Copper (I) iodide-catalyzed one-step preparation of functionalized allenes from terminal alkynes: Amine effect

Article abstract of DOI:10.1002/adsc.201100772

An efficient one-step synthesis of functionalized allenes from readily available functionalized terminal alkynes and aldehydes by applying the effect of a dialkylamine has been developed. The protocol is catalyzed by copper(I) iodide and the dialkylamine

Full text of DOI:10.1002/adsc.201100772

UPDATES
DOI: 10.1002/adsc.201100772
Copper (I) Iodide-Catalyzed One-Step Preparation of
Functionalized Allenes from Terminal Alkynes: Amine Effect
Jinqiang Kuang,a Hongwen Luo,a and Shengming Maa,b,*
a
Shanghai Key Laboratory of Green Chemistry and Chemical Process, Department of Chemistry, East China Normal
University, 3663 North Zhongshan Lu, Shanghai 200062, Peopleꢀs Republic of China
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of
b
Sciences, 345 Lingling Lu, Shanghai 200032, Peopleꢀs Republic of China
E-mail: masm@sioc.ac.cn
Received: October 6, 2011; Published online: March 7, 2012
Supporting information for this article is available on the WWW under
http://dx.doi.org/10.1002/adsc.201100772.
Abstract: An efficient one-step synthesis of func-
tionalized allenes from readily available functional-
ized terminal alkynes and aldehydes by applying
the effect of a dialkylamine has been developed.
The protocol is catalyzed by copper(I) iodide and
the dialkylamine is believed to play a very impor-
tant role in the transformation.
1,3-disubstituted allenes may be prepared via the re-
action of terminal alkynes with aldehydes by using
0.8 equivalents of ZnI2 with very limited success for
aliphatic aldehydes.[5] In the meantime, it was report-
ed that microwave may promote such one-step trans-
formations.[6,7] Thus, in terms of atom economy and
for large-scale synthesis as well as the generality for
aliphatic aldehydes, an efficient catalytic version of
such a reaction is of high interest for the future of
allene chemistry.[7] In this paper, we wish to report a
CuI-catalyzed one-step synthesis of allenes with func-
tional groups ready for further transformation from
terminal alkynes and aldehydes, especially aliphatic
ones, by using dialkylamines (Scheme 1).
Keywords: amine effect; catalysis; copper(I) iodide;
synthesis of allenes
Introduction
Due to the recent extensive studies on the chemistry Results and Discussion
of allenes, this class of compounds is becoming more
and more versatile in organic synthesis.[1] Thus, a one- For the purpose of developing a practical catalytic
step procedure from the most commonly available version of such a reaction with direct inclusion of
chemicals in a synthetic laboratory will surely become functional groups, we initiated our study with the re-
one of the hottest research topics in this area.[2]
A
action of 1-phenyl-2-propyn-1-ol 1a, instead of a
one-step synthesis of terminal allenes from terminal simple non-functionalized terminal alkyne, and n-bu-
alkynes with paraformaldehyde has been realized tanal by using 10 mol% CuI as the catalyst to screen
with 0.5 equivalents of a Cu(I) salt.[3,4] In addition, the effect of amine: all the amines or cyclic urea
shown in Figure 1 failed to affect the reaction shown
in Table 1. With the original base used by Crabbꢁ
Scheme 1. Synthesis of allenes from 1-alkynes and alde-
hydes.
Figure 1. Amines failing to promote the reaction shown in
Table 1 within 11 h.
Adv. Synth. Catal. 2012, 354, 933 – 944
ꢂ 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
933

Jinqiang Kuang et al.
UPDATES
Table 1. Effect of amines.
Table 2. The effect of catalyst.
Entry Amine
Time [h] Yield of 2a [%][a]
Entry Catalyst
Time
[h]
Yield of 2a
Yield of 3a
1
2
3
4
5
6
i-Pr2NH
Cy2NH
N-ethylisopropylamine 20
2-methylpiperidine
n-Pr2NH
22
20
31[b]
27
38
20
56
[%][a]
[%][a]
1
2
3
4
5
6
7
8
9
10
CuBr
CuBr
CuCl
CuCN
CuBr2
CuBr2
CuACTHNUTRGEN(UNG OAc)2 17
ZnCl2
ZnI2
25
46
25
25
25
46
58
40
43
–
55
44
2
52
68
19
–
24
17
27
70
25
10
50
42
18
32
68
11
11
11
n-Bu2NH
70
[a]
[b]
NMR yield with CH2Br2 as the internal standard.
16% of 1a was recovered.
40
40
et al., the reaction was slow (entry 1, Table 1); with
the amine used in our modified protocol,[4] the reac-
tion was finished within 20 h, however, the yield is
still low (entry 2, Table 1); interestingly, the reaction
CuACTHNUTRGEN(UNG OTf)2 21
11[b] AgI
21
[a]
with isopropylACHTUNGTRENNUNG(ethyl)amine was completed within 20 h
NMR yield determined by using 1,3,5-trimethylbenzene
as the internal standard.
10 mol% of 1a was recovered.
to afford allenol 2a in 38% yield, indicating the im-
portance of the replacement of one isopropyl group
with the ethyl group (compare entry 1 with entry 3,
Table 1); with this notion in mind, such a cyclic
amine, 2-methylazacyclohexane, was tried, unfortu-
nately, the yield was even lower. Thus, we decided to
replace both secondary alkyl groups with a normal
alkyl group, i.e., dipropylamine. To our delight, with
this amine the yield was improved to 56%! Quite ex-
citingly, dibutylamine is even better, improving the
yield to 70% (entry 6, Table 1).
[b]
Table 3. The effect of solvent.
Then we started to screen different Cu(I), Cu(II) or
Zn(II) catalysts with n-Bu2NH as the amine. The re-
sults shown in Table 2 clearly indicate that ZnCl2 and
Entry Solvent Time
[h]
Yield of 2a
Yield of 3a
[%][a]
[%][a]
[5]
ZnI2 are not good enough (entries 8 and 9) and CuI
is still the best.
1
2
3
4
5
6
7
dioxane 11
70
61
<2
66
complicated
6
59
–
DME
22.5
14
46
9
–
79
–
A quick screen on the solvent revealed that diox-
ane and o-xylene are among the best (entries 1 and 7,
Table 3).
Optimization on the ratio of each reactant led to a
set of optimal conditions for such a catalytic reaction:
alkyne, 1.6 equivalents of n-PrCHO, and 1.4 equiva-
lents of n-Bu2NH with 10 mol% of CuI in dioxane.
Then the scope of this catalytic reaction has been
studied with the results shown in Table 4. It should be
noted that the reaction is very smooth for the synthe-
DMSO 13
THF
DCE
17
12
hexane 13
o-
16
xylene
[a]
NMR yield determined by using 1,3,5-trimethylbenzene
as the internal standard.
sis of functionalized allenes[8,9] with hydroxy (en- (entry 17). We previously noted that the reaction of
tries 1–13 and 17), amide (entries 14–16), and ether terminal alkynes with aliphatic aldehydes using ZnI2
functionalities (entries 18 and 19). Primary, secondary, was not very general: limited substrates have been ap-
and tertiary propargylic alcohols may all be applied plied.[5] The current method nicely complements this
(entries 1–12) and other non-propargylic w-alkynols issue as demonstrated by more examples in Table 4
may also afford the corresponding allene products and Scheme 2.
934
asc.wiley-vch.de
ꢂ 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 2012, 354, 933 – 944

Copper (I) Iodide-Catalyzed One-Step Preparation of Functionalized Allenes from Terminal Alkynes
Table 4. CuI-catalyzed one-step synthesis of functionalized
allenes from terminal alkynes, n-butanal, and dibutylamine.
Entry
R
CuI [mol%]/ Isolated
T [oC]/t [h]
yield
of 2 [%]
7 in-situ generated in the step of intramolecular hy-
dride-transfer (see Scheme 3),[3,10,11] thus, each alde-
hyde required a specific dialkylamine (e.g., dipropyl-
1
2
3
4
5
6
7
8
PhCH(OH) (1a)
PhCH(OH) (1a)
4-ClC6H4CH(OH) (1b)
10/130/12
10/130/13
10/130/12
73 (2a)
66[b] (2a)
77 (2b)
68 (2c)
74 (2d)
60 (2e)
60 (2f)
64 (2g)
73 (2h)
72 (2i)
65 (2j)
59 (2k)
62 (2l)
49 (2m)
58 (2n)
54 (2o)
54 (2p)
55 (2q)
40 (2r)
66 (2s)
AHCTUNGTRENGaNNU mine for propanal; i-Bu2NH for iso-butanal), which
4-MeOC6H4CH(OH) (1c) 10/130/12
R[a] (1d)
10/130/12
10/130/36
10/150/18
10/150/16
10/150/21.5
10/150/26
10/150/26
20/150/26
is not so convenient for practical use. Further screen-
ing on the amine led to the observation that i-Bu2NH
may be used as a common amine without contamina-
tion of the allenol derived from i-Bu2NH, although
n-C7H15CH(OH) (1e)
n-C9H19CH(OH) (1f)
c-CyCH(OH) (1g)
c-(CH2)5C(OH) (1h)
4-MeC6H4CMe(OH) (1i)
n-C6H13CMe(OH) (1j)
Ph2C(OH) (1k)
9
10
11
12
13
14
15
16
17
18
19
20
Table 5. CuI-catalyzed one-step synthesis of functionalized
allenes from terminal alkynes, aldehydes, and diisobutylami-
ne.[a]
4-EtC6H4CH(OH)CH2 (1l) 10/150/19
TsNHCH2 (1m)
20/150/46
20/150/41
20/150/48
15/150/28
20/150/28
20/150/8.5
15/150/43
n-C5H11CH
ACHTUNGTRENNUNG
n-C7H15CHACHTUNGTRENNUNG
HOACHTUNGTRENNUNG(CH2)9 (1p)
BnOCH2 (1q)
THPOCH2 (1r)
n-C8H17 (1s)
Entry
1
R’
T [oC]/ Isolated
t [h]
yield [%]
1
2
3
1a
1a
1a
1a
Et
Cy
130/18
130/18
49 (2w)
39 (2x)
55 (2y)
45 (2z)
41 (2aa)
[a]
R=c-3,4-OCH2OC6H3CH(OH).
n-C5H11 140/12
i-PrCH2 140/12
[b]
The reaction was carried out in 8.0-mmol scale in 20 mL
of dioxane.
4
5b
prop-2-yn-1-ol (1t) n-C7H15 130/8
[a]
The allene derived from alkyne and isobutyral is less
than 5% in the allene product, if there is any.
20 mol% of CuI were used.
[b]
Scheme 2. CuI-catalyzed reaction of 1b with paraformalde-
hyde, propanal or isobutanal.
This reaction may also be applied to paraformalde-
hyde forming terminal allenols (the first reaction in
Scheme 2). We also noticed that if the dialkylamine
used does not match with the aldehyde, a mixture of
allenes was produced [Eq. (1)]. This was caused by
the formation of butanal from the hydrolysis of imine Scheme 3. Proposed mechanism.
Adv. Synth. Catal. 2012, 354, 933 – 944
ꢂ 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
asc.wiley-vch.de
935

Jinqiang Kuang et al.
UPDATES
ol 1b (166.8 mg, 1.00 mmol), 3 mL of dioxane, n-butanal
the yields are not as high as those shown in Table 4
(Table 5).
(142 mL, d=0.817 gmLÀ1, 116.0 mg, 1.61 mmol), and di
ACHTUNGTRENNUNG(n-
butyl)amine (238 mL, d=0.762 gmLÀ1, 181.4 mg, 1.40 mmol)
under an argon atmosphere. The resulting mixture was
sealed with the screw cap and stirred at 1308C. When the re-
action was complete as monitored by TLC upon cooling
(during the reaction, the starting alkyne 1b was consumed
quickly and the corresponding propargylic amine was pro-
duced, which was then transformed to the allene product 2b
at a relatively slow rate), the reaction mixture was cooled to
room temperature and filtered. Evaporation and column
chromatography on silica gel afforded the corresponding
allene 2b as a pair of diastereoisomers (eluent: petroleum
ether/ethyl acetate=20/1, then 15/1), liquid; yield: 172.0 mg
A rationale for this transformation is proposed
(Scheme 3): the interaction of the terminal alkyne
with CuI in the presence of a base would form the 1-
alkynyl copper intermediate 4, which would react
with the in-situ generated iminonium intermediate 5
to yield propargylic amine 3. Intramolecular hydride
transfer would yield the allene product with the re-
generation of CuI to finish the catalytic cycle. The in-
situ generated butanal would lead to the formation of
the by-product shown in Eq. (1).
1
(77%); H NMR (300 MHz, CDCl3): d=7.32 (s, 4H, ArH),
5.41–5.30 (m, 2H, 2ꢃC=CH), 5.24–5.16 (m, 1H, OCH), 2.22
(bs, 1H, OH), 2.08–1.94 (m, 2H, CH2), 1.52–1.33 (m, 2H,
CH2), 0.98–0.85 (m, 3H, CH3); 13C NMR (75.4 MHz,
CDCl3): d=[202.4, 202.2], [141.6, 141.5], [133.21, 133.17],
128.4, [127.5, 127.4], [95.8, 95.7], [95.2, 94.9], [71.7, 71.5],
[30.7, 30.6], [22.21, 22.19], 13.6; MS (EI): m/z=224 [M+
(37Cl), 0.26], 222 [M+ (35Cl), 0.72], 205 [M+ (35Cl)ÀOH,
0.51], 187 (M+ÀCl, 4.55), 141 (100); IR (neat): n=3362,
2959, 2930, 2872, 1963, 1595, 1491, 1461, 1405, 1260, 1190,
Conclusions
In conclusion, we have developed an efficient catalyt-
ic one-step synthesis of functionalized allenes from
readily available functionalized terminal alkynes and
aldehydes by applying the effect of the amine, which
may be explained by the intermediacy of an iminoni-
um intermediate formed from amines and aldehydes
as well as the intramolecular hydride transfer in the
step of transforming propargylic amines to final al-
lenes.[3,10,11] Due to the easy availability of all the start-
ing compounds as well as the catalyst and the poten-
tial of the functionalized allenes, this method will be
of high interest to organic and medicinal chemists.
Further studies in this area are being actively pursued
in our laboratory.
1013 cmÀ1
;
HR-MS (EI): m/z=222.0809, calcd. for
C13H1535ClO (M+): 222.0811.
The following compounds (2a, 2c–2z) were prepared ac-
cording to this procedure.
1-Phenylhepta-2,3-dien-1-ol (2a): The reaction of CuI
(19.0 mg, 0.10 mmol), 1-phenyl-2-propyn-1-ol 1a (133.7 mg,
1.01 mmol), 3 mL of dioxane, n-butanal (142 mL, d=
Experimental Section
General
Aldehydes were freshly distilled before use. CuI was pur-
chased from Sinopharm Chemical Reagent Co., Ltd and
used without further treatment. Dioxane was dried over
sodium wire with benzophenone as indicator and distilled
freshly before use. n-Pr2NH, n-Bu2NH, and i-Bu2NH were
dried over anhydrous barium oxide and distilled.[12] All the
temperatures stated refer to the oil baths used.
0.817 gmLÀ1, 116.0 mg, 1.61 mmol), and di
ACHTNUTRGNEUNG(n-butyl)amine
(238 mL, d=0.762 gmLÀ1, 181.4 mg, 1.40 mmol) afforded the
corresponding allene 2a[13] as a pair of diastereoisomers
(eluent: petroleum ether/ethyl acetate=20/1, then 15/1),
Typical Procedure: Synthesis of 1-(4-Chlorophenyl)-
hepta-2,3-dien-1-ol (2b)
1
liquid; yield: 139.6 mg, (73%). H NMR (300 MHz, CDCl3):
d=7.46–7.21 (m, 5H, ArH), 5.47–5.28 (m, 2H, 2ꢃC=CH),
5.27–5.15 (m, 1H, OCH), 2.24 (bs, 1H, OH), 2.10–1.91 (m,
2H, CH2), 1.52–1.33 (m, 2H, CH2), 1.00–0.80 (m, 3H, CH3);
13C NMR (75.4 MHz, CDCl3): d=[202.5, 202.2], [143.1,
143.0], 128.2, [127.4, 127.3], [126.0, 125.9], [95.83, 95.78],
[94.4, 94.1], [72.3, 72.1], [30.63, 30.56], [22.14, 22.10], 13.5;
MS (EI): m/z=188 (M+, 1.38), 107 (100); IR (neat): n=
3362, 3063, 3030, 2959, 2930, 2872, 1963, 1603, 1493, 1453,
1335, 1258, 1193, 1010 cmÀ1.
To an oven-dried reaction tube with a screw cap were added
CuI (18.9 mg, 0.099 mmol), 1-(4-chlorophenyl)-2-propyn-1-
1-(4-Methoxyphenyl)hepta-2,3-dien-1-ol (2c): The reac-
tion of CuI (19.0 mg, 0.10 mmol), 1-(4-methoxyphenyl)-2-
propyn-1-ol 1c (162.0 mg, 1.00 mmol), n-butanal (142 mL,
936
asc.wiley-vch.de
ꢂ 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 2012, 354, 933 – 944

Copper (I) Iodide-Catalyzed One-Step Preparation of Functionalized Allenes from Terminal Alkynes
1609, 1503, 1487, 1441, 1377, 1243, 1123, 1093, 1038 cmÀ1
;
HR-MS (EI): m/z=232.1100, calcd. for C14H16O3 (M+):
232.1099.
Tetradeca-4,5-dien-7-ol (2e): The reaction of CuI
(19.1 mg,
0.10 mmol),
1-decyn-3-ol
1e
(153.4 mg,
d=0.817 gmLÀ1, 116.0 mg, 1.61 mmol), and di
ACTHNUGRTENUNG(n-butyl)a-
mine (238 mL, d=0.762 gmLÀ1, 181.4 mg, 1.40 mmol) in
3 mL of dioxane afforded 2c as a pair of diastereoisomers
(eluent: petroleum ether/ethyl acetate=20/1, then 15/1, then
10/1), liquid; yield: 148.6 mg (68%). 1H NMR (300 MHz,
CDCl3): d=7.32 (d, J=8.7 Hz, 2H, ArH), 6.89 (d, J=
8.7 Hz, 2H, ArH), 5.47–5.29 (m, 2H, 2ꢃC=CH), 5.24–5.12
(m, 1H, OCH), 3.80 (s, 3H, OCH3), 2.19 (bs, 1H, OH),
2.10–1.94 (m, 2H, CH2), 1.55–1.34 (m, 2H, CH2), 1.00–0.84
(m, 3H, CH3); 13C NMR (75.4 MHz, CDCl3): d=[202.3,
202.0], [159.03, 158.99], [135.4, 135.3], [127.4, 127.3],
[113.71, 113.70], [96.1, 96.0], [94.8, 94.4], [71.9, 71.7], 55.2,
[30.78, 30.70], [22.24, 22.20], [13.56, 13.55]; MS (EI): m/z=
218 (M+, 1.29), 137 (100); IR (neat): n=3419, 2958, 2931,
2871, 2836, 1962, 1611, 1586, 1511, 1462, 1378, 1302, 1246,
1172, 1109, 1034 cmÀ1; HR-MS (EI): m/z=218.1305, calcd.
for C14H18O2 (M+): 218.1307.
0.99 mmol), n-butanal (142 mL, d=0.817 gmLÀ1, 116.0 mg,
1.61 mmol), and di
(n-butyl)amine (238 mL, d=0.762 gmLÀ1,
AHCTUNGTRENNUNG
181.4 mg, 1.40 mmol) in 3 mL of dioxane afforded 2e as a
pair of diastereoisomers (eluent: petroleum ether/ethyl ace-
tate=20/1, then 10/1), liquid: yield: 125.4 mg (60%).
1H NMR (300 MHz, CDCl3): d=5.36–5.13 (m, 2H, 2ꢃC=
CH), 4.20–4.03 (m, 1H, OCH), 2.07–1.93 (m, 2H, CH2),
1.67–1.17 (m, 15H, OH and 7ꢃCH2), 0.99–0.81 (m, 6H, 2ꢃ
CH3); 13C NMR (75.4 MHz, CDCl3): d=[202.3, 202.1], [95.7,
95.6], [94.0, 93.6], [70.3, 69.9], [37.52, 37.47], 31.8, 30.8,
[29.5, 29.4], 29.2, [25.42, 25.37], 22.6, 22.3, 14.0, [13.59,
13.58]; MS (EI): m/z=192 (M+ÀH2O, 1.21), 181 (M+ÀC2H5,
6.80), 67 (100); IR (neat): n=3356, 2957, 2926, 2856, 1963,
1462, 1378, 1336, 1122, 1018 cmÀ1; HR-MS (EI): m/z=
210.1986, calcd. for C14H26O (M+): 210.1984.
1-(3’,4’-Methylenedioxyphenyl)hepta-2,3-dien-1-ol
(2d):
The reaction of CuI (19.0 mg, 0.10 mmol), 1-(3’,4’-methyle-
Hexadeca-4,5-dien-7-ol (2f): The reaction of CuI
(19.1 mg, 0.10 mmol), 1-dodecyn-3-ol 1f (182.6 mg,
nedioxyphenyl)prop-2-yn-1-ol 1d (176.6 mg, 1.00 mmol), n-
butanal (142 mL, d=0.817 gmLÀ1, 116.0 mg, 1.61 mmol), and
1.00 mmol), n-butanal (142 mL, d=0.817 gmLÀ1, 116.0 mg,
1.61 mmol), and diACTHNUTRGNEUNG
(n-butyl)amine (238 mL, d=0.762 gmLÀ1,
diACHTUNGTRENNUNG
(n-butyl)amine (238 mL, d=0.762 gmLÀ1, 181.4 mg,
181.4 mg, 1.40 mmol) in 3 mL of dioxane afforded 2f as a
pair of diastereoisomers (eluent: petroleum ether/ethyl ace-
tate=20/1, then 10/1), liquid; yield: 143.0 mg (60%).
1H NMR (300 MHz, CDCl3): d=5.35–5.13 (m, 2H, 2ꢃC=
CH), 4.17–4.05 (m, 1H, OCH), 2.07–1.93 (m, 2H, CH2),
1.72–1.62 (m, 1H, OH), 1.62–1.16 (m, 18H, 9ꢃCH2), 1.00–
0.80 (m, 6H, 2ꢃCH3); 13C NMR (75.4 MHz, CDCl3): d=
[202.3, 202.0], [95.7, 95.6], [94.1, 93.7], [70.3, 69.9], [37.54,
37.49], 31.9, 30.8, 29.6, 29.54, 29.50, 29.3, [25.43, 25.39], 22.7,
22.3, 14.1, 13.6; MS (EI): m/z=209 (M+ÀC2H5, 5.96), 194
(M+ÀC3H8, 4.95), 67 (100); IR (neat): n=3346, 2957, 2924,
2854, 1963, 1463, 1378, 1258, 1123, 1010 cmÀ1; HR-MS (EI):
m/z=238.2299, calcd. for C16H30O (M+): 238.2297.
1.40 mmol) in 3 mL of dioxane afforded 2d as a pair of dia-
stereoisomers (eluent: petroleum ether/ethyl acetate=20/1,
then 15/1, then 10/1), liquid; yield: 172.8 mg (74%).
1H NMR (300 MHz, CDCl3): d=6.89 (s, 1H, ArH), 6.85 (d,
J=8.1 Hz, 1H, ArH), 6.77 (d, J=8.1 Hz, 1H, ArH), 5.94 (s,
2H, OCH2O), 5.45–5.30 (m, 2H, 2ꢃC=CH), 5.20–5.08 (m,
1H, OCH), 2.24 (bs, 1H, OH), 2.10–1.95 (m, 2H, CH2 in
Pr), 1.53–1.35 (m, 2H, CH2 in Pr), 1.00–0.85 (m, 3H, CH3);
13C NMR (75.4 MHz, CDCl3): d=[202.2, 202.0], 147.6,
[147.0, 146.9], [137.3, 137.2], [119.5, 119.4], 108.0, [106.8,
106.7], 100.9, [96.04, 95.98], [95.0, 94.7], [72.1, 71.9], [30.8,
30.7], [22.3, 22.2], [13.57, 13.56]; MS (EI): m/z=232 (M+,
5.39), 65 (100); IR (neat): n=3383, 2959, 2930, 2777, 1962,
Adv. Synth. Catal. 2012, 354, 933 – 944
ꢂ 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
asc.wiley-vch.de
937

Jinqiang Kuang et al.
UPDATES
1-Cyclohexylhepta-2,3-dien-1-ol (2g): The reaction of CuI
(19.0 mg,
0.10 mmol),
1-cyclohexyl-2-propyn-1-ol
1g
(137.8 mg, 1.00 mmol), n-butanal (142 mL, d=0.817 gmLÀ1,
181.4 mg, 1.40 mmol) in 3 mL of dioxane afforded 2i as a
pair of diastereoisomers (eluent: petroleum ether/ethyl ace-
tate=20/1, then 10/1), liquid; yield: 156.4 mg (72%).
1H NMR (300 MHz, CDCl3): d=7.41 (d, J=8.1 Hz, 2H,
ArH), 7.17 (d, J=7.8 Hz, 2H, ArH), 5.58–5.48 (m, 1H, C=
CH), 5.47–5.34 (m, 1H, C=CH), 2.36 (s, 3H, ArCH3), 2.23–
2.15 (m, 1H, OH), 2.13–1.98 (m, 2H, CH2), 1.64 (s, 3H,
CCH3), 1.55–1.38 (m, 2H, CH2), 1.02–0.88 (m, 3H, CH3);
13C NMR (75.4 MHz, CDCl3): d=[200.9, 200.8], [144.52,
144.46], 136.4, [128.75, 128.73], [124.9, 124.8], [101.01,
100.96], [95.6, 95.5], [73.1, 73.0], [30.92, 30.90], [30.4, 30.3],
[22.4, 22.3], 21.0, 13.7; MS (EI): m/z=216 (M+, 0.71), 201
(M+ÀCH3, 2.16), 135 (100); IR (neat): n=3390, 2960, 2929,
2872, 1963, 1512, 1456, 1410, 1369, 1335, 1284, 1208, 1183,
1088, 1061, 1020 cmÀ1; HR-MS (EI): m/z=216.1516, calcd.
for C15H20O (M+): 216.1514.
116.0 mg, 1.61 mmol), and diACTHNUTRGNEUGN(n-butyl)amine (238 mL, d=
0.762 gmLÀ1, 181.4 mg, 1.40 mmol) in 3 mL of dioxane af-
forded 2g as a pair of diastereoisomers (eluent: petroleum
ether/ethyl acetate=20/1, then 10/1), liquid; yield: 123.7 mg
1
(64%). H NMR (300 MHz, CDCl3): d=5.34–5.11 (m, 2H,
2ꢃC=CH), 3.93–3.80 (m, 1H, OCH), 2.06–1.92 (m, 2H,
CH2), 1.92–1.58 (m, 6H, 3ꢃCH2), 1.52–1.32 (m, 3H, CH2
and OH), 1.32–0.83 (m, 8H, 2ꢃCH2 and CH and CH3);
13C NMR (75.4 MHz, CDCl3): d=[202.7, 202.3], [94.1, 94.0],
[93.9, 93.5], [74.6, 74.0], [44.1, 44.0], 30.9, 28.7, [28.4, 28.2],
26.5, [26.14, 26.11], [26.08, 26.03], 22.3, 13.6; MS (EI): m/z=
194 (M+, 0.35), 165 (M+ÀC2H5, 1.06), 133 (M+ÀC3H7ÀH2O,
1.35), 41 (100); IR (neat): n=3384, 2924, 2852, 1962, 1450,
1378, 1261, 1175, 1141, 1083, 1010 cmÀ1; HR-MS (EI): m/z=
194.1670, calcd. for C13H22O (M+): 194.1671.
7-Methyltrideca-4,5-dien-7-ol (2j): The reaction of CuI
(19.0 mg, 0.10 mmol), 3-methyl-l-nonyn-3-ol 1j (153.7 mg,
1-(Hexa-1,2-dienyl)cyclohexanol (2h): The reaction of CuI
(19.1 mg,
0.10 mmol),
1-ethynyl-cyclohexan-1-ol
1h
1.00 mmol), n-butanal (142 mL, d=0.817 gmLÀ1, 116.0 mg,
1.61 mmol), and diACTHNUTRGNEUNG
(n-butyl)amine (238 mL, d=0.762 gmLÀ1,
181.4 mg, 1.40 mmol) in 3 mL of dioxane afforded 2j as a
pair of diastereoisomers (eluent: petroleum ether/ethyl ace-
tate=20/1, then 10/1), liquid; yield: 136.1 mg (65%).
1H NMR (300 MHz, CDCl3): d=5.37–5.26 (m, 1H, C=CH),
5.26–5.18 (m, 1H, C=CH), 2.08–1.92 (m, 2H, CH2), 1.70 (s,
1H, OH), 1.63–1.15 (m, 15H, 6ꢃCH2 and CH3), 0.99–0.80
(m, 6H, 2ꢃCH3); 13C NMR (75.4 MHz, CDCl3): d=[200.7,
200.6], [100.25, 100.23], [95.0, 94.9], [71.59, 71.56], [42.9,
42.8], 31.8, [31.03, 30.99], 29.7, [28.1, 28.0], 24.1, 22.6, [22.4,
22.3], 14.1, 13.7; MS (EI): m/z=210 (M+, 0.50), 195
(M+ÀCH3, 1.22), 181 (M+ÀC2H5, 1.02), 153 (M+ÀC4H9,
3.26), 129 (100); IR (neat): n=3385, 2958, 2931, 2860, 1963,
1462, 1375, 1128, 1091, 1063 cmÀ1; HR-MS (EI): m/z=
210.1985, calcd. for C14H26O (M+): 210.1984.
(124.2 mg, 1.00 mmol), n-butanal (142 mL, d=0.817 gmLÀ1,
116.0 mg, 1.61 mmol), and di(n-butyl)amine (238 mL, d=
AHCTUNGTRENNUNG
0.762 gmLÀ1, 181.4 mg, 1.40 mmol) in 3 mL of dioxane af-
forded 2h as a liquid (eluent: petroleum ether/ethyl ace-
tate=20/1, then 10/1); yield: 131.1 mg (73%). 1H NMR
(300 MHz, CDCl3): d=5.37–5.18 (m, 2H, 2ꢃC=CH), 2.07–
1.92 (m, 2H, CH2), 1.73–1.26 (m, 13H, 6ꢃCH2 and OH),
0.93 (t, J=7.4 Hz, 3H, CH3); 13C NMR (75.4 MHz, CDCl3):
d=201.3, 100.2, 94.6, 70.6, 38.3, 30.9, 25.5, 22.6, 22.5, 22.4,
13.7; MS (EI): m/z=180 (M+, 1.28), 99 (100); IR (neat): n=
3364, 2930, 2856, 1962, 1449, 1379, 1344, 1317, 1247, 1186,
1147, 1057, 1035 cmÀ1; HR-MS (EI): m/z=180.1514, calcd.
for C12H20O (M+): 180.1514.
1,1-Diphenylhepta-2,3-dien-1-ol (2k): The reaction of CuI
2-p-Tolylocta-3,4-dien-2-ol (2i): The reaction of CuI
(19.0 mg, 0.10 mmol), 2-(p-tolyl)but-3-yn-2-ol 1i (160.6 mg,
1.00 mmol), n-butanal (142 mL, d=0.817 gmLÀ1, 116.0 mg,
(38.0 mg,
(208.0 mg, 1.00 mmol), n-butanal (142 mL, d=0.817 gmLÀ1,
116.0 mg, 1.61 mmol), and di(n-butyl)amine (238 mL, d=
0.762 gmLÀ1, 181.4 mg, 1.40 mmol) in 3 mL of dioxane af-
0.10 mmol),
1,1-diphenyl-2-propyn-1-ol
1k
AHCTUNGTRENNUNG
1.61 mmol), and diACHTUNGTRENNUNG
(n-butyl)amine (238 mL, d=0.762 gmLÀ1,
938
asc.wiley-vch.de
ꢂ 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 2012, 354, 933 – 944

Copper (I) Iodide-Catalyzed One-Step Preparation of Functionalized Allenes from Terminal Alkynes
CDCl3): d=7.76 (d, J=8.1 Hz, 2H, ArH in Ts), 7.31 (d, J=
7.8 Hz, 2H, ArH in Ts), 5.26–5.12 (m, 1H, C=CH), 5.10–
4.97 (m, 1H, ArH), 4.70–4.51 (m, 1H, NH), 3.60–3.50 (m,
2H, NCH2), 2.43 (s, 3H, CH3 in Ts), 1.98–1.86 (m, 2H, CH2
in Pr), 1.45–1.29 (m, 2H, CH2 in Pr), 0.89 (t, J=7.3 Hz, 3H,
CH3 in Pr); 13C NMR (75.4 MHz, CDCl3): d=203.4, 143.4,
137.0, 129.7, 127.1, 94.5, 87.6, 41.9, 30.5, 22.1, 21.5, 13.6; MS
(EI): m/z=265 (M+, 1.41), 91 (100); IR (neat): n=3280,
2959, 2871, 1965, 1599, 1495, 1423, 1325, 1158, 1094,
forded 2k as a liquid (eluent: petroleum ether/ethyl ace-
tate=20/1, then 10/1); yield: 155.8 mg (59%). 1H NMR
(300 MHz, CDCl3): d=7.48–7.39 (m, 4H, ArH), 7.38–7.19
(m, 6H, ArH), 5.93–5.84 (m, 1H, C=CH), 5.44–5.32 (m, 1H,
C=CH), 2.68 (s, 1H, OH), 2.06–1.91 (m, 2H, CH2), 1.45–
1.28 (m, 2H, CH2), 0.87 (t, J=7.5 Hz, 3H, CH3); 13C NMR
(75.4 MHz, CDCl3): d=200.9, 146.24, 146.18, 127.80, 127.78,
126.9, 126.62, 126.55, 100.7, 96.6, 77.2, 66.7, 30.7, 22.1, 13.5;
MS (EI): m/z=264 (M+, 1.07), 77 (100); IR (neat): n=3463,
3060, 3028, 2959, 2930, 2871, 1963, 1658, 1599, 1492, 1447,
1336, 1278, 1166, 1060, 1031, 1002 cmÀ1; HR-MS (EI): m/z=
264.1512, calcd. for C19H20O (M+): 264.1514.
1069 cmÀ1
;
HR-MS (EI): m/z=265.1135, calcd for
C14H19NO2S (M+): 265.1137.
N-Tosyl(dodeca-4,5-dien-7-yl)amine (2n): The reaction of
CuI (37.6 mg, 0.20 mmol), N-tosyl(oct-1-yn-3-yl)amide 1n
1-(4-Ethylphenyl)octa-3,4-dien-1-ol (2l): The reaction of
CuI (18.9 mg, 0.10 mmol), 1-(4-ethylphenyl)but-3-yn-1-ol 1l
(174.1 mg, 1.00 mmol), n-butanal (142 mL, d=0.817 gmLÀ1,
(279.4 mg, 1.00 mmol), n-butanal (115.7 mg, 1.61 mmol), and
diACTHNUGRTENUNG(n-butyl)amine (181.7 mg, 1.41 mmol) in 3 mL of dioxane
afforded 2n as a pair of diastereoisomers (eluent: petroleum
ether/DCM/ethyl acetate=60/20/1, then 40/40/1), liquid:
195.9 mg (58%). 1H NMR (300 MHz, CDCl3): d=7.74 (d,
J=8.7 Hz, 2H, ArH in Ts), 7.28 (d, J=7.8 Hz, 2H, ArH in
Ts), 5.21–5.00 (m, 1H, C=CH), 4.99–4.86 (m, 1H, C=CH),
4.67–4.48 (m, 1H, NH), 3.84–3.67 (m, 1H, NCH), 2.42 (s,
3H, CH3 in Ts), 1.96–1.76 (m, 2H, CH2), 1.61–1.11 (m, 10H,
5ꢃCH2), 0.95–0.76 (m, 6H, 2ꢃCH3); 13C NMR (75.4 MHz,
CDCl3): d=[202.3, 202.0], 143.0, [138.2, 138.1], [129.41,
129.39], 127.1, [95.0, 94.5], [93.0, 92.8], [52.7, 52.3], [36.2,
36.1], [31.4, 31.3], [30.63, 30.60], 24.9, 22.4, [22.3, 22.2], 21.4,
13.9, [13.59, 13.58]; MS (EI): m/z=335 (M+, 0.94), 91 (100);
IR (neat): n=3276, 2957, 2930, 2860, 1965, 1599, 1496, 1426,
1328, 1159, 1094, 1041 cmÀ1; HR-MS (EI): m/z=335.1920,
calcd. for C19H29NO2S (M+): 335.1919.
116.0 mg, 1.61 mmol), and diACTHNUTRGNEUGN(n-butyl)amine (238 mL, d=
0.762 gmLÀ1, 181.4 mg, 1.40 mmol) in 3 mL of dioxane af-
forded 2l as a pair of diastereoisomers (eluent: petroleum
ether/ethyl acetate=20/1, then 10/1), liquid; yield: 143.0 mg
1
(62%). H NMR (300 MHz, CDCl3): d=7.28 (d, J=7.8 Hz,
2H, ArH), 7.18 (d, J=7.8 Hz, 2H, ArH), 5.20–5.00 (m, 2H,
2ꢃC=CH), 4.80–4.66 (m, 1H, OCH), 2.64 (q, J=7.6 Hz,
2H, CH2 in Et), 2.50–2.38 (m, 2H, OCCH2), 2.20–2.10 (m,
1H, OH), 2.02–1.85 (m, 2H, CH2 in Pr), 1.49–1.30 (m, 2H,
CH2 in Pr), 1.23 (t, J=7.5 Hz, 3H, CH3 in Et), 0.97–0.83 (m,
3H, CH3 in Pr); 13C NMR (75.4 MHz, CDCl3): d=[205.2,
205.1], [143.5, 143.4], [141.01, 140.95], 127.8, [125.90,
125.87], [91.13, 91.07], 86.8, [73.6, 73.4], [39.2, 39.1], [30.84,
30.77], 28.5, [22.3, 22.2], 15.6, 13.6; MS (EI): m/z=230 (M+,
1.04), 79 (100); IR (neat): n=3389, 2964, 2932, 2899 2872,
2839, 1962, 1513, 1456, 1421, 1377, 1319, 1258, 1200, 1179,
1115, 1062, 1044, 1018 cmÀ1; HR-MS (EI): m/z=230.1674,
calcd. for C16H22O (M+): 230.1671.
N-Tosyl(tetradeca-4,5-dien-7-yl)amine (2o): The reaction
of CuI (37.9 mg, 0.20 mmol), N-tosyl(dec-1-yn-3-yl)amide 1o
(306.5 mg, 1.00 mmol), n-butanal (116.0 mg, 1.61 mmol), and
N-Tosyl(hepta-2,3-dienyl)amine (2m): The reaction of CuI
(38.7 mg, 0.20 mmol), N-tosylpropargylamine 1m (209.3 mg,
1.00 mmol), n-butanal (116.0 mg, 1.61 mmol), and diACTHNUGTRNEUNG(n-bu-
tyl)amine (180.8 mg, 1.40 mmol) in 3 mL of dioxane afford-
ed 2m as a liquid (eluent: petroleum ether/DCM/ethyl ace-
1
tate=40/40/1); yield: 131.1 mg (49%). H NMR (300 MHz,
Adv. Synth. Catal. 2012, 354, 933 – 944
ꢂ 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
asc.wiley-vch.de
939

Jinqiang Kuang et al.
UPDATES
di
G
(m, 2H, CH2 in Pr), 1.52–1.36 (m, 2H, CH2 in Pr), 0.93 (t,
J=7.4 Hz, 3H, CH3 in Pr); 13C NMR (75.4 MHz, CDCl3):
d=205.1, 138.2, 128.3, 127.8, 127.5, 91.6, 88.2, 71.5, 68.6,
30.6, 22.3, 13.5; MS (EI): m/z=173 (M+ÀC2H5, 1.24), 172
(M+ÀOCH2, 6.96), 143 (M+ÀOCH2ÀC2H5, 11.40), 91 (100);
IR (neat): n=3031, 2959, 2931, 2870, 1963, 1454, 1352, 1204,
1093, 1074, 1028 cmÀ1; HR-MS (EI): m/z=202.1361, calcd.
for C14H18O (M+): 202.1358.
afforded 2o as a pair of diastereoisomers (eluent: petroleum
ether/DCM/ethyl acetate=60/20/1, then 40/40/1), liquid;
yield: 195.2 mg (54%). H NMR (300 MHz, CDCl3): d=7.74
(d, J=8.1 Hz, 2H), 7.28 (d, J=8.1 Hz, 2H), 5.22–5.00 (m,
1H, C=CH), 4.99–4.86 (m, 1H, C=CH), 4.71–4.45 (m, 1H,
NH), 3.83–3.66 (m, 1H, NCH), 2.42 (s, 3H, CH3 in Ts),
1.97–1.77 (m, 2H, CH2), 1.61–1.11 (m, 14H, 7ꢃCH2), 0.96–
0.78 (m, 6H, 2ꢃCH3); 13C NMR (75.4 MHz, CDCl3): d=
[202.3, 202.0], [143.03, 143.01], [138.1, 138.0], [129.43,
129.40], 127.1, [95.0, 94.6], 94.5, [93.0, 92.8], [52.7, 52.3],
[36.2, 36.1], 31.7, [30.64, 30.61], 29.09, 25.2, 22.6, [22.3, 22.2],
21.4, 14.0, 13.6; MS (EI): m/z=363 (M+, 1.11), 91 (100); IR
(neat): n=3274, 2927, 2857, 1965, 1599, 1496, 1456, 1329,
1159, 1094 cmÀ1; HR-MS (EI): m/z=363.2230, calcd for
C21H33NO2S (M+): 363.2232.
1-(Tetrahydropyran-2-yl)oxyhepta-2,3-diene (2r): The re-
action of CuI (37.8 mg, 0.20 mmol), 3-(tetrahydropyran-2-
Pentadeca-10,11-dien-1-ol (2p): The reaction of CuI
(28.5 mg, 0.15 mmol), 10-undecyn-1-ol 1p (168.8 mg,
yl)oxy-1-propyne 1r (141.9 mg, 1.01 mmol), n-butanal
(142 mL, d=0.817 gmLÀ1, 116.0 mg, 1.61 mmol), and di
ACHTUNGTRENNUNG(n-
butyl)amine (238 mL, d=0.762 gmLÀ1, 181.4 mg, 1.40 mmol)
in 3 mL of dioxane afforded 2r as a pair of diastereoisomers
(eluent: petroleum ether/ethyl acetate=30/1, then 20/1),
liquid; yield: 79.7 mg (40%). 1H NMR (300 MHz, CDCl3):
d=5.31–5.09 (m, 2H, C=CH), 4.69 (t, J=3.5 Hz, 1H, CH in
THP), 4.28–4.13 (m, 1H, one proton from OCH2C=C),
4.08–3.96 (m, 1H, one proton from OCH2C=C), 3.95–3.81
(m, 1H, one proton from OCH2 in THP), 3.59–3.43 (m, 1H,
one proton from OCH2 in THP), 2.06–1.92 (m, 2H, CH2 in
Pr), 1.91–1.32 (m, 8H, 3ꢃCH2 in THP and CH2 in Pr), 0.99–
0.84 (m, 3H, CH3); 13C NMR (75.4 MHz, CDCl3): d=
[204.93, 204.91], [97.5, 97.4], [91.7, 91.6], [88.3, 88.2], 65.4,
[62.14, 62.09], [30.60, 30.57], 30.5, 25.4, [22.3, 22.2], [19.45,
19.39], 13.5; MS (EI): m/z=139 (M+ÀCHOC2H4, 1.78), 85
(100); IR (neat): n=2942, 2872, 1964, 1465, 1384, 1342,
1284, 1201, 1183, 1118, 1078, 1053, 1023 cmÀ1; HR-MS (EI):
m/z=139.1125, calcd. for C9H15O (M+-CHOC2H4): 139.1123.
Tetradeca-4,5-diene (2s): The reaction of CuI (28.5 mg,
0.20 mmol), 1-decyne 1s (180 mL, d=0.766 gmLÀ1, 137.9 mg,
1.00 mmol), n-butanal (142 mL, d=0.817 gmLÀ1, 116.0 mg,
1.61 mmol), and diACHTUNGTRENNUNG
(n-butyl)amine (238 mL, d=0.762 gmLÀ1,
181.4 mg, 1.40 mmol) in 3 mL of dioxane afforded 2p as a
liquid (eluent: petroleum ether/ethyl acetate=20/1, then 10/
1
1); yield: 120.7 mg (54%). H NMR (300 MHz, CDCl3): d=
5.12–4.99 (m, 2H, 2ꢃC=CH), 3.62 (t, J=6.6 Hz, 2H,
OCH2), 2.04–1.85 (m, 4H, 2ꢃCH2), 1.70–1.20 (m, 17H, OH
and 8ꢃCH2), 0.91 (t, J=7.4 Hz, 3H); 13C NMR (75.4 MHz,
CDCl3): d=203.9, 90.8, 90.6, 62.9, 32.7, 31.1, 29.5, 29.38,
29.36, 29.2, 29.0, 28.9, 25.7, 22.4, 13.6; IR (neat): n=3331,
2926, 2854, 1962, 1462, 1057 cmÀ1; MS (EI): m/z=149
(M+ÀH2OÀC4H9, 0.93), 136 (M+ÀH2OÀC4H9ÀCH, 1.68),
81 (100); HR-MS (EI): m/z=224.2137, calcd for C15H28O
(M+): 224.2140.
1-Benzyloxyhepta-2,3-diene (2q): The reaction of CuI
(37.8 mg, 0.20 mmol), 1-benzyloxy-2-propyne 1q (147.0 mg,
1.00 mmol), n-butanal (142 mL, d=0.817 gmLÀ1, 116.0 mg,
1.61 mmol), and diACTHNUTRGNEUNG
(n-butyl)amine (238 mL, d=0.762 gmLÀ1,
181.4 mg, 1.40 mmol) in 3 mL of dioxane afforded 2s[14] as a
liquid [eluent: petroleum ether (30–608C)]; yield: 128.2 mg
(66%). H NMR (300 MHz, CDCl3): d=5.12–5.01 (m, 2H,
1.01 mmol), n-butanal (142 mL, d=0.817 gmLÀ1, 116.0 mg,
1
1.61 mmol), and di
N
181.4 mg, 1.40 mmol) in 3 mL of dioxane afforded 2q as a
liquid (eluent: petroleum ether/ethyl acetate=100/1); yield:
112.1 mg (55%). H NMR (300 MHz, CDCl3): d=7.40–7.21
(m, 5H, ArH), 5.30–5.12 (m, 2H, 2ꢃC=CH), 4.53 (s, 2H,
PhCH2), 4.04 (dd, J=6.5, 2.6 Hz, 2H, C=CCH2O), 2.09–1.93
2ꢃC=CH), 2.04–1.88 (m, 4H, 2ꢃCH2), 1.50–1.20 (m, 14H,
7ꢃCH2), 0.98–0.82 (m, 6H, 2ꢃCH3); 13C NMR (75.4 MHz,
CDCl3): d=204.0, 90.8, 90.6, 31.9, 31.2, 29.5, 29.4, 29.3, 29.1,
29.0, 22.7, 22.5, 14.1, 13.6; MS (EI): m/z=194 (M+, 0.65), 96
(100); IR (neat): n=2958, 2925, 2855, 1963, 1463, 1378,
1
940
asc.wiley-vch.de
ꢂ 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 2012, 354, 933 – 944

Copper (I) Iodide-Catalyzed One-Step Preparation of Functionalized Allenes from Terminal Alkynes
1337, 1288, 1069 cmÀ1; HR-MS (EI): m/z=194.2038, calcd.
for C14H26 (M+): 194.2035.
1-(4-Chlorophenyl)buta-2,3-dien-1-ol (2t): The reaction of
CuI (19.0 mg, 0.10 mmol), 1-(4-chlorophenyl)-2-propyn-1-ol
propyn-1-ol 1b (166.1 mg, 1.00 mmol), isobutyral (146 mL,
d=0.794 gmLÀ1, 115.9 mg, 1.61 mmol), and di
ACHTNUTRGNEUNG(i-butyl)amine
(244 mL, d=0.74 gmLÀ1, 180.6 mg, 1.40 mmol) in 3 mL of di-
oxane afforded 2v as a pair of diastereoisomers (eluent: pe-
troleum ether/ethyl acetate=10/1), liquid; yield: 105.7 mg
1
(48%). H NMR (300 MHz, CDCl3): d=7.31 (s, 4H, ArH),
1b (166.3 mg, 1.00 mmol), paraformaldehyde (47.9 mg,
5.48–5.33 (m, 2H, 2ꢃC=CH), 5.23–5.14 (m, 1H, OCH),
2.40–2.21 (m, 2H, OH and CH in i-Pr), 1.05–0.93 (m, 6H,
2ꢃCH3); 13C NMR (75.4 MHz, CDCl3): d=[200.9, 200.5],
[141.6, 141.5], [133.22, 133.17], 128.4, [127.5, 127.4], [103.1,
102.5], [97.2, 97.0], [71.8, 71.4], [27.91, 27.88], [22.38, 22.37],
22.3; MS (EI): m/z=209 [M+ (37Cl)ÀCH3, 0.17], 207 [M+
(35Cl)ÀCH3, 0.50], 187 (M+ÀCl, 2.01), 141 (100); IR (neat):
n=3357, 2962, 2868, 1961, 1596, 1491, 1465, 1405, 1382,
1365, 1297, 1221, 1191, 1127, 1091, 1044, 1013 cmÀ1; HR-MS
(EI): m/z=222.0812, calcd. for C13H1535ClO (M+): 222.0811.
1-Phenylhexa-2,3-dien-1-ol (2w): The reaction of CuI
(19.0 mg, 0.10 mmol), 1-phenyl-2-propyn-1-ol 1a (132.1 mg,
1.60 mmol), and diACHTUNGTRENNUNG
(n-butyl)amine (238 mL, d=0.762 gmLÀ1,
181.4 mg, 1.40 mmol) in 3 mL of dioxane afforded 2t[15] as a
liquid (eluent: petroleum ether/ethyl acetate=10/1, then 5/
1
1); yield: 119.9 mg (67%). H NMR (300 MHz, CDCl3): d=
7.31 (s, 4H, ArH), 5.38 (q, J=6.5 Hz, 1H, C=CH), 5.22 (dt,
J=6.3, 2.1 Hz, 1H, OCH), 4.92 (dd, J=6.8, 2.3 Hz, 2H, C=
CH2), 2.54 (bs, 1H, OH); 13C NMR (75.4 MHz, CDCl3): d=
207.1, 141.2, 133.4, 128.5, 127.4, 94.9, 78.3, 71.3; MS (EI):
m/z=182 [M+ (37Cl), 1.05], 180 [M+ (35Cl), 3.17], 141 (100);
IR (neat): n=3333, 2875, 1955, 1597, 1491, 1406, 1226, 1191,
1091, 1034, 1013 cmÀ1.
1-(4-Chlorophenyl)hexa-2,3-dien-1-ol (2u): The reaction
of CuI (19.2 mg, 0.10 mmol), 1-(4-chlorophenyl)-2-propyn-1-
1.00 mmol), propanal (93.0 mg, 1.60 mmol), and diACTHNUTRGNE(UNG i-butyl)a-
mine (180.9 mg, 1.40 mmol) in 3 mL of dioxane afforded 2w
as a pair of diastereoisomers (eluent: petroleum ether/ethyl
acetate=15/1), liquid; yield: 85.5 mg (49%). 1H NMR
(300 MHz, CDCl3): d=7.43–7.22 (m, 5H, ArH), 5.49–5.35
(m, 2H, 2ꢃC=CH), 5.26–5.14 (m, 1H, OCH), 2.51–2.16 (m,
1H, OH), 2.14–1.96 (m, 2H, CH2), 1.08–0.90 (m, 3H, CH3);
13C NMR (75.4 MHz, CDCl3): d=[202.0, 201.7], [143.2,
143.0], [128.29, 128.28], [127.52, 127.47], [126.1, 126.0],
[96.8, 96.7], 96.4, [72.3, 72.0], [21.73, 21.69], [13.3, 13.2]; MS
(EI): m/z=174 (M+, 2.52), 107 (100); IR (neat): n=3343,
3063, 3030, 2966, 2932, 2872, 1961, 1603, 1493, 1453, 1377,
1325, 1193, 1133, 1006 cmÀ1; HR-MS (EI): m/z=174.1043,
calcd. for C12H14O (M+): 174.1045.
ol 1b (167.9 mg, 1.01 mmol), propanal (116 mL, d=
0.80 gmLÀ1, 92.8 mg, 1.60 mmol), and di
ACTHNUTRGNE(NUG n-propyl)amine
(192 mL, d=0.738 gmLÀ1, 141.7 mg, 1.40 mmol) in 3 mL of
dioxane afforded 2u as a pair of diastereoisomers (eluent:
petroleum ether/ethyl acetate=10/1), liquid; yield: 130.0 mg
1
(62%). H NMR (300 MHz, CDCl3): d=7.31 (s, 4H, ArH),
5.50–5.32 (m, 2H, 2ꢃC=CH), 5.23–5.14 (m, 1H, OCH), 2.29
(bs, 1H, OH), 2.12–1.96 (m, 2H, CH2), 1.05–0.93 (m, 3H,
CH3); 13C NMR (75.4 MHz, CDCl3): d=[202.1, 201.8],
[141.6, 141.5], [133.1, 133.0], 128.3, [127.4, 127.3], [96.9,
96.5], [96.4, 96.3], [71.7, 71.4], [21.64, 21.61], [13.2, 13.1];
MS (EI): m/z=210 [M+ (37Cl), 0.49], 208 [M+ (35Cl), 1.41],
141 (100); IR (neat): n=3366, 2967, 2872, 1962, 1680, 1596,
4-Cyclohexyl-1-phenylbuta-2,3-dien-1-ol (2x): The reac-
tion of CuI (18.8 mg, 0.10 mmol), 1-phenyl-2-propyn-1-ol 1a
(132.1 mg, 1.00 mmol), cyclohexal (179.7 mg, 1.60 mmol),
1491, 1458, 1406, 1377, 1323, 1189, 1091, 1046, 1013 cmÀ1
;
HR-MS (EI): m/z=208.0655, calcd. for C12H1335ClO (M+):
208.0655.
and diACTHNURTGNEU(GN i-butyl)amine (181.6 mg, 1.41 mmol) in 3 mL of diox-
ane afforded 2x[11f] as a pair of diastereoisomers (eluent: pe-
troleum ether/ethyl acetate=15/1), liquid; yield: 88.2 mg
1-(4-Chlorophenyl)-5-methyl-hexa-2,3-dien-1-ol (2v): The
reaction of CuI (19.2 mg, 0.10 mmol), 1-(4-chlorophenyl)-2-
Adv. Synth. Catal. 2012, 354, 933 – 944
ꢂ 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
asc.wiley-vch.de
941

Jinqiang Kuang et al.
UPDATES
1
[143.14, 143.05], 128.3, [127.53, 127.47], [126.1, 125.9],
[95.32, 95.27], [93.4, 93.1], [72.4, 72.2], [38.1, 38.0], [28.34,
28.31], 22.14, [22.09, 22.07]; MS (EI): m/z=202 (M+, 1.70),
107 (100); IR (neat): n=3331, 3063, 3030, 2955, 2869, 2840,
1963, 1603, 1493, 1454, 1384, 1367, 1336, 1261, 1193, 1170,
1106, 1080, 1008 cmÀ1; HR-MS (EI): m/z=202.1359, calcd.
for C14H18O (M+): 202.1358.
(39%). H NMR (300 MHz, CDCl3): d=7.44–7.22 (m, 5H,
ArH), 5.51–5.40 (m, 1H, C=CH), 5.40–5.30 (m, 1H, C=CH),
5.26–5.16 (m, 1H, OCH), 2.35–2.13 (m, 1H, OH), 2.10–1.90
(m, 1H, CH in Cy), 1.83–1.56 (m, 5H, 2ꢃCH2 and one
proton of another CH2), 1.39–0.96 (m, 5H, 2ꢃCH2 and one
proton of another CH2); 13C NMR (75.4 MHz, CDCl3): d=
[201.2, 200.9], [143.1, 143.0], [128.24, 128.22], [127.5, 127.4],
[126.1, 126.0], [101.0, 100.6], [96.93, 96.86], [72.3, 72.1],
[37.04, 37.01], 32.8, 26.0, 25.9; MS (EI): m/z=228 (M+,
1.25), 107 (100); IR (neat): n=3333, 3063, 3030, 2923, 2850,
1961, 1603, 1493, 1449, 1193, 1013 cmÀ1.
Typical Procedure for the Synthesis of Undeca-2,3-
dien-1-ol (2aa)
1-Phenylnona-2,3-dien-1-ol (2y): The reaction of CuI
(19.4 mg, 0.10 mmol), 1-phenyl-2-propyn-1-ol 1a (132.1 mg,
To an oven-dried reaction tube with a screw cap were added
CuI (38.3 mg, 0.20 mmol), prop-2-yn-1-ol 1t (56.3 mg,
1.00 mmol), octanal (203.7 mg, 1.59 mmol), diACTHUNRTGNEUNG(i-butyl)amine
(179.9 mg, 1.39 mmol), and 3 mL of dioxane under an argon
atmosphere. The resulting mixture sealed with the screw cap
was then stirred in an oil bath at room temperature and
heated to 1308C gradually (in 15 min). When the reaction
was complete after being stirred at 1308C for 8 h as moni-
tored by TLC upon cooling (during the reaction, prop-2-yn-
1-ol was consumed quickly and the corresponding propar-
gylic amine was produced, which was then transformed to
the allene product at a relatively slow rate), the reaction
mixture was cooled to room temperature and then filtered.
Evaporation and column chromatography on silica gel af-
forded allene 2aa[8k] as a liquid (eluent: petroleum ether/
ethyl acetate=20/1, then 10/1); yield: 70 mg (41%).
1H NMR (300 MHz, CDCl3): d=5.35–5.18 (m, 2H, 2ꢃC=
CH), 4.08 (dd, J=5.4, 3.0 Hz, 2H, OCH2), 2.06–1.92 (m,
3H, OH and CH2), 1.50–1.10 (m, 10H, 5ꢃCH2), 0.92–0.79
(m, 3H, CH3); 13C NMR (75.4 MHz, CDCl3): d=203.0, 93.7,
91.6, 60.7, 31.8, 29.1, 29.04, 28.97, 28.6, 22.6, 14.0; MS (EI):
m/z=135 (M+ÀH2OÀCH3, 0.72), 121 (M+ÀH2OÀC2H5,
3.24), 55 (100); IR (neat): n=3313, 2956, 2925, 2855, 1964,
1463, 1378, 1212, 1136, 1012 cmÀ1; HR-MS (EI): m/z=
168.1515, calcd. for C11H20O (M+): 168.1514.
1.00 mmol), hexanal (159.7 mg, 1.60 mmol), and di
ACHTUNGTRENNUNG
ACHTUNGTRENUN(NG i-butyl)-
2y[11f] as a pair of diastereoisomers (eluent: petroleum ether/
ethyl acetate=10/1), liquid; yield: 119.6 mg (55%).
1H NMR (300 MHz, CDCl3): d=7.45–7.21 (m, 5H, ArH),
5.47–5.29 (m, 2H, 2ꢃC=CH), 5.27–5.15 (m, 1H, OCH),
2.39–2.16 (m, 1H, OH), 2.12–1.94 (m, 2H, CH2), 1.50–1.20
(m, 6H, 3ꢃCH2), 0.97–0.80 (m, 3H, CH3); 13C NMR
(75.4 MHz, CDCl3): d=[202.2, 202.0], [143.2, 143.0], 128.4,
[127.6, 127.5], [126.1, 126.0], [96.1, 96.0], [95.3, 95.0], [72.4,
72.1], 31.2, [28.73, 28.68], 28.6, 22.4, 14.0; MS (EI): m/z=
216 (M+, 1.18), 107 (100); IR (neat) n=3317, 3063, 3030,
2957, 2871, 1964, 1605, 1493, 1456, 1379, 1326, 1194, 1138,
1107, 1080, 1009 cmÀ1; HR-MS (EI): m/z=216.1512, calcd.
for C15H20O (M+): 216.1514.
6-Methyl-1-phenylhepta-2,3-dien-1-ol (2z): The reaction
of CuI (19.5 mg, 0.10 mmol), 1-phenyl-2-propyn-1-ol 1a
(131.4 mg,
1.00 mmol),
3-methylbutanal
(138.2 mg,
1.61 mmol), and diACHTUNGTRENNUNG(i-butyl)amine (181.6 mg, 1.41 mmol) in
3 mL of dioxane afforded 2y as a pair of diastereoisomers
(eluent: petroleum ether/ethyl acetate=15/1), liquid; yield:
89.7 mg (45%). 1H NMR (300 MHz, CDCl3): d=7.43–7.22
(m, 5H, ArH), 5.44–5.26 (m, 2H, 2ꢃC=CH), 5.26–5.16 (m,
1H, OCH), 2.55–2.11 (bs, 1H, OH), 2.04–1.84 (m, 2H,
CH2), 1.80–1.54 (m, 1H, CH in iPr), 1.04–0.80 (m, 6H, 2ꢃ
CH3); 13C NMR (75.4 MHz, CDCl3): d=[202.9, 202.7],
1 g-Scale Reaction
To an oven-dried reaction tube with a screw cap were added
CuI (152.2 mg, 0.80 mmol), 1-phenyl-2-propyn-1-ol 1a
942
asc.wiley-vch.de
ꢂ 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 2012, 354, 933 – 944

Copper (I) Iodide-Catalyzed One-Step Preparation of Functionalized Allenes from Terminal Alkynes
0.50), 272 (100); IR (neat): n=3396, 2957, 2932, 2871, 1493,
1455, 1378, 1306, 1174, 1124, 1076, 1004 cmÀ1; HR-MS (EI):
m/z=315.2557, calcd. for C21H33NO (M+): 315.2562.
Acknowledgements
Financial support from the National Basic Research Program
of China (No. 2009CB825300) and National Natural Science
Foundation of China (No. 20732005) is greatly appreciated.
We thank Ms. Minyan Wang in this group for reproducing
the results of entries 2 and 18 in Table 4, the third reaction in
Scheme 2, and entry 5 in Table 5.
(1.0547 g, 7.99 mmmol), 20 mL of dioxane, n-butanal
(1.13 mL, d=0.817 gmLÀ1, 923.2 mg, 116.0 mg, 12.8 mmol),
and di
G
,
1.4478 g,
11.2 mmol) under an argon atmosphere. The resulting mix-
ture sealed with the screw cap was then stirred in an oil
bath at room temperature and heated to 1308C gradually
(in 20 min). When the reaction was complete after stirring
at 1308C for 13 h as monitored by TLC upon cooling
(during the reaction, 1a was consumed quickly and the cor-
responding propargylic amine was produced, which was
then transformed to the allene product at a relatively slow
rate). The reaction mixture was cooled to room temperature
and then filtered. Evaporation and column chromatography
on silica gel afforded allene 2a[2] as a liquid (eluent: petrole-
um ether/DCM/ethyl acetate=60/20/1); yield: 0.9854 g
(66%).
References
[1] For recent reviews on the chemistry of allenes, see:
a) K. K. Wang, Chem. Rev. 1996, 96, 207–222; b) J. A.
Marshall, Chem. Rev. 2000, 100, 3163–3185; c) A. S. K.
Hashmi, Angew. Chem. 2000, 112, 3737–3740; Angew.
Chem. Int. Ed. 2000, 39, 3590–3593; d) R. Zimmer,
C. U. Dinesh, E. Nandanan, F. A. Khan, Chem. Rev.
2000, 100, 3067–3125; e) X. Lu, C. Zhang, Z. Xu, Acc.
Chem. Res. 2001, 34, 535–544; f) R. W. Bates, V. Satch-
aroen, Chem. Soc. Rev. 2002, 31, 12–21; g) S. Ma, Acc.
Chem. Res. 2003, 36, 701–712; h) L. Brandsma, N. A.
Nedolya, Synthesis 2004, 735–745; i) M. A. Tius, Acc.
Chem. Res. 2003, 36, 284–290; j) L. L. Wei, H. Xiong,
R. P. Hsung, Acc. Chem. Res. 2003, 36, 773–782; k) S.
Ma, Palladium-Catalyzed Two- or Three-Component
Cyclization of Functionalized Allenes in Palladium in
Organic Synthesis, (Ed.: J. Tsuji), pp. 183–210, Springer,
Berlin, Heidelberg, 2005; l) S. Ma, Chem. Rev. 2005,
105, 2829–2871; m) S. Ma, Aldrichimica Acta 2007, 40,
91–102; n) H. Kim, L. J. Williams, Curr. Opin. Drug
Disc. Devel. 2008, 11, 870–894; o) M. Brasholz, H.-U.
Reissig, R. Zimmer, Acc. Chem. Res. 2009, 42, 45–56;
p) S. Ma, Acc. Chem. Res. 2009, 42, 1679–1688.
Synthesis of 4-(N,N-Dibutylamino)-1-phenylhept-2-
yn-1-ol (3a)
[2] For reviews or highlights on the synthesis of allenes,
see: a) L. K. Sydnes, Chem. Rev. 2003, 103, 1133–1150;
b) Modern Allene Chemistry, (Eds.: N. Krause, A. S. K.
Hashmi), Vols. 1 and 2, Wiley-VCH, Weinheim, 2004;
c) N. Krause, A. Hoffmann-Rçder, Tetrahedron 2004,
60, 11671–11694; d) G. B. Hammond, ACS Symp. Ser.
2005, 911, 204–215; e) R. Saeeng, M. Isobe, Chem. Lett.
2006, 35, 552–557; f) K. M. Brummond, J. E. Deforrest,
Synthesis 2007, 795–818; g) M. Ogasawara, Tetrahe-
dron: Asymmetry 2009, 20, 259–271; h) S. Yu, S. Ma,
Chem. Commun. 2011, 47, 5384–5418.
[3] a) P. Crabbꢁ, H. Fillion, D. Andrꢁ, J.-L. Luche, J.
Chem. Soc. Chem. Commun. 1979, 859–860; b) S.
Searles, Y. Li, B. Nassim, M-T. R. Lopes, P. T. Tran, P.
Crabbꢁ, J. Chem. Soc. Perkin Trans. 1 1984, 747–751;
c) S. Ma, H. Hou, S. Zhao, G. Wang, Synthesis 2002,
1643–1645; d) U. Kazmaier, S. Lucas, M. Klein, J. Org.
Chem. 2006, 71, 2429–2433.
To an oven-dried reaction tube with a screw cap were added
CuI (9.8 mg, 0.051 mmol), 1-phenyl-2-propyn-1-ol 1a
(65.8 mg, 0.50 mmol), 1.50 mL of dioxane, n-butanal
(58.3 mg, 0.81 mmol), and diACTHNUTRGNEUGN(n-butyl)amine (89.6 mg,
0.69 mmol) under an argon atmosphere. The resulting mix-
ture was sealed with the screw cap and stirred at 508C.
When the reaction was complete as monitored by TLC, the
reaction mixture was cooled to room temperature. Evapora-
tion and column chromatography on silica gel afforded the
3a as a pair of diastereoisomers (eluent: petroleum ether/
ethyl acetate=10/1), liquid; yield: 125.0 mg (79%).
1H NMR (300 MHz, CDCl3): d=7.62–7.51 (m, 2H, ArH),
7.43–7.27 (m, 3H, ArH), 5.53–5.45 (bs, 1H, OCH), 3.60–3.45
(m, 1H, NCH), 2.58–2.43 (m, 2H, CH2), 2.40–2.27 (m, 2H,
CH2), 2.22–2.01 (bs, 1H, OH), 1.68–1.53 (m, 2H, CH2),
1.53–1.16 (m, 10H, 5ꢃCH2), 1.00–0.80 (m, 9H, 3ꢃCH3);
13C NMR (75.4 MHz, CDCl3): d=[141.24, 141.23], 128.4,
128.1, 126.6, [86.18, 86.16], 84.0, 64.5, 53.3, 51.3, [36.08,
36.07], 30.6, 20.6, 19.8, 14.0, 13.8; MS (EI): m/z=315 (M+,
[4] J. Kuang, S. Ma, J. Org. Chem. 2009, 74, 1763–1765.
[5] J. Kuang, S. Ma, J. Am. Chem. Soc. 2010, 132, 1786–
1787.
Adv. Synth. Catal. 2012, 354, 933 – 944
ꢂ 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
asc.wiley-vch.de
943

Jinqiang Kuang et al.
UPDATES
[6] H. Nakamura, T. Sugiishi, Y. Tanaka, Tetrahedron Lett.
2008, 49, 7230–7233.
[9] S. Ma, F. Yu, W. Gao, J. Org. Chem. 2003, 68, 5943–
5949.
[7] For limited success on the CuI-catalyzed one-step syn-
thesis of allenes in low yields (14–64%) from terminal
alkynes and aldehydes under the irradiation of micro-
wave, see: S. Kitagaki, M Komizu, C. Mukai, Synlett
2011, 1129–1132. According to the reported examples,
the tolerance of functional groups is also rather poor.
[8] For the reports on the reactions of allenols, see: a) L.-I.
Olsson, A. Claesson, Synthesis 1979, 743–745; b) S. S.
Nikam, K. H. Chu, K. K. Wang, J. Org. Chem. 1986, 51,
745–747; c) J. A. Marshall, X.-J. Wang, J. Org. Chem.
1990, 55, 2995–2996; d) J. A. Marshall, K. G. Pinney, J.
Org. Chem. 1993, 58, 7180–7184; e) J. A. Marshall,
C. A. Sehon, J. Org. Chem. 1995, 60, 5966–5968; f) S.
Ma, W. Gao, Tetrahedron Lett. 2000, 41, 8933–8936;
g) A. Hoffmann-Rçder, N. Krause, Org. Lett. 2001, 3,
2537–2538; h) R. W. Friesen, M. Blouin, J. Org. Chem.
1993, 58, 1653–1654; i) S. Ma, S. Zhao, J. Am. Chem.
Soc. 1999, 121, 7943–7944; j) C. Fu, J. Li, S. Ma, Chem.
Commun. 2005, 4119–4121; k) J. Li, C. Fu, G. Chen, G.
Chai, S. Ma, Adv. Synth. Catal. 2008, 350, 1376–1382;
l) Y. Deng, X. Jin, S. Ma, J. Org. Chem. 2007, 72, 5901–
5904; m) Y. Deng, Y. Yu, S. Ma, J. Org. Chem. 2008,
73, 585–589.
[10] a) V. K. Y. Lo, M.-K. Wong, C.-M. Che, Org. Lett. 2008,
10, 517–519; b) V. K.-Y. Lo, C.-Y. Zhou, M.-K. Wong,
C.-M. Che, Chem. Commun. 2010, 46, 213–215.
[11] a) H. Nakamura, T. Kamakura, M. Ishikura, J.-F. Biell-
mann, J. Am. Chem. Soc. 2004, 126, 5958–5959; b) H.
Nakamura, S. Tashiro, T. Kamakura, Tetrahedron Lett.
2005, 46, 8333–8336; c) H. Nakamura, S. Onagi, T. Ka-
makura, J. Org. Chem. 2005, 70, 2357–2360; d) H. Na-
kamura, S. Onagi, Tetrahedron Lett. 2006, 47, 2539–
2542; e) H. Nakamura, T. Kamakura, S. Onagi, Org.
Lett. 2006, 8, 2095–2098; f) H. Nakamura, M. Ishikura,
T. Sugiishi, T. Kamakura, J.-F. Biellmann, Org. Biomol.
Chem. 2008, 6, 1471–1477.
[12] P. Crabbꢁ, B. Nassim, M-T. R. Lopes, Org. Synth. 1985,
63, 203.
[13] S. Redon, A.-L. B. Berkaoui, X. Pannecoucke, F. Out-
urquin, Tetrahedron 2007, 63, 3707–3717.
[14] C. J. Elsevier, P. Vermeer, J. Org. Chem. 1989, 54,
3726–3730.
[15] E. Yoneda, S. Zhang, D. Zhou, K. Onitsuka, S. Takaha-
shi, J. Org. Chem. 2003, 68, 8571–8576.
944
asc.wiley-vch.de
ꢂ 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 2012, 354, 933 – 944