)
ppm. C7H12O (112.17): calcd. C 74.95, H 10.78; found C 74.80, H
10.70.
3,5-Dimethylhex-1-yn-3-ol (3d): Colorless oil. IR (film): ν = 3401,
˜
3311, 2982, 2957, 2872, 2110, 1468, 1455, 1387, 1370, 1355, 1294,
1263, 1157, 1143, 1091, 1045, 935, 922, 861, 723, 652, 630,
1
560 cm–1. H NMR (CDCl3): δ = 2.44 (s, 1 H, 1-H), 2.09 (s, 1 H,
OH), 1.98–1.89 (m, 1 H, 5-H), 1.59 (d, 3J = 6.1 Hz, 2 H, 4-H), 1.49
(s, 3 H, 3-Me), 1.02–0.98 (m, 6 H, 5-Me) ppm. 13C NMR (CDCl3):
δ = 88.6 (C-2), 71.9 (C-1), 68.4 (C-3), 52.0 (C-4), 31.2 (C-5), 25.5
(3-Me), 24.7–24.5 (2 C, 5-Me) ppm. C8H14O (126.20): calcd. C
76.14, H 11.18; found C 71.59, H 10.80.
Experimental Section
3,4,4-Trimethylpent-1-yn-3-ol (3e): Colorless oil. IR (film): ν =
˜
General Remarks: All chemicals and solvents were commercially
sourced, and were used without further purification. The described
procedure does not require degassing of the DMSO or the use of
an inert atmosphere. The benefit of DMSO as a solvent is that it
is stable up to 150 °C for a long time (24 h, weight loss: 0.1–
1.0%).[29] 1H and 13C NMR spectra were recorded with a Bruker
3467, 3310, 2971, 2913, 2876, 2109, 1481, 1468, 1456, 1395, 1371,
1318, 1232, 1222, 1146, 1107, 1088, 1007, 920, 895, 651, 630 cm–1.
1H NMR (CDCl3): δ = 2.42 (s, 1 H, 1-H), 2.16 (s, 1 H, OH), 1.44
(s, 3 H, 3-Me), 1.03 (s, 9 H, 4-Me) ppm. 13C NMR (CDCl3): δ =
88.0 (C-2), 74.2 (C-3), 72.3 (C-1), 38.3 (C-4), 25.4 (3 C, 4-Me), 25.2
(3-Me) ppm. C8H14O (126.20): calcd. C 76.14, H 11.18; found C
AVANCE 400 instrument (400.1 and 101.6 MHz, respectively) 76.55, H 11.34.
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1-Ethynylcyclohexanol (3f):[30] Colorless oil. IR (film): ν = 3369,
2,6), 31.6 (3 C, Me), 27.7 (C-Me3), 25.8 (C-4), 24.0 (C-3,5) ppm.
˜
3307, 2935, 2861, 2104, 1463, 1451, 1396, 1350, 1342, 1332, 1318,
1278, 1259, 1181, 1158, 1136, 1070, 1033, 967, 952, 905, 852, 647,
C12H20O (180.29): calcd. C 79.94, H 11.18; found C 79.86, H 11.11.
3,5-Dimethyl-1-phenylhex-1-yn-3-ol (3m): Yellow oil. IR (film): ν =
˜
1
630 cm–1. H NMR (CDCl3): δ = 2.58 (s, 1 H, OH), 2.47 (s, 1 H,
3370, 2955, 2929, 2870, 1598, 1490, 1467, 1444, 1358, 1368, 1292,
1155, 1143, 1070, 1044, 919, 755, 691 cm–1. 1H NMR (CDCl3): δ
= 7.40–7.37 (m, 2 H, 2,6-HPh), 7.27–7.25 (m, 3 H, 3,4,5-HPh), 2.22
ϵCH), 1.92–1.89 (m, 4 H, 2,6-H), 1.58–1.52, 1.27–1.18 (m, 6 H,
3,4,5-H) ppm. 13C NMR (CDCl3): δ = 88.2 (-Cϵ), 72.5 (ϵCH),
68.8 (C-1), 40.1 (C-2,6), 25.5 (C-4), 23.5 (C-3,5) ppm. C8H12O
(124.18): calcd. C 77.38, H 9.74; found C 77.34, H 9.73.
3
(s, 1 H, OH), 2.04–1.95 (m, 1 H, 5-H), 1.67 (d, J = 6.2 Hz, 1 H,
3-H), 1.56 (m, 3 H, 3-Me), 1.05–1.02 (m, 6 H, 6-H, 5-Me) ppm.
2-Phenylbut-3-yn-2-ol (3g):[24] Colorless crystals, m.p. 43–47 °C. IR 13C NMR (CDCl3): δ = 132.0 (C-2,6Ph), 128.7 (C-3,5Ph), 128.6,
(film): ν = 3288, 2983, 2929, 2120, 1489, 1448, 1366, 1225, 1151,
123.3 (C-4Ph, C-1Ph), 93.8 (C-2), 83.9 (C-1), 68.9 (C-3), 52.4 (C-4),
31.4 (3-Me), 25.7, 24.7, 24.6 (C-5, C-6, 5-Me) ppm. C14H18O
(202.30): calcd. C 83.12, H 8.97; found C 83.16, H 9.04.
˜
1
1091, 1054, 933, 766, 701, 660, 586 cm–1. H NMR (CDCl3): δ =
7.66–7.64 (m, 2 H, 2,6-HPh), 7.37–7.34 (m, 2 H, 3,5-HPh), 7.30–
7.27 (m, 1 H, 4-HPh), 2.65 (s, 1 H, 4-H), 2.37 (s, 1 H, OH), 1.77 (s,
3 H, Me) ppm. 13C NMR (CDCl3): δ = 145.4 (C-1Ph), 128.8 (C-
3,5Ph), 128.3 (C-4Ph), 125.3 (C-2,6Ph), 87.7 (C-3), 73.5 (C-4), 70.3
(C-2), 33.5 (Me) ppm. C10H10O (146.19): calcd. C 82.16, H 6.89;
found C 81.73, H 6.76.
1-(Phenylethynyl)cyclohexanol (3n):[14] Colorless crystals, m.p.
56 °C. IR (film): ν = 3282, 2936, 2855, 1597, 1570, 1490, 1444,
˜
1344, 1333, 1297, 1259, 1187, 1158, 1135, 1072, 1029, 965, 917,
904, 856, 839, 785, 759, 693 cm–1. 1H NMR (CDCl3): δ = 7.42–
7.40 (m, 2 H, 2,6-HPh), 7.29–7.27 (m, 3 H, 3,4,5-HPh), 2.12–1.98
(m, 5 H, OH, 2Ј,6Ј-H), 1.75–1.58 (m, 4 H, 3,5-HcHex), 1.30–1.21
(m, 2 H, 4-HcHex) ppm. 13C NMR (CDCl3): δ = 132.1 (C-2,6Ph),
128.7 (C-3,5Ph), 128.6 (C-4Ph), 123.4 (C-1Ph), 93.3 (C-2), 84.8 (C-
2-(2-Naphthyl)but-3-yn-2-ol (3h):[24] Yellow oil. IR (film): ν = 3537,
˜
3391, 3294, 3058, 2986, 2931, 2113, 1921, 1670, 1631, 1600, 1578,
1507, 1445, 1369, 1322, 1272, 1220, 1187, 1128, 1080, 1052, 953,
934, 902, 860, 820, 749, 669, 651, 566, 478 cm–1. 1H NMR (CDCl3):
1), 69.5 (C-OH), 40.5 (C-2,6cHex), 25.7 (C-4cHex), 23.8 (C-3,5cHex
)
δ = 8.10 (s, 1 H, 1-HNaphth), 7.84–7.79 (m, 3 H, 4,5,8-HNaphth), ppm. C14H16O (200.28): calcd. C 83.96, H 8.05; found C 83.71, H
7.72–7.70 (m, 1 H, 3-HNaphth), 7.47–7.45 (m, 2 H, 6,7-HNaphth), 2.70
(s, 1 H, 4-H), 2.57 (s, 1 H, OH), 1.85 (s, 3 H, 1-CH3) ppm. 13C
NMR (CDCl3): δ = 142.6 (C-2Ј), 133.4–123.7 (9 CNaphth), 87.7 (C-
3), 73.7 (C-4), 70.4 (C-2), 33.4 (C-1) ppm. C14H12O (196.25): calcd.
C 85.68, H 6.16; found C 85.60, H 6.19.
7.96.
2,4-Diphenylbut-3-yn-2-ol (3o):[14] Colorless crystals, m.p. 71 °C. IR
(film): ν = 3300, 3081, 3066, 3056, 3025, 2986, 2977, 2926, 2240,
2199, 1951, 1884, 1808, 1759, 1597, 1489, 1451, 1442, 1405, 1366,
1316, 1291, 1270, 1212, 1179, 1141, 1088, 1073, 1050, 127, 940,
˜
2-(Pyridin-4-yl)but-3-yn-2-ol (3i):[24] Colorless crystals, m.p. 181– 919, 770, 755, 703, 691, 588 cm–1. 1H NMR (CDCl3): δ = 7.72–
182 °C. IR (film): ν = 3232, 2977, 2923, 2851, 2112, 1951, 1700,
7.70 [m, 2 H, 2,6-HPh(1)], 7.47–7.44, 7.38–7.34, 7.30–7.26 [m, 8 H,
˜
1606, 1562, 1478, 1434, 1415, 1369, 1327, 1228, 1214, 1162, 1103,
3,4,5-HPh(1), HPh(2)], 2.52 (s, 1 H, OH), 1.84 (s, 1 H, 1-H) ppm. 13
C
1
1082, 1067, 1008, 942, 888, 820, 744, 729, 702, 616, 586 cm–1. H
NMR (CDCl3): δ = 146.1 [C-1Ph(1)], 132.1–125.4 [10 C, C-
2,3,4,5,6Ph(1,2)], 123.0 [C-1Ph(2)], 92.9 (C-3), 85.4 (C-4), 70.8 (C-2),
3
NMR [(CD3)2CO]: δ = 8.54 (d, J = 5.6 Hz, 2 H, 2,6-HPyr), 7.57
3
(d, J = 5.6 Hz, 2 H, 3,5-HPyr), 3.78 (s, 1 H, OH), 3.14 (s, 1 H, 4- 33.7 (Me) ppm. C16H14O (222.29): calcd. C 86.45, H 6.35; found
H), 1.69 (s, 3 H, Me) ppm. 13C NMR [(CD3)2CO]: δ = 155.9 (C-
Pyr), 150.5 (C-2,6Pyr), 120.9 (C-3,5Pyr), 87.9 (C-3), 74.2 (C-4), 68.7
C 86.52, H 6.00.
4
2-(2-Naphthyl)-4-phenylbut-3-yn-2-ol (3p):[16] Yellow oil. IR (film):
(C-2), 33.7 (Me) ppm. C9H9NO (147.18): calcd. C 73.45, H 6.16,
N 9.52; found C 73.23, H 5.99, N 9.16.
ν = 3382, 3057, 2982, 2919, 2850, 2234, 1951, 1802, 1752, 1700,
˜
1672, 1631, 1599, 1574, 1507, 1489, 1442, 1354, 1322, 1273, 1182,
1159, 1128, 1108, 1077, 1049, 940, 910, 859, 843, 819, 754, 691,
668, 646, 617, 569 cm–1. 1H NMR (CDCl3): δ = 8.16 (s, 1 H, 1-
1-(Oct-1-yn-1-yl)cyclohexanol (3j):[2g] Pale yellow oil. IR (film): ν =
˜
3392, 2932, 2858, 1698, 1448, 1379, 1341, 1332, 1258, 1179, 1132,
1066, 1057, 964, 904 cm–1. 1H NMR (CDCl3): δ = 2.19 (t, 3J =
7.0 Hz, 2 H, CH2-Me), 1.86–1.83, 1.70–1.62, 1.56–1.45, 1.41–1.34,
HNaphth), 7.85–7.80 (m, 3 H, 4,5,8-HNaphth), 7.50–7.45 (m, 5 H,
3,6,7-HNaphth, 2,6-HPh), 7.32–7.30 (m, 3 H, 3,4,5-HPh), 2.60 (s, 1
H, OH), 1.93 (s, 3 H, 1-H) ppm. 13C NMR (CDCl3): δ = 143.4
(C-2Naphth), 133.5 (C-10Naphth), 133.3 (C-9Naphth), 132.2 (C-2,6Ph),
129.0–128.0 (C-4,5,8Naphth, C-3,4,5Ph), 126.7 (C-7Naphth), 126.6,
3
1.31–1.24 [m, 19 H, (CH2)Cyclohexyl, (CH2)Alkyne, OH], 0.88 (t, J =
6.9 Hz, 3 H, Me) ppm. 13C NMR (CDCl3): δ = 85.2, 84.3 (CϵC),
69.2 (C-1), 40.8 (C-2,6), 31.7, 29.2, 28.9, 25.7, 23.9, 23.0, 19.1 (8
C, CH2), 14.4 (Me) ppm. C14H24O (208.34): calcd. C 80.71, H 124.0, 123.9, 123.0 (C-1,3,6Naphth, C-1Ph), 92.9 (C-3), 85.6 (C-4),
11.61; found C 80.46, H 11.48.
70.9 (C-2), 33.6 (Me) ppm. C20H16O (272.35): calcd. C 88.20, H
5.92; found C 88.11, H 5.73.
1-(Cyclohexylethynyl)cyclohexanol (3k): Colorless crystals, m.p. 43–
45 °C. IR (film): ν = 3368, 2928, 2854, 2662, 2235, 1706, 1448,
4-Phenyl-2-(pyridin-4-yl)but-3-yn-2-ol (3q): Colorless crystals, m.p.
˜
1395, 1342, 1332, 1316, 1298, 1285, 1258, 1178, 1134, 1068, 1059,
1030, 965, 905, 889, 851 cm–1. 1H NMR (CDCl3): δ = 2.43–2.37
(m, 1 H, ϵC-CH), 2.17 (s, 1 H, OH), 1.87–1.17 (m, 20 H) ppm.
13C NMR (CDCl3): δ = 89.4, 84.3 (CϵC), 69.1 (C-OH), 40.8 (C-
2,6), 33.1 (C-2Ј,6Ј), 29.2 (C-1Ј), 26.3 (C-4Ј), 25.7 (C-4), 25.1 (C-
99–100 °C. IR (film): ν = 3309, 3139, 3035, 2985, 2930, 2806, 1601,
˜
1490, 1443, 1412, 1366, 1352, 1296, 1222, 1209, 1181, 1143, 1096,
1
1068, 1005, 945, 905, 852, 757, 607, 588 cm–1. H NMR (CDCl3):
δ = 8.52 (m, 2 H, 2,6-HPyr), 7.60 (m, 2 H, 3,5-HPyr), 7.42–7.40 (m,
2 H, 2,6-HPh), 7.31–7.29 (m, 3 H, 3,4,5-HPh), 4.63 (s, 1 H, OH),
3Ј,5Ј), 24.0 (C-3,5) ppm. C14H22O (206.33): calcd. C 81.50, H 10.75; 1.81 (s, 3 H, 1-H) ppm. 13C NMR (CDCl3): δ = 155.7 (C-4Pyr),
found C 81.57, H 11.00.
149.9 (C-2,6Pyr), 132.1 (C-2,6Ph), 129.2 (C-4Ph), 128.8 (C-3,5Ph),
122.6, 120.6 (C-1Ph, C-3,5Pyr), 91.9 (C-3), 85.6 (C-4), 69.5 (C-2),
33.6 (Me) ppm. C15H13NO (223.27): calcd. C 80.69, H 5.87, N 6.27;
found C 80.66, H 5.79, N 6.03.
1-(3,3-Dimethylbut-1-yn-1-yl)cyclohexanol (3l): Colorless crystals,
m.p. 54–57 °C. IR (film): ν = 3349, 3179, 2968, 2932, 2859, 1474,
˜
1448, 1361, 1345, 1332, 1294, 1259, 1252, 1204, 1183, 1170, 1075,
1038, 967, 903, 889, 850 cm–1. 1H NMR (CDCl3): δ = 1.87–1.83,
1-(3-Butoxyprop-1-yn-1-yl)cyclohexanol (3r): Colorless oil. IR
1.70–1.63, 1.56–1.50 (m, 10 H, CH2, OH), 1.21 (m, 9 H, Me) ppm. (film): ν = 3411, 2935, 2860, 1448, 1380, 1282, 1259, 1172, 1101,
˜
1
13C NMR (CDCl3): δ = 93.9, 82.6 (CϵC), 69.1 (C-OH), 40.9 (C-
1025, 1010, 966, 930, 904 cm–1. H NMR (CDCl3): δ = 4.17 (s, 2
6
www.eurjoc.org
© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 0000, 0–0

Job/Unit: O42275
/KAP1
Date: 03-06-14 19:09:19
Pages: 9
Alkynylation of Aldehydes and Ketones
H, 3-H), 3.50 (t, 3J = 6.6 Hz, 2 H, O-CH2-CH2), 2.17 (s, 1 H, OH), 1653, 1599, 1576, 1490, 1464, 1443, 1369, 1337, 1307, 1254, 1224,
1
1.91–1.84, 1.70–1.64, 1.60–1.51, 1.42–1.33, 1.28–1.21 (m, 14 H, 1182, 1142, 1071, 1009, 998, 971, 916, 884, 818, 758, 691 cm–1. H
3
CH2), 0.91 (t, J = 7.4 Hz, 3 H, Me) ppm. 13C NMR (CDCl3): δ NMR (CDCl3): δ = 7.44–7.42 (m, 2 H, 2,6-HPh), 7.37 (d, 3J =
3
= 90.2 (C-1), 80.7 (C-2), 70.1, 58.6 (CH2-OCH2), 69.0 (C-OH), 40.3
1.84 Hz, 1 H, 5-HFur) 7.30–7.23 (m, 3 H, 3,4,5-HPh), 6.47 (d, J =
3
3
(C-2,6cHex), 32.0 (C-2alkyne), 25.6 (C-4cHex), 23.7 (C-3,5cHex), 19.7 3.18 Hz, 1 H, 3-HFur), 6.31 (dd, J = 1.84, J = 3.18 Hz, 1 H, 4-
(C-3alkyne), 14.2 (Me) ppm. C13H22O2 (210.32): calcd. C 74.24, H
10.54; found C 74.19, H 11.61.
HFur), 5.66 (s, 3 H, 1-H), 3.00 (s, 1 H, OH) ppm. 13C NMR
(CDCl3): δ = 153.3 (C-2Fur), 143.3 (C-5Fur), 132.1 (C-2,6Ph), 129.0
(C-4Ph), 128.6 (C-3,5Ph), 122.5 (C-1Ph), 110.8, 108.1 (C-3,4Fur),
86.7, 86.0 (CϵC), 58.9 (C-OH) ppm. C13H10O2 (198.22): calcd. C
78.77, H 5.09; found C 78.50, H 5.01.
Tridec-1-yn-3-ol (5a): Pale yellow oil, b.p. 95–100 °C/1 Torr. IR
(film): ν = 3312, 2925, 2855, 2114, 1719, 1467, 1378, 1337, 1312,
˜
1251, 1022, 901, 721, 653, 626 cm–1. 1H NMR (C6D6): δ = 4.05 (m,
1 H, 3-H), 2.00 (s, 1 H, OH), 1.65 (m, 1 H, 1-H), 1.54–1.52, 1.24–
1.22, 1.19–1.15 (m, 18 H, CH2), 0.84 (m, 3 H, Me) ppm. 13C NMR
(C6D6): δ = 85.9 (C-2), 72.6 (C-1), 62.3 (C-OH), 38.2 (C-4), 32.3,
30.1, 30.0, 29.9, 29.8, 29.7, 25.5, 23.1 (8 C), 14.4 (Me) ppm.
C13H24O (196.33): calcd. C 79.53, H 12.32; found C 79.80, H 12.29.
Supporting Information (see footnote on the first page of this arti-
1
cle): Copies of H and 13C NMR spectra.
[1] a) A. E. Favorsky, Zh. Russ. Khim. O-Va. 1906, 37, 643; b) M.
Smith, J. March, March’s Advanced Organic Chemistry, 6th ed.,
Wiley, New York, 2007, p. 1360.
1-Phenylprop-2-yn-1-ol (5b):[23] Pale yellow oil, b.p. 118 °C/15 Torr.
IR (film): ν = 3361, 3292, 3107, 3065, 3033, 2916, 2883, 2119, 1691,
˜
[2] a) P. J. Stang, F. Diederich (Eds.), Modern Acetylene Chemistry,
Wiley-VCH, Weinheim, Germany, 1995; b) B. A. Trofimov,
Curr. Org. Chem. 2002, 6, 1121–1162; c) S. Ch. Ammal, N.
Yoshikai, Y. Inada, Y. Nishibayashi, E. Nakamura, J. Am.
Chem. Soc. 2005, 127, 9428–9438; d) R. U. Braun, M. Ansorge,
T. J. J. Müller, Chem. Eur. J. 2006, 12, 9081–9094; e) C. Bru-
neau, P. H. Dixneuf, Angew. Chem. Int. Ed. 2006, 45, 2176–
2203; Angew. Chem. 2006, 118, 2232–2260; f) G. Li, L. Zhang,
Angew. Chem. Int. Ed. 2007, 46, 5156–5159; Angew. Chem.
2007, 119, 5248–5251; g) M. Egi, Y. Yamaguchi, N. Fujiwara,
S. Akai, Org. Lett. 2008, 10, 1867–1870; h) M. Yoshimatsu, T.
Otani, S. Matsuda, T. Yamamoto, A. Sawa, Org. Lett. 2008,
10, 4251–4254; i) B. M. Trost, A. H. Weiss, Adv. Synth. Catal.
2009, 351, 963–983; j) L. Ye, L. Zhang, Org. Lett. 2009, 11,
3646–3649; k) C.-J. Li, Acc. Chem. Res. 2010, 43, 581–590; l)
X. Zhang, W. T. Teo, S. Sally, P. W. H. Chan, J. Org. Chem.
2010, 75, 6290–6293; m) S. Zhang, X. Liu, T. Wang, Adv.
Synth. Catal. 2011, 353, 1463–1466; n) D. Yu, Y. G. Zhang,
Green Chem. 2011, 13, 1275–1279; o) D. Yu, M. X. Tan, Y. G.
Zhang, Adv. Synth. Catal. 2012, 354, 969–974; p) B. A. Trofi-
mov, E. Yu. Schmidt, I. A. Bidusenko, I. A. Ushakov, N. I.
Protsuk, N. V. Zorina, A. I. Mikhaleva, Tetrahedron 2012, 68,
1241–1246; q) T. Kimura, K. Kamata, N. Mizuno, Angew.
Chem. Int. Ed. 2012, 51, 6700–6703; Angew. Chem. 2012, 124,
6804–6807; r) K. A. Jo, M. Maheswara, E. Yoon, Y. Y. Lee, H.
Yun, E. J. Kang, J. Org. Chem. 2012, 77, 2924–2928; s) D. Tej-
edor, G. Méndez-Abt, L. Cotos, F. García-Tellado, Chem. Soc.
Rev. 2013, 42, 458–471.
1603, 1494, 1455, 1394, 1327, 1305, 1275, 1192, 1080, 1021, 1001,
1
947, 919, 821, 762, 739, 699, 650, 573 cm–1. H NMR (C6D6): δ =
7.37–7.35 (m, 2 H, 2,6-HPh), 7.06–6.96 (m, 3 H, 3,4,5-HPh), 5.09 (s,
1 H, 1-H), 2.10 (s, 1 H, 3-H), 1.81 (s, 1 H, OH) ppm. 13C NMR
(C6D6): δ = 141.0 (C-1Ph), 128.7–126.9 (5 CPh), 84.3 (C-2), 74.6 (C-
3), 64.4 (C-OH) ppm. C9H8O (132.16): calcd. C 81.79, H 6.10;
found C 81.58, H 6.27.
1-(2-Furyl)prop-2-yn-1-ol (5c):[23] Pale yellow oil, b.p. 110 °C/
30 Torr. IR (film): ν = 3367, 3292, 2876, 2664, 2124, 1625, 1566,
˜
1501, 1386, 1307, 1227, 1187, 1144, 1074, 1010, 964, 907, 883, 822,
744, 668, 618, 598 cm–1. 1H NMR (C6D6): δ = 6.96 (m, 1 H, 5-
HFur), 6.21 (m, 1 H, 4-HFur), 5.93 (m, 1 H, 3-HFur), 5.19 (s, 1 H,
1-H), 2.40 (m, 1 H, OH), 2.08 (m, 1 H, 3-H) ppm. 13C NMR
(C6D6): δ = 153.4 (C-2Fur), 143.0 (C-5Fur), 110.6 (C-3Fur), 107.9 (C-
4Fur), 81.8 (C-2), 74.1 (C-3), 58.1 (C-OH) ppm. C7H6O2 (122.12):
calcd. C 68.85, H 4.95; found C 68.80, H 5.08.
1-(2-Thienyl)prop-2-yn-1-ol (5d):[23] Pale yellow oil. IR (film): ν =
˜
3520, 3353, 3290, 3107, 2875, 2120, 1649, 1434, 1413, 1381, 1356,
1291, 1274, 1230, 1170, 1128, 1019, 935, 919, 853, 841, 757,
1
707 cm–1. H NMR (CDCl3): δ = 7.29 (m, 1 H, 5-HTh), 7.18 (m, 1
4
H, 4-HTh), 6.96 (m, 1 H, 3-HTh), 5.63 (m, 1 H, 1-H), 2.67 (d, J =
2.1 Hz, 1 H, 3-H), 2.60 (s, 1 H, OH) ppm. 13C NMR (CDCl3): δ =
144.3 (C-2Th), 127.2, 126.7, 126.2 (C-3,4,5Th), 83.2 (C-2), 74.8 (C-
3), 60.5 (C-1) ppm. C7H6OS (138.18): calcd. C 60.84, H 4.38, S
23.20; found C 60.92, H 4.50, S 22.42.
[3] a) R. J. Tedeschi, Acetylene-Based Chemicals from Coal and
Other Natural Resources, Marcel Dekker, New York, 1982; b)
R. J. Tedeschi, Encyclopedia of Physical Science and Technol-
ogy, Academic Press, San Diego, 1992; c) C. Mercer, P. Chab-
ardes, Pure Appl. Chem. 1994, 66, 1509–1518.
1-Phenyltridec-1-yn-3-ol (5e): Yellow oil. IR (film): ν = 3339, 2925,
˜
2855, 1490, 1467, 1443, 1378, 1339, 1255, 1127, 1070, 1028, 755,
691 cm–1. 1H NMR (CDCl3): δ = 7.42–7.40 (m, 2 H, 2,6-HPh),
7.29–7.28 (m, 3 H, 3,4,5-HPh), 4.59–4.56 (m, 1 H, 3-H), 1.96 (s, 1
H, OH), 1.81–1.75, 1.51–1.46, 1.30–1.25 (m, 18 H, CH2), 0.88–0.85
(m, 3 H, Me) ppm. 13C NMR (CDCl3): δ = 132.1 (C-2,6Ph), 128.8
(C-4Ph), 128.7 (C-3,5Ph), 123.2 (C-1Ph), 90.7 (C-2), 85.2 (C-1), 63.5
(C-3), 38.4, 32.3, 30.0–29.7, 25.7, 23.1 (9 C, CH2), 14.5 (Me) ppm.
C19H28O (272.43): calcd. C 83.77, H 10.36; found C 83.66, H 10.24.
[4] a) D. E. Frantz, R. Fassler, C. S. Tomooka, E. M. Carreira,
Acc. Chem. Res. 2000, 33, 373–381; b) D. E. Frantz, R. Fassler,
E. M. Carreira, J. Am. Chem. Soc. 2000, 122, 1806–1807; c) H.
Sasaki, D. Boyall, E. M. Carreira, Helv. Chim. Acta 2001, 84,
964–971; d) S. Nakamura, S. Kusuda, K. Kawamura, T. Toru,
J. Org. Chem. 2002, 67, 640–647; e) J. Chun, H.-S. Byun, R.
Bittman, Tetrahedron Lett. 2002, 43, 8043–8045; f) P. Asch-
wanden, E. M. Carreira, in: Acetylene Chemistry (Eds.: F. Di-
ederich, P. J. Stang, R. R. Tykwinski), Wiley-VCH, Weinheim,
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1,3-Diphenylprop-2-yn-1-ol (5f): Pale yellow oil, b.p. 176–182 °C/
1 Torr. IR (film): ν = 3370, 3062, 3032, 1658, 1599, 1575, 1490,
˜
1451, 1385, 1339, 1308, 1287, 1217, 1190, 1032, 1019, 998, 962,
917, 821, 757, 720, 691 cm–1. 1H NMR (CDCl3): δ = 7.59–7.27 (m,
10 H, HPh), 5.66 (m, 1 H, 1-H), 2.46 (s, 1 H, OH) ppm. 13C NMR
(CDCl3): δ = 141.1 [C(OH)-C-1Ph], 132.2, 129.1–127.2 (10CPh),
122.8 (ϵC-C-1Ph), 89.2 (C-2), 87.1 (C-3), 65.5 (C-1) ppm. C15H12O
(208.26): calcd. C 86.51, H 5.81; found C 86.77, H 5.69.
1-(2-Furyl)-3-phenylprop-2-yn-1-ol (5g): Pale yellow oil, b.p. 140–
145 °C/1 Torr. IR (film): ν = 3370, 3150, 3061, 2873, 2665, 2238,
˜
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Date: 03-06-14 19:09:19
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B. A. Trofimov et al.
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Published Online: ᭿
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Job/Unit: O42275
/KAP1
Date: 03-06-14 19:09:19
Pages: 9
Alkynylation of Aldehydes and Ketones
Synthetic Methods
E. Y. Schmidt, N. A. Cherimichkina,
I. A. Bidusenko, N. I. Protzuk,
B. A. Trofimov* ................................ 1–9
A single organic catalyst selectively promotes the alkynylation of a variety of ketones and
aldehydes with diverse alkynes.
Alkynylation of Aldehydes and Ketones
Using the Bu4NOH/H2O/DMSO Catalytic
Composition: A Wide-Scope Methodology
Keywords: Synthetic methods / C–C bond
formation / Alkynes / Aldehydes / Ketones
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