Regioselective addition of allylindium reagents to allenes in functionalized 1,6-diols bearing allenynes

Article abstract of DOI:10.1002/ejoc.200800027

Addition reactions of allylindium reagents generated in situ from indium and allyl halides to functionalized allenyne 1,6-diols proceeded regioselectively through anti-Markovnikov addition to produce exclusively dienyne 1,6-diols in good yields in THF at

Full text of DOI:10.1002/ejoc.200800027

FULL PAPER
DOI: 10.1002/ejoc.200800027
Regioselective Addition of Allylindium Reagents to Allenes in Functionalized
1,6-Diols Bearing Allenynes
Sundae Kim[a] and Phil Ho Lee*[a]
Keywords: Electrophilic addition / Allenes / Allylation / Indium
Addition reactions of allylindium reagents generated in situ
from indium and allyl halides to functionalized allenyne 1,6-
diols proceeded regioselectively through anti-Markovnikov
addition to produce exclusively dienyne 1,6-diols in good
yields in THF at 70 °C. In the case of 3-bromo-2-methylpro-
pene, lithium iodide was used as an additive.
(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2008)
homologs of propargyl alcohol (3, n = 2, 3, and 4) afforded
the addition products with Markovnikov selectivity.[7] More
recently, it was reported that allylation of unactivated ter-
minal alkynes by treatment with allylindiums provided
branched 1,4-dienes through regioselective Markovnikov
addition.[8] As part of our continuing effort to expand the
synthetic utility of indium, we report herein stereoselective
allylindation of allenyne 1,6-diols having an allenol and two
alkynol moieties with an allylindium reagent (Figure 1).
Introduction
The carbometalation of C–C multiple bonds such as al-
kenes, alkynes, and allenes is a very important organic
transformation.[1] In particular, the addition of allylmetal
compounds to C–C multiple bonds is a significant method
for constructing carbon skeletons. To date, various allylmet-
alations have been reported on the basis of the nucleophilic
character of allylmetals generated from allyl halides and
metals (Ta, Zr, Zn, Al, Ti, Si, Sn, and Ga).[2] Recently, in-
dium metal has emerged as the metal with the most poten-
tial, because of its advantages with regard to ease of prepa-
ration, handling, toxicity, and availability.[3] Although a
variety of addition reaction of allylindiums with carbonyl-
and imine-derived functional groups have been reported,[4]
the addition of allylindiums to C–C multiple bonds have
received relatively little attention. Therefore, there is still
strong need for efficient addition reactions of allylindiums
to C–C multiple bonds. Reactions of allylindiums with
homoallenyl alcohols (1 and 2) bearing a methyl or isopro-
pyl group at the C1 or C4 position afforded the correspond-
ing allylation products with anti-Markovnikov selectivity.[5]
However, because the presence of a hydroxy group was es-
sential for accelerating the allylation reaction, the addition
reaction of allylindiums with nonfunctionalized or hydroxy-
protected alkynes and allenes did not proceed. In DMF,
treatment of allylindiums with propargyl alcohol and
homopropargyl alcohol gave the corresponding allylation
products with mainly anti-Markovnikov selectivity.[6] Al-
though the reaction of propargyl alcohol with allylindium
gave predominantly the anti-Markovnikov product in THF,
Figure 1. Structures of allenol, alkynol, and allenyne 1,6-diol.
Results and Discussion
We first investigated various experimental conditions in
a model reaction of functionalized allenyne 1,6-diol 4c with
allylindium generated in situ from 3-bromo-2-methylpro-
pene and indium (Table 1). 1,6-Diol 4c was prepared from
highly selective addition of the 3,6-dianion reagent derived
from 1,6-dibromo-2,4-hexadiyne and indium to benzalde-
hyde (2 equiv.) in THF.[9] Treatment of 4c with allylindium
produced addition product 5d in 55% yield in DMF at
100 °C after 15 h (Table 1, Entry 1). The use of LiI as an
additive did not give the desired product (Table 1, Entry 2).
However, by heating the reaction mixture at reflux (70 °C)
in THF gave regioselectively dienyne 1,6-diol 5d in 30%
yield together with starting material 4c (43%; Table 1, En-
try 3). The allylindium reagent obtained from indium
(1.5 equiv.) and 3-bromo-2-methylpropene (2.25 equiv.) in-
[a] National Research Laboratory for Catalytic Organic Reaction,
Department of Chemistry and Institute for Basic Science,
Kangwon National University
Chunchon 200-701, Republic of Korea
Fax: +82-33-253-7582
E-mail: phlee@kangwon.ac.kr
Supporting information for this article is available on the
WWW under http://www.eurjoc.org or from the author.
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© 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2008, 2262–2266

Regioselective Addition of Allylindium Reagents to Allenyne 1,6-Diols
creased the yield (39%) of 5d, but starting material 4c did afforded dienyne 1,6-diol 5d in 65% yield in THF at 70 °C
not disappear (Table 1, Entry 4). A variety of additives such after 16 h, which indicates that the present method pro-
as LiI, LiBr, and I2 were examined to increase the product ceeded regioselectively via anti-Markovnikov addition
yield. Among them, the use of lithium iodide (1.5 equiv.) (Table 1, Entry 5). No trace of the corresponding Markov-
nikov addition product was detected by NMR spectroscopy
Table 1. Reaction optimization.[a]
in this reaction. 3-Iodo-2-methylpropene was detected in
the H NMR spectrum after treatment with lithium iodide
1
in THF, which indicates that the bromine atom in 3-bromo-
2-methylpropene was substituted for an iodine atom, and
the reaction of the corresponding iodide then proceeded
smoothly with indium to produce the organoindium rea-
gent. Surprisingly, addition products resulting from ad-
dition of the allylindium to the triple bond were not ob-
served. These results imply that homoallenyl alcohol is
more reactive than homopropargyl alcohols directed
towards the allylindium reagent. THF was the best solvent
among several reaction media (DMF, THF, PhCH3,
CH3CN, THF/H2O, and DMF/H2O) that were evaluated.
The stereochemistry of the double bond in dienyne 1,6-diol
5d was proved to be (E) by NOE experiments.
Entry Solvent
Additive T [°C]
t [h]
Yield [%][b]
1
2
DMF
DMF
THF
THF
THF
–
100
140
70
15
15
18
18
16
55
LiI[c]
–
trace
30(43)[d]
39(30)[d]
65
3
4[e]
5
–
70
70
LiI[c]
[a] In (1.0 equiv.) and 3-bromo-2-methylpropene (1.5 equiv.) were
used. [b] Isolated yield. [c] LiI (1.5 equiv.) was used. [d] Recovery
yield of 4c. [e] In (1.5 equiv.) and 3-bromo-2-methylpropene
(2.25 equiv.) were used.
Table 2. Regioselective allylation of allylindium to allenes in 1,6-diols having allenynes.[a]
[a] In (1.0 equiv.) and allyl iodide (1.5 equiv.) were used. [b] In (1.0 equiv.), allyl halide (1.5 equiv.), and LiI (1.5 equiv.) were used.
Eur. J. Org. Chem. 2008, 2262–2266
© 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
2263

S. Kim, P. H. Lee
FULL PAPER
To demonstrate the efficiency and scope of the present protonated by the hydroxy proton to afford (E)-allyl alcohol
method, allylindium reagents generated in situ from the re- indium salt 8 followed by aqueous workup to provide dien-
action of indium with allyl bromide and 3-bromo-2-methyl- yne 1,6-diol 5.
propene were treated with a variety of allenyne 1,6-diols,
and the results are summarized in Table 2. Under the opti-
mized conditions, allylindium added to diol 4a in THF to Conclusions
give dienyne–1,6-diol 5a in 65% yield (Table 2, Entry 1).
Compound 4b obtained from cyclohexanecarboxaldehyde
produced desired compound 5b in 69% yield (Table 2, En-
We demonstrated that the addition of allylindium rea-
gents to functionalized allenyne 1,6-diols proceeds regiose-
lectively through anti-Markovnikov addition to produce ex-
try 2). Reaction of 4c with allylindium afforded 5c in 72%
clusively dienyne 1,6-diols in good yields. These results
yield under the optimum conditions (Table 2, Entry 3). The
should open more opportunities in the search of efficient
presence of various substituents such as chloride, methoxy,
and selective new C–C bond-forming reactions because of
the possible applications of the functionalized dienyne 1,6-
diols.
methyl, hydroxy, and methoxycarbonyl groups on the aro-
matic rings did not affect the efficiency of the present reac-
tions (Table 2, Entries 5–11). It is noteworthy that protec-
tion of the hydroxy group is not necessary under the present
reaction conditions (Table 2, Entry 10). The reaction of al-
lenyne 1,6-diol 4e obtained from 4-chlorobenzaldehyde, in-
Experimental Section
dium, and 1,6-dibromo-2,4-hexadiyne with allylindium and
2-methylallylindium provided regioselectively function-
alized dienyne 1,6-diols 5e and 5f in 68 and 73% yield,
respectively (Table 2, Entries 5 and 6). In the case of the
allylindium reagent obtained from 3-bromo-2-methylpro-
pene and indium, a longer reaction time (16 h) was needed
to complete the reaction (Table 2, Entries 4 and 6). Al-
lenyne 1,6-diol 4i derived from 2,4,6-trimethylbenzaldehyde
turned out to be compatible with the employed reaction
conditions (Table 2, Entry 9). Compound 4l obtained from
2-furaldehyde worked equally well with indium and allyl io-
dide (Table 2, Entry 12). In all cases, no corresponding
Markovnikov addition products to the allene group or ad-
dition products of allylindium reagents to the triple bond
were formed in any of the reactions. Although the present
reaction mechanism has not been established, a possible re-
action pathway is described in Scheme 1. Addition of al-
lylindiums to allenyne 1,6-diols can occur regioselectively
and stereoselectively through hydroxy-chelated bicyclic
transition state 6 to afford (E)-1,5-dienynes 5. The hydroxy
group in homoallenyl alcohol can coordinate to the indium
atom in the allylindium reagent, which would produce bicy-
clic transition state 6 composed of chelated five- and six-
membered rings (Zimmerman–Traxler model). The re-
sulting vinylindium compound 7 could be spontaneously
Typical Experimental Procedures for 5d: Indium (57.4 mg,
0.5 mmol) and lithium iodide (100.0 mg, 0.75 mmol) in dry THF
(1 mL) was slowly added to 3-bromo-2-methylpropene (101.0 mg,
0.75 mmol) at room temperature under a nitrogen atmosphere. Af-
ter 15 min, compound 1c (145.0 mg, 0.5 mmol) was added to the
indium reagent in dry THF (1 mL), and the mixture was then
stirred at 70 °C for 16 h. After cooling to room temperature, the
reaction mixture was quenched with 10% HCl (1 mL). The aque-
ous layer was extracted with diethyl ether (3ϫ10 mL), and the
combined organic phase were washed with water and brine, dried
with MgSO4, filtered, and concentrated under reduced pressure.
The residue was purified by silica gel column chromatography
(EtOAc/hexane, 1:3; Rf = 0.3) to give 5d (108.0 mg, 65%). 1H NMR
(400 MHz, CDCl3, 25 °C, TMS): δ = 7.26–7.17 (m, 10 H), 5.86 (t,
J = 7.23 Hz, 1 H), 5.04 (s, 1 H), 4.67–4.62 (m, 1 H), 4.65 (s, 1 H),
4.60 (s, 1 H), 2.68–2.63 (m, 4 H), 2.33–2.28 (m, 2 H), 2.01 (t, J =
7.53 Hz, 2 H), 1.62 (s, 3 H) ppm. 13C NMR (100 MHz, CDCl3)
Isomer A: δ = 145.4, 143.0, 142.5, 138.13, 128.8, 128.7, 128.24,
128.1, 126.74, 126.7, 126.2, 110.9, 93.6, 79.3, 77.1, 72.8, 37.2, 30.9,
28.7, 22.8 ppm. Isomer B: δ = 145.4, 143.0, 142.5, 138.09, 128.8,
128.7, 128.22, 128.1, 126.72, 126.7, 126.2, 110.9, 93.6, 79.3, 77.1,
72.8, 37.2, 30.9, 28.7, 22.8 ppm. IR (KBr, neat): ν = 3388, 3064,
˜
3029, 2907, 1451, 1043 cm–1. HRMS (EI): calcd. for C24H26O2
[M]+ 346.1933; found 346.1935.
(E)-5-Pent-4-enylidenedodec-6-yne-4,9-diol
(5a):
1H
NMR
(400 MHz, CDCl3, 25 °C, TMS): δ = 5.87–5.26 (m, 2 H), 5.03 (d,
J = 17.1 Hz, 1 H), 4.98 (d, J = 10.2 Hz, 1 H), 4.00 (t, J = 6.77 Hz,
1 H), 3.81–3.76 (m, 1 H), 2.75 (s, 1 H), 2.61 (dd, J = 4.75, 4.75 Hz,
1 H), 2.50 (dd, J = 6.52, 6.52 Hz, 1 H), 2.34 (q, J = 7.32 Hz, 2 H),
2.18–2.13 (m, 2 H), 1.65–1.61 (m, 2 H), 1.60–1.46 (m, 4 H), 1.41–
1.28 (m, 3 H), 0.93 (q, J = 7.4 Hz, 6 H) ppm. 13C NMR (100 MHz,
CDCl3) Isomer A: δ = 138.3, 136.98, 127.6, 115.4, 93.3, 78.7, 75.65,
70.3, 38.9, 38.5, 33.4, 29.8, 28.9, 19.26, 14.4, 14.3 ppm. Isomer B:
δ = 138.3, 136.96, 127.6, 115.4, 93.3, 78.7, 75.7, 70.2, 38.9, 38.5,
33.4, 29.8, 28.9, 19.25, 14.4, 14.3 ppm. IR (KBr, neat): ν = 3357,
˜
3077, 2958, 2932, 2872, 1640, 1464, 1016 cm–1. HRMS (EI): calcd.
for C17H28O2 [M]+ 264.2089; found 264.2091.
(E)-1,6-Dicyclohexyl-2-pent-4-enylidenehex-3-yne-1,6-diol (5b): 1H
NMR (400 MHz, CDCl3, 25 °C, TMS): δ = 5.85–5.76 (m, 1 H),
5.78 (t, J = 7.26 Hz, 1 H), 5.04 (d, J = 17.1 Hz, 1 H), 4.98 (d, J =
10.1 Hz, 1 H), 3.65 (d, J = 7.87 Hz, 1 H), 3.53–3.48 (m, 1 H), 2.64
(dd, J = 4.5, 4.5 Hz, 1 H), 2.55 (dd, J = 6.87, 6.87 Hz, 1 H), 2.41–
2.33 (m, 2 H), 2.19–2.14 (m, 2 H), 2.01–1.92 (m, 3 H), 1.77–1.66
Scheme 1. Plausible mechanism for the addition of allylindiums to
allenyne 1,6-diol.
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Eur. J. Org. Chem. 2008, 2262–2266

Regioselective Addition of Allylindium Reagents to Allenyne 1,6-Diols
(m, 9 H), 1.58–1.46 (m, 4 H), 1.30–0.85 (m, 10 H) ppm. 13C NMR
(100 MHz, CDCl3) Isomer A: δ = 138.3, 138.0, 126.5, 115.4, 93.4,
(E)-2-Pent-4-enylidene-1,6-di-p-tolylhex-3-yne-1,6-diol (5h): 1H
NMR (400 MHz, CDCl3, 25 °C, TMS): δ = 7.23–7.09 (m, 8 H),
80.8, 78.8, 74.6, 43.0, 42.4, 33.5, 29.9, 29.8, 29.5, 29.3, 28.67, 26.9, 5.93 (t, J = 7.21 Hz, 1 H), 5.83–5.72 (m, 1 H), 5.07 (d, J = 3.74 Hz,
26.8, 26.6, 26.5, 26.4, 26.3, 26.26 ppm. Isomer B: δ = 138.3, 137.9, 1 H), 5.01 (d, J = 17.1 Hz, 1 H), 4.97 (d, J = 10.1 Hz, 1 H), 4.72–
126.6, 115.4, 93.4, 80.9, 78.8, 74.6, 43.0, 42.3, 33.5, 29.9, 29.8, 29.6, 4.68 (m, 1 H), 2.70 (d, J = 6.29 Hz, 2 H), 2.63 (s, 1 H), 2.59 (s, 1
29.4, 28.74, 26.9, 26.8, 26.6, 26.5, 26.4, 26.3, 26.26 ppm. IR (KBr,
H), 2.34–2.29 (m, 2 H), 2.33 (s, 3 H), 2.32 (s, 3 H), 2.12 (q, J =
7.14 Hz, 2 H) ppm. 13C NMR (100 MHz, CDCl3) Isomer A: δ =
140.1, 139.6, 138.3, 137.9, 137.7, 137.39, 129.5, 129.4, 127.05,
126.68, 126.2, 115.5, 93.6, 79.3, 77.0, 72.6, 33.4, 30.9, 29.9,
21.57 ppm. Isomer B: δ = 140.1, 139.6, 138.3, 137.8, 137.7, 137.4,
129.5, 129.4, 127.07, 126.7, 126.2, 93.6, 79.3, 77.0, 72.6, 33.4, 30.9,
neat): ν = 3366, 2923, 2851, 1448, 1263 cm–1. HRMS (EI): calcd.
˜
for C23H36O2 [M]+ 344.2715; found 344.2714.
(E)-2-Pent-4-enylidene-1,6-diphenylhex-3-yne-1,6-diol
(5c):
1H
NMR (400 MHz, CDCl3, 25 °C, TMS): δ = 7.37–7.27 (m, 10 H),
5.98 (t, J = 7.27 Hz, 1 H), 5.84–5.74 (m, 1 H), 5.14 (s, 1 H), 5.03
(d, J = 17.1 Hz, 1 H), 4.98 (d, J = 10.5 Hz, 1 H), 4.75–4.72 (m, 1
H), 2.75–2.73 (m, 2 H), 2.37–2.32 (m, 4 H), 2.15 (q, J = 7.15 Hz,
2 H) ppm. 13C NMR (100 MHz, CDCl3) Isomer A: δ = 142.5,
142.0, 137.8, 137.41, 128.4, 128.3, 127.83, 127.7, 126.4, 126.3,
125.7, 115.1, 93.1, 78.9, 76.7, 72.3, 33.0, 30.5, 29.5 ppm. Isomer B:
δ = 142.5, 142.0, 137.8, 137.38, 128.4, 128.3, 127.85, 127.7, 126.4,
126.3, 125.7, 115.1, 93.0, 78.9, 76.7, 72.3, 33.0, 30.5, 29.5 ppm. IR
29.9, 21.59 ppm. IR (KBr, neat): ν = 3375, 3022, 2976, 2920, 1513,
˜
1042 cm–1. HRMS (EI): calcd. for C25H28O2 [M]+ 360.2089; found
360.2087.
(E)-2-Pent-4-enylidene-1,6-bis(2,4,6-trimethylphenyl)hex-3-yne-1,6-
1
diol (5i): H NMR (400 MHz, CDCl3, 25 °C, TMS): δ = 6.80 (s, 2
H), 6.79 (s, 2 H), 5.79–5.71 (m, 1 H), 5.68–5.63 (m, 1 H), 5.57 (s,
1 H), 5.18–5.13 (m, 1 H), 4.98 (d, J = 17.2 Hz, 1 H), 4.94 (d, J =
10.1 Hz, 1 H), 2.97–2.90 (m, 1 H), 2.68–2.60 (m, 1 H), 2.39–2.34
(m, 8 H), 2.32–2.29 (m, 8 H), 2.30 (s, 3 H), 2.29 (s, 3 H), 2.09 (q,
J = 7.1 Hz, 2 H) ppm. 13C NMR (100 MHz, CDCl3) Isomer A: δ
= 138.4, 137.6, 137.5, 137.4, 136.5, 135.5, 135.2, 134.6, 130.56,
130.2, 125.1, 115.3, 93.63, 79.7, 72.1, 70.5, 33.5, 30.1, 27.7, 21.3,
21.2, 21.1 ppm. Isomer B: δ = 138.4, 137.6, 137.5, 137.3, 136.6,
135.6, 135.1, 134.5, 130.58, 130.3, 125.1, 115.3, 93.57, 79.7, 72.0,
(KBr, neat): ν = 3407, 3064, 3029, 2926, 1454, 1049 cm–1. HRMS
˜
(EI): calcd. for C23H24O2 [M]+ 332.1776; found 332.1779.
(E)-1,6-Bis(4-chlorophenyl)-2-pent-4-enylidenehex-3-yne-1,6-diol
1
(5e): H NMR (400 MHz, CDCl3, 25 °C, TMS): δ = 7.30–7.18 (m,
8 H), 5.94 (t, J = 7.27 Hz, 1 H), 5.82–5.71 (m, 1 H), 5.08 (s, 1 H),
5.02 (d, J = 17.0 Hz, 1 H), 4.98 (d, J = 11.2 Hz, 1 H), 4.71 (t, J =
6.58 Hz, 1 H), 2.84 (s, 1 H), 2.75 (s, 1 H), 2.70 (d, J = 6.58 Hz, 2
H), 2.32–2.27 (m, 2 H), 2.13 (q, J = 6.62 Hz, 2 H) ppm. 13C NMR
(100 MHz, CDCl3) Isomer A: δ = 141.0, 140.4, 138.0, 137.7,
133.53, 133.3, 128.5, 128.4, 127.7, 127.65, 127.2, 126.04, 92.8, 78.8,
76.1, 71.64, 32.9, 30.3, 29.4 ppm. Isomer B: δ = 141.0, 140.4, 138.0,
137.7, 133.51, 133.3, 128.5, 128.4, 127.7, 127.65, 127.2, 126.00,
70.3, 33.5, 30.1, 27.6, 21.3, 21.2, 21.0 ppm. IR (KBr, neat): ν =
˜
3398, 2920, 1611, 1447 cm–1. HRMS (EI): calcd. for C29H36O2
[M]+ 416.2715; found 416.2713.
(E)-1,6-Bis(3-hydroxyphenyl)-2-pent-4-enylidenehex-3-yne-1,6-diol
1
(5j): H NMR (400 MHz, [D6]DMSO, 25 °C, TMS): δ = 9.26 (s, 1
H), 9.23 (s, 1 H), 7.05 (t, J = 7.79 Hz, 2 H), 6.77 (s, 1 H), 6.73–
6.65 (m, 3 H), 6.60 (t, J = 8.3 Hz, 2 H), 5.97 (t, J = 7.15 Hz, 1 H),
5.81–5.71 (m, 1 H), 5.43 (dd, J = 4.12, 4.34 Hz, 1 H), 5.36 (d, J =
4.15 Hz, 1 H), 5.01 (d, J = 17.2 Hz, 1 H), 4.95 (d, J = 10.6 Hz, 1
H), 4.83 (s, 1 H), 4.53–4.48 (m, 1 H), 2.65–2.59 (m, 1 H), 2.57–2.52
(m, 1 H), 2.17 (q, J = 7.15 Hz, 1 H), 2.05 (q, J = 6.75 Hz, 2 H)
ppm. 13C NMR (100 MHz, [D6]DMSO) Isomer A: δ = 157.4,
157.2, 146.3, 145.4, 138.4, 134.6, 129.0, 128.9, 128.0, 117.8, 117.3,
115.5, 114.2, 114.1, 113.80, 113.2, 93.4, 79.2, 75.33, 71.77, 33.1,
30.4, 29.0 ppm. Isomer B: δ = 157.4, 157.2, 146.3, 145.4, 138.4,
134.5, 129.0, 128.9, 127.98, 117.9, 117.3, 115.5, 114.2, 114.1, 113.8,
113.2, 93.4, 79.22, 75.27, 71.81, 33.1, 30.4, 29.0 ppm. IR (KBr,
92.8, 78.8, 76.1, 71.59, 32.9, 30.3, 29.4 ppm. IR (KBr, neat): ν =
˜
3379, 3076, 2977, 2909, 1490, 1090, 1013 cm–1. HRMS (EI): calcd.
for C23H22Cl2O2 [M]+ 400.0997; found 400.0994.
(E)-1,6-Bis(4-chlorophenyl)-2-(4-methylpent-4-enylidene)hex-3-yne-
1
1,6-diol (5f): H NMR (400 MHz, CDCl3, 25 °C, TMS): δ = 7.31–
7.21 (m, 8 H), 5.96 (t, J = 7.24 Hz, 1 H), 5.10 (s, 1 H), 4.75–4.73
(m, 1 H), 4.74 (s, 1 H), 4.67 (s, 1 H), 2.74–2.72 (m, 2 H), 2.54 (s, 1
H), 2.45 (s, 1 H), 2.37 (q, J = 7.24 Hz, 2 H), 2.09 (q, J = 7.45 Hz,
2 H), 1.70 (s, 3 H) ppm. 13C NMR (100 MHz, CDCl3) Isomer A:
δ = 144.8, 140.9, 140.4, 138.3, 133.57, 133.4, 128.6, 128.4, 127.6,
127.2, 125.82, 92.7, 78.8, 76.1, 71.7, 36.7, 30.4, 28.2, 22.3 ppm. Iso-
mer B: δ = 144.8, 140.9, 140.4, 138.3, 133.56, 133.4, 128.6, 128.4,
127.7, 127.2, 125.79, 92.7, 78.8, 76.1, 71.6, 36.7, 30.3, 28.2,
neat): ν = 3268, 2908, 1455, 1277, 1023, 998 cm–1. HRMS (EI):
˜
calcd. for C23H24O4 [M]+ 364.1675; found 364.1676.
22.3 ppm. IR (KBr, neat): ν = 3375, 3073, 2911, 1490, 1090,
˜
(E)-1,6-Bis[(4-methoxycarbonyl)phenyl]-2-pent-4-enylidenehex-3-
yne-1,6-diol (5k): 1H NMR (400 MHz, CDCl3, 25 °C, TMS): δ =
7.97–7.91 (m, 4 H), 7.40–7.37 (m, 2 H), 7.34–7.30 (m, 2 H), 5.96
(t, J = 7.22 Hz, 1 H), 5.79–5.69 (m, 1 H), 5.15 (s, 1 H), 4.99 (d, J
= 17.0 Hz, 1 H), 4.96 (d, J = 9.91 Hz, 1 H), 4.82–4.76 (m, 1 H),
3.86 (s, 6 H), 3.40 (s, 1 H), 3.35 (s, 1 H), 2.74–2.71 (m, 2 H), 2.32–
2.25 (m, 2 H), 2.13–2.08 (m, 2 H) ppm. 13C NMR (100 MHz,
CDCl3) Isomer A: δ = 159.9, 159.72, 138.7, 135.3, 133.8, 133.7,
130.4, 129.1, 127.6, 122.64, 115.3, 114.3, 114.1, 95.34, 80.4, 76.8,
72.58, 55.7, 35.7, 31.0, 30.3 ppm. Isomer B: δ = 159.9, 159.71,
138.7, 135.3, 133.8, 133.7, 130.4, 129.1, 127.6, 122.6, 115.3, 114.3,
114.0, 95.31, 80.4, 76.7, 72.62, 55.7, 35.7, 31.0, 30.3 ppm. IR (KBr,
1013 cm–1. HRMS (EI): calcd. for C24H24Cl2O2 [M]+ 414.1153;
found 414.1153.
(E)-1,6-Bis(3-methoxyphenyl)-2-pent-4-enylidenehex-3-yne-1,6-diol
(5g): 1H NMR (400 MHz, CDCl3, 25 °C, TMS): δ = 7.25–7.19 (m,
2 H), 6.94–6.84 (m, 4 H), 6.82–6.79 (m, 2 H), 5.95 (t, J = 7.23 Hz,
1 H), 5.83–5.73 (m, 1 H), 5.09 (s, 1 H), 5.02 (d, J = 17.1 Hz, 1 H),
4.97 (d, J = 10.1 Hz, 1 H), 4.72 (q, J = 6.1 Hz, 1 H), 3.77 (s, 3 H),
3.76 (s, 3 H), 2.76–2.71 (m, 4 H), 2.33 (q, J = 7.37 Hz, 2 H), 2.14
(q, J = 7.07 Hz, 2 H) ppm. 13C NMR (100 MHz, CDCl3) Isomer
A: δ = 159.7, 159.5, 144.3, 143.8, 137.8, 137.43, 129.4, 129.2,
126.38, 118.6, 118.1, 115.1, 113.27, 113.1, 111.9, 111.2, 93.16, 78.8,
76.6, 72.3, 55.2, 32.9, 30.5, 29.4 ppm. Isomer B: δ = 159.7, 159.5,
144.3, 143.8, 137.8, 137.38, 129.4, 129.2, 126.36, 118.6, 118.1,
115.1, 113.29, 113.2, 111.9, 111.2, 93.19, 78.8, 76.6, 72.3, 55.2, 32.9,
neat): ν = 3450, 3075, 2951, 1721, 1436, 1282, 1111 cm–1. HRMS
˜
(EI): calcd. for C27H28O6 [M]+ 448.1886; found 446.1886.
(E)-1,6-Difuran-2-yl-2-pent-4-enylidenehex-3-yne-1,6-diol (5l): 1H
NMR (400 MHz, CDCl3, 25 °C, TMS): δ = 7.36 (s, 2 H), 6.35–6.31
30.5, 29.4 ppm. IR (KBr, neat): ν = 3407, 3074, 2917, 2835, 1600,
˜
1260, 1042 cm–1. HRMS (EI): calcd. for C25H28O4 [M]+ 392.1988; (m, 2 H), 6.29–6.26 (m, 2 H), 6.00 (t, J = 7.20 Hz, 1 H), 5.85–5.75
found 392.1987.
(m, 1 H), 5.12 (s, 1 H), 5.03 (d, J = 17.1 Hz, 1 H), 4.98 (d, J =
Eur. J. Org. Chem. 2008, 2262–2266
© 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
2265

S. Kim, P. H. Lee
FULL PAPER
Yamada, H. Odaka, K. Utimoto, T. Fujii, I. Furukawa, Chem.
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10.2 Hz, 1 H), 4.83 (t, J = 6.05 Hz, 1 H), 2.91 (d, J = 6.05 Hz, 2
H), 2.75 (s, 2 H), 2.40–2.34 (m, 2 H), 2.15 (q, J = 7.05 Hz, 2 H)
ppm. 13C NMR (100 MHz, CDCl3) Isomer A: δ = 155.3, 155.19,
142.7, 142.62, 138.7, 138.1, 124.03, 115.6, 110.7, 110.6, 107.3,
107.0, 92.7, 79.2, 71.22, 66.6, 33.2, 29.9, 27.7 ppm. Isomer B: δ =
155.2, 155.16, 142.7, 142.59, 138.7, 138.1, 124.0, 115.6, 110.7,
110.6, 107.4, 107.1, 92.6, 79.1, 71.16, 66.6, 33.2, 29.9, 27.7 ppm. IR
(KBr, neat): ν = 3366, 2977, 2914, 1639, 1504, 1143, 1010, 737 cm–1.
˜
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HRMS (EI): calcd. for C19H20O4 [M]+ 312.1362; found 312.1364.
Supporting Information (see footnote on the first page of this arti-
cle): Experimental procedure and data of compounds 4a–l; 1H and
13C NMR spectra for compounds 4c, 4h, 4k, 5c, 5h, 5k.
Acknowledgments
This work was supported by KOSEF through the National Re-
search Lab. Program funded by the Ministry of Science and Tech-
nology (No. M10600000203-06J0000-20310) and by the Korea Sci-
ence and Engineering Foundation (KOSEF, R01-2006-000-11283-
0). The NMR and mass data were obtained from the central instru-
mental facility in Kangwon National University.
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Received: January 10, 2008
Published Online: March 10, 2008
2266
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Eur. J. Org. Chem. 2008, 2262–2266