Rh(I)-catalyzed allenic Pauson-Khand reaction: First construction of the bicyclo[6.3.0]undecadienone ring system

Article abstract of DOI:10.1016/j.tet.2005.08.088

The Rh(I)-catalyzed Pauson-Khand reaction of allenynes afforded the bicyclo[6.3.0]undecadienones as well as their benzo and furo derivatives. In addition, a novel [RhCl(CO)₂]₂-catalyzed [2,3]-sigmatropic rearrangement of the sulfinic

Full text of DOI:10.1016/j.tet.2005.08.088

Tetrahedron 61 (2005) 10983–10994
Rh(I)-catalyzed allenic Pauson–Khand reaction: first construction
of the bicyclo[6.3.0]undecadienone ring system
*
Chisato Mukai, Toshiyuki Hirose, Satoshi Teramoto and Shinji Kitagaki
Division of Pharmaceutical Sciences, Graduate School of Natural Science and Technology, Kanazawa University, Kakuma-machi,
Kanazawa 920-1192, Japan
Received 29 July 2005; revised 22 August 2005; accepted 22 August 2005
Available online 19 September 2005
Abstract—The Rh(I)-catalyzed Pauson–Khand reaction of allenynes afforded the bicyclo[6.3.0]undecadienones as well as their benzo and
furo derivatives. In addition, a novel [RhCl(CO)2]2-catalyzed [2,3]-sigmatropic rearrangement of the sulfinic ester species of propargyl
alcohols was developed.
q 2005 Elsevier Ltd. All rights reserved.
1. Introduction
Rh(I)-catalyzed ring-closing reactions. In particular, we
were interested in the preparation of the bicyclo[6.3.0]-
undecadienone skeleton,7 because to our best knowledge no
reports on the synthesis of the bicyclo[6.3.0] ring system by
PKR is so far available. We now describe the first example
of PKR for the preparation of bicyclo[6.3.0]undeca-1,8-
dien-10-ones, and their benzo and furo congeners.
The Co2(CO)6-mediated Pauson–Khand reaction (PKR)1 of
enynes is well recognized as one of the most convenient and
straightforward methods for the construction of the
bicyclo[3.3.0]octenone as well as bicyclo[4.3.0]nonenone
ring systems. However, this attractive ring-closing reaction
could not be generally used for the preparation of the
C1-carbon homologated bicyclic framework, namely a
bicyclo[5.3.0]decenone skeleton.2,3 Recent efforts from
this laboratory4 have led to the development of an effective
method for the construction of bicyclo[5.3.0] ring system
based on the Rh(I)-catalyzed PKR of allenynes.5 Thus, a
solution of 3-(phenylsulfonyl)octa-1,2-dien-7-yne deriva-
tives 1 was heated in the presence of a catalytic amount of
[RhCl(CO)2]2 or Rh[Cl(CO)dppp]2 in toluene under CO
pressure to produce the corresponding 2-phenylsulfonyl-
bicyclo[5.3.0]deca-1,7-dien-9-ones 2 in high to reasonable
yields (Scheme 1).6 Our endeavors were then directed
towards confirming the limitations of this newly developed
2. Results and discussion
The simple linear allenyne 7 was chosen as a first starting
material for Rh(I)-catalyzed PKR and prepared as follows
(Scheme 2). Treatment of 7-iodo-1-(trimethylsilyl)hept-1-
yne (3)8 with the acetylide, derived from 3-(tert-butyl-
diphenylsiloxy)prop-1-yne, afforded the coupled product 4
in 51% yield, the desilylation of which was subsequently
carried out by exposure to tetrabutylammonium fluoride
(TBAF) to provide the propargyl alcohol derivative 5 in
93% yield. The Sonogashira reaction of 5 with iodobenzene
furnished the phenylacetylene derivative 6 in 79% yield,
and this compound was transformed into the desired
allenyne 7 in a 68% overall yield by successive exposure
to benzenesulfenyl chloride (PhSCl) and m-chloroper-
benzoic acid (mCPBA).4 With the required allenyne 7 in
hand, this compound was used for the ring-closing reaction
in the presence of a catalytic amount (5 mol%) of
[RhCl(CO)dppp]2 in refluxing toluene for 7 h under an
atmosphere of CO, that had been established for the
preparation of bicyclo[4.3.0]nona-1,6-dien-8-ones and
bicyclo[5.3.0]deca-1,7-dien-9-ones.4 However, no eight-
membered bicyclic compounds could be detected in the
reaction mixture. Changing the catalyst from
[RhCl(CO)dppp]2 to [RhCl(CO)2]2 (5 mol%) in refluxing
Scheme 1.
Keywords: Pauson–Khand reaction; Allenyne; Bicyclo[6.3.0]undecadie-
none; [2,3]-Sigmatropic rearrangement; [RhCl(CO)2]2; [RhCl(CO)dppp]2.
Corresponding author. Tel.: C81 76 234 4411; fax: C81 76 234 4410;
e-mail: cmukai@kenroku.kanazawa-u.ac.jp
*
0040–4020/$ - see front matter q 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2005.08.088

10984
C. Mukai et al. / Tetrahedron 61 (2005) 10983–10994
procedure described for the preparation of 7 from 5. Upon
exposure to 10 mol% of [RhCl(CO)2]2 in refluxing xylene
for 2.5 h, the allenyne 11 underwent the ring-closing
reaction to furnish the bicyclo[6.3.0] derivative 12 in 43%
yield. When a similar reaction was performed in the
presence of [RhCl(CO)dppp]2 instead of [RhCl(CO)2]2,
the desired compound 12 was also obtained, but the yield
was much lower (29%) compared to [RhCl(CO)2]2
(Scheme 3). As a result, the introduction of a gem-
bis(methoxycarbonyl) group on the carbon appendage of
the allenynes made significant improvement in the chemical
yield of the cyclized products (23–43%).
Our endeavors then turned to application of this Rh(I)-
catalyzed PKR to the 1,2-disubstituted-aromatic substrates
bearing a butyne as well as a buta-1,2-diene residue in
which the template effect of the aromatic ring would be
expected to facilitate the ring-closing step like the gem-
bis(methoxycarbonyl) moiety of 11. According to the
literature procedure,11 4-bromo-1-(trimethylsilyl)but-1-
yne12 was transformed into the corresponding zinc reagent
14 in situ, which was then coupled with the iodobenzene
derivative 1313 under the Negishi coupling conditions14 to
provide 15. A tert-butyldimethylsilyl (TBS) group on the
primary hydroxyl moiety of 15 was removed by acid
treatment to furnish 16 in a 62% overall yield. The second
coupling reaction between the benzyl bromide derivative
17, derived from 16 using a conventional procedure in 99%,
and the indium species 18, prepared in situ from the reaction
Scheme 2. Reagents and conditions: (a) nBuLi, THF–DMPU, K78 8C to rt,
(51%); (b) TBAF, THF, rt, (93%); (c) PhI, Pd(PPh3)2Cl2, CuI, Pr2NH,
THF, rt, (79%); (d) PhSCl, Et3N, THF, K78 8C; (e) mCPBA, CH2Cl2, 0 8C,
(68%); (f) 20 mol% of [RhCl(CO)2]2, 1 atm of CO, refluxing xylene, (23%).
i
toluene for 96 h led to the isolation of the desired
bicyclo[6.3.0]undeca-1,8-dien-10-one 8 in a low yield
(11%). When the ring-closing reaction was carried out in
the presence of 10 mol% of [RhCl(CO)2]2 in refluxing
xylene, compound 8 was obtained in 18% yield. Although
the increasing load of the catalyst (20 mol%) with a higher
reaction temperature (in refluxing xylene for 0.5 h) brought
about further improvement of the chemical yield (23%), a
satisfactory chemical yield of 8 has not yet been attained.
The other catalysts were examined, but the chemical yields
were much less than 23%. For instance, the allenyne 7 was
exposed to 10 mol% of (PPh3)3RhCl in refluxing xylene to
furnish 8 in 14% yield.
n
of 3-(tert-butyldimethylsiloxy)prop-1-yne with BuLi and
InCl3,15 under the palladium coupling conditions gave 19,
which was subsequently desilylated by TBAF to produce 20
in a 65% overall yield. Compound 20 was converted into the
phenylacetylene derivative 21 under the Sonogashira
conditions (73%) and two compounds, 20 and 21, were
then transformed into the corresponding allenynes 22 (50%)
and 23 (43%) by the standard method (Scheme 4).
We next investigated the Rh(I)-catalyzed PKR of the
allenyne 11 possessing a gem-bis(methoxycarbonyl)
functionality on the carbon appendage hoping for the
Thorpe-Ingold-type effect9 in the ring-closing step. Thus,
the dimethyl malonate was successively alkylated with
5-iodopent-1-yne10 and 4-iodo-1-(tert-butyldiphenyl-
siloxy)but-2-yne4b to afford the dialkylated product, which
was subsequently desilylated with TBAF to produce 9 in a
44% overall yield. Conversion of 9 into the allenyne 11 via
10 (71 and 77%, respectively) was realized according to the
A solution of 22 and 10 mol% of [RhCl(CO)2]2 in xylene was
refluxed for 0.5 h (disappearance of the starting material was
Scheme 3. Reagents and conditions: (a) 5-iodopent-1-yne, NaH, THF, 0 8C
to rt; (b) 4-iodo-1-(TBDPSO)but-2-yne, NaH, THF, 0 8C to rt; (c) TBAF,
THF, rt, (44%); (d) PhI, Pd(PPh3)2Cl2, CuI, Pr2NH, THF, rt, (77%); (e)
PhSCl, Et3N, THF, K78 8C; (f) mCPBA, CH2Cl2, 0 8C, (71%); (g)
10 mol% of [RhCl(CO)2]2, 1 atm of CO, refluxing xylene, (43%).
Scheme 4. Reagents and conditions: (a) Pd(PPh3)4, DMA, 80 8C; (b) TsOH,
THF, rt, (62%); (c) CBr4, PPh3, CH2Cl2, 0 8C to rt, (99%); (d) Pd(dppf)Cl2,
THF, reflux; (e) TBAF, THF, 0 8C, (65%); (f) PhI, Pd(PPh3)2Cl2, CuI,
iPr2NH, THF, rt, (73%); (g) PhSCl, Et3N, THF, K78 8C; (h) mCPBA,
CH2Cl2, 0 8C, 22 (50%), 23 (43%).
i

C. Mukai et al. / Tetrahedron 61 (2005) 10983–10994
Table 1. Rh(I)-catalyzed ring-closing reaction of compounds 22 and 23
10985
Entry
Substrate
R
Rh (mol%)
Solvent
Temperature
Time (h)
Product
Yield (%)
1
2
3
4
5
22
22
22
23
23
H
H
H
Ph
Ph
10a
10
5b
Xylene
Toluene
Toluene
Xylene
Xylene
Reflux
80 8C
80 8C
Reflux
Reflux
0.5
1
4
2
2
24
24
24
25
25
63
87
90
83
76
10c
5
a Compound 24 was isolated in 35% yield when [RhCl(CO)2]2 was used.
b When 2.5 mol% of [RhCl(CO)dppp]2 was employed in toluene at 80 8C for 24 h, 24 was obtained in 66% yield along with the recovery of compound 22 in 4%
yield.
c No reaction took place in toluene at 80 8C for 24 h.
monitored by TLC) to produce the cyclized product 24 in
35% yield. Upon exposure to [RhCl(CO)dppp]2 instead of
[RhCl(CO)2]2 under the same conditions, 22 produced 24 in a
significantly improved yield (63%) (Table 1, entry 1). The
best result (90%) was obtained when 22 was treated with
5 mol% of [RhCl(CO)dppp]2 in toluene at 80 8C for 4 h
(entry 3). A similar result was observed when 10 mol% of
[RhCl(CO)dppp]2 was used (entry 2). Interestingly, the
optimized conditions for the preparation of 24 (5 or 10 mol%
of [RhCl(CO)dppp]2 in toluene at 80 8C) was found to be no
longer effective for the phenyl congener 23 resulting in no
reaction. The desired phenyl derivative 25 was constructed in
83 and 76% yields when 23 was heated in refluxing xylene
(entries 4 and 5). Thus, we have succeeded in the synthesis of
the benzene ring-fused bicyclo[6.3.0]undecadienone frame-
works in high yields by taking advantage of the template
effect of the aromatic ring.
propargyl alcohols resulting in the formation of the
corresponding allenyl sulfones. Thus, we became interested
in determining if the Rh(I) catalyst would be able to catalyze
the [2,3]-sigmatropic rearrangement of sulfinic esters
35–37. To this end, the simpler sulfinic ester 41, derived
from the propargyl alcohol 38, was treated with 5 mol% of
[RhCl(CO)2]2 in toluene at 80 8C for 0.5 h under an
atmosphere of N2 to give the rearranged product 44 in
57% yield (Scheme 6). It should be noted that 44 was
obtained in 28% yield when heated at 80 8C in toluene in the
absence of [RhCl(CO)2]2 for 36 h. This result was different
from the case of 35, having a more sterically congested
framework (1,2-disubstituted benzene ring), where no
rearranged product could be isolated (Scheme 5).
[RhCl(CO)2]2 was found to accelerate the transformation
of 41 into 44 more effectively even at room temperature. As
a matter of fact, 44 was formed in 82% yield upon exposure
of 41 to 5 mol% of [RhCl(CO)2]2 in toluene at room
temperature for 0.5 h. Neither [RhCl(CO)dppp]2 nor
RhCl(PPh3)3 was active for this transformation at room
temperature leading to the complete recovery of the starting
material. [RhCl(COD)]2 and [IrCl(COD)]2 furnished the
desired product 44 at room temperature in the respective
Investigation of the Rh(I)-catalyzed PKR of the regio-
isomers 32–34 regarding the benzene ring of allenynes 22
and 23 was the next objective of this program. Three
propargyl alcohol derivatives 29–31 were prepared by
conventional means as depicted in Scheme 5. Unexpectedly,
the direct transformation of the propargyl alcohols 29–31
into the allenyl sulfones 32–34 by the standard two-step
procedure was troublesome. In fact, compound 29 was
successively exposed to PhSCl and mCPBA, however, the
desired allenyl sulfone 32 could not be isolated in more than
trace quantities. Thus, an alternative method for the
preparation of the allenyl sulfones 32–34 was necessary.
One of the possible solutions for this issue would involve
the consecutive formation of benzene sulfinic ester
derivatives from the propargyl alcohol derivatives and
their thermal [2,3]-sigmatropic rearrangement.16 Treatment
of the propargyl alcohols 29–31 with benenesulfinyl
i
chloride17 in THF in the presence of Pr2NEt at K78 8C
provided the corresponding sulfinic ester derivatives 35–37
without any difficulties. The thermal [2,3]-sigmatropic
rearrangement of compounds 35 was attempted under
several conditions, but the desired 32 was obtained only in
trace quantities. The major product isolated from the
reaction mixture was the hydrolyzed product 29 (15–33%).
Scheme 5. Reagents and conditions: (a) 3-(tert-butyldimethylsiloxy)prop-
1-yne, Pd(PPh3)2Cl2, CuI, Et3N, THF, rt, (85%); (b) Pd(PPh3)4, DMA,
i
80 8C; (c) TBAF, THF, 0 8C, (74%); (d) PhI, Pd(PPh3)2Cl2, CuI, Pr2NH,
THF, rt, (73%); (e) 10% aqueous HCl, THF, rt, (78% from 27); (f) PhSCl,
Et3N, THF, K78 8C; (g) mCPBA, CH2Cl2, 0 8C; (h) PhSOCl, Pr2NEt,
i
Hiroi and co-workers18 reported the efficient Pd-catalyzed
[2,3]-sigmatropic rearrangement of the sulfinic esters of
THF, K78 8C, 35 (94%), 36 (93%), 37 (86%); (i) 5 mol% of [RhCl(CO2)]2,
toluene, rt, 32 (26%), 33 (56%), 34 (75%) and recovery of 37 (16%).

10986
C. Mukai et al. / Tetrahedron 61 (2005) 10983–10994
was exposed to a catalytic amount of [RhCl(CO)dppp]2 in
refluxing toluene under an atmosphere of CO to give the
ring-closed product 49 in 39% yield. The phenyl congener
33 provided the bicyclo[6.3.0] derivative 50 in a higher
yield (44%) under typical ring-closing conditions. For the
TMS derivative 34, [RhCl(CO)2]2 was found to be superior
to [RhCl(CO)dppp]2 furnishing 51 in 28% yield
([RhCl(CO)dppp]2 gave 51 in 5% yield). Although the ring-
closed products 49–51 could be constructed by the Rh(I)-
catalyzed PKR irrespective of the substituent at the triple bond
terminus, the yields of which were much less than those of
their regioisomers 24 and 25 (see Table 1, Scheme 7).
Scheme 6. Reagents and conditions: (a) nBuLi, THF, K78 8C, 38 (97%), 39
(94%), 40 (79%); (b) PhSOCl, iPr2NEt, THF, K78 8C, 41 (75%), 42 (90%),
43 (65%); (c) 5 mol% of [RhCl(CO2)]2, toluene, rt, 44 (82%), 45 (86%), 46
(78%), 48 (63%).
yields of 58 and 74%, although a prolonged reaction time
was necessary for complete consumption of the starting
material (24 h in both cases). Toluene has so far provided
the best result (82%) compared to other solvents like
CH2Cl2, acetonitrile, DMF, and 1,4-dioxane (11–64%). The
secondary and tertiary propargyl alcohols 42 and 43,
derived from the corresponding alcohols 39 and 40,19
respectively, were then submitted to the best conditions
(5 mol% of [RhCl(CO)2]2 in toluene at room temperature
for 0.25–1 h) to afford the corresponding allenyl sulfones 45
and 46 in the respective yields of 86 and 78%. The
phenylacetylene derivative 47, which was prepared by the
reaction of 2-phenylprop-2-yn-1-ol with benzenesulfinyl
chloride17 and has a structure similar to 35, was chosen as
the next substrate. Compound 47 was treated with 5 mol%
of [RhCl(CO)2]2 in toluene at room temperature for 2 h to
provide the rearranged product 48 in a slightly lower yield
(63%) compared to those of 44–46. Thus, it became evident
that [RhCl(CO)2]2 was effective for our purpose under mild
conditions.
Scheme 7. Reagents and conditions: (a) [RhCl(CO)dppp]2 was used. (b)
[RhCl(CO2)]2, was used.
By taking application of this method to total synthesis of
natural products into account, we next investigated the
Rh(I)-catalyzed PKR of the furan derivative 59 as a
preliminary examination, because a 1,2-disubstituted furan
moiety would not only serve as the template in the ring-
closing step, but also provide some opportunities for further
chemical elaboration leading to more complex function-
alities. Thus, the substrate 59 for the ring-closing reaction
was prepared as depicted in Scheme 8.
With these results available, we examined the Rh(I)-
catalyzed synthesis of the allenyl sulfones 32–34 from
35–37 (Scheme 5). It took a prolonged reaction time (70 h)
for consumption of the starting material, but gave the
desired product 32 in 26% yield when the sulfinic ester 35
was exposed to the best conditions (5 mol% of
[RhCl(CO)2]2 in toluene at room temperature). Heating
the reaction mixture in toluene at 80 8C did not produce any
improvement in the chemical yield (27%). The similar
reaction was carried out under an atmosphere CO instead of
N2, hoping for spontaneous PKR, to afford the allenyl
sulfone 32 in 30% yield as the sole isolatable product. The
bicyclo[6.3.0] derivative (PKR product) could not be
observed in the reaction mixture. In contrast to the case of
35 into 32, the transformation of the TMS and phenyl
congeners 36 and 37 into the corresponding allenyl sulones
33 and 34 smoothly proceeded at room temperature in the
respective yields of 56 and 75%.
n
Scheme 8. Reagents and conditions: (a) LiTMEDA, BuLi, then I2, THF,
K78 8C; (b) ethylene glycol, TsOH, benzene, reflux; (c) 3-(tert-
butyldiphenylsiloxy)prop-1-yne, Pd(PPh3)2Cl2, CuI, Et3N, THF, rt,
(52%); (d) 10% aqueous HCl, THF, rt; (e) 53, Et2O, 0 8C to rt, (85%);
i
(f) MOMCI, Pr2NEt, CH2Cl2, 0 8C to rt, (95%); (g) TBAF, THF, rt,
(90%); (h) PhI, Pd(PPh3)2Cl2, CuI, Et3N, THF, rt, (91%); (i) PhSOCI,
iPr2NEt, THF, K78 8C, (98%); (j) 5 mol% of [RhCl(CO2)]2, toluene, rt,
(55%); (k) 10 mol% of [RhCl(CO)dppp]2, CO, toluene, reflux, (39%).
According to the procedure described for the conversion of
22 into 24 (Table 1, entry 3), the prepared allenyl sulfone 32

C. Mukai et al. / Tetrahedron 61 (2005) 10983–10994
10987
3-Furaldehyde was iodinated by the literature procedure20 to
afford 2-iodo-3-furaldehyde, the acetalization of which with
ethylene glycol was followed by the Sonogashira coupling
reaction with 3-(tert-butyldiphenylsiloxy)prop-1-yne pro-
viding 52 in a 52% overall yield. The carbon-homologation
of 52 was performed by consecutive acid hydrolysis and the
Grignard reaction with 53 to produce 54 in 85% yield, and
the resulting secondary hydroxyl group of 54 was
subsequently protected with a methoxymethyl (MOM)
group to furnish 55 in 95% yield. Conversion of 55 into
the target molecule 59 (55% from 58) was easily achieved
by the aforementioned procedures via compounds 56 (90%),
57 (91%), and 58 (98%). The Rh(I)-catalyzed PKR of
compound 59 carried out in refluxing toluene in the
presence of 10 mol% of [RhCl(CO)dppp]2 under an
atmosphere of CO for 2 h to furnish the desired
bicyclo[6.3.0] skeleton 60 in 39% yield. Several different
conditions were examined, but found to be inferior to the
above result. It is noteworthy that compound 60 was directly
prepared in 16% yield from the sulfinic ester derivative 58
by refluxing in toluene in the presence of 10 mol% of
[RhCl(CO)2]2 under an atmosphere of CO. Compound 60
has a furan ring as well as a protected hydroxyl group, both
of which would provide the foothold for further chemical
modification of the functionalities.
disappearance of the starting material monitored by TLC.
The reaction mixture was quenched by addition of water and
extracted with AcOEt. The extract was washed with water
and brine, dried and concentrated to dryness. The residue
was passed through a short pad of silica gel with hexane–
AcOEt to afford the crude sulfoxide. To a solution of the
crude sulfoxide in CH2Cl2 (0.1 M) was added a solution of
mCPBA (1.5 equiv) in CH2Cl2 at 0 8C. The reaction mixture
was stirred until complete disappearance of the starting
material monitored by TLC. The reaction mixture was
quenched by addition of saturated aqueous Na2S2O3 and
saturated aqueous NaHCO3, and extracted with CH2Cl2.
The extract was washed with water and brine, dried, and
concentrated to dryness. The residue was chromatographed
with hexane–AcOEt to afford allenyl sulfones. Chemical
yields were summarized in Schemes.
4.1.1. 10-Phenyl-3-(phenylsulfonyl)deca-1,2-dien-9-yne
(7). A colorless oil: IR 2253, 1971, 1940, 1308,
1
1150 cmK1; H NMR d 7.93–7.86 (m, 2H), 7.66–7.47 (m,
3H), 7.40–7.23 (m, 5H), 5.34 (t, 2H, JZ3.6 Hz), 2.35 (t, 2H,
JZ6.6 Hz), 2.31–2.21 (m, 2H), 1.62–1.35 (m, 6H); 13C
NMR d 207.7, 140.1, 133.4, 131.4, 129.0, 128.1, 128.0,
127.5, 123.9, 113.2, 89.9, 84.4, 80.8, 28.2, 27.9, 26.8, 26.5,
19.2; MS m/z 350 (MC, 0.5); HRMS calcd for C22H22O2S
350.1340, found 350.1336.
3. Conclusions
4.1.2. 5,5-Bis(methoxycarbonyl)-10-phenyl-3-(phenyl-
sulfonyl)deca-1,2-dien-9-yne (11). A colorless oil: IR
In summary, we have shown that the Rh(I)-catalyzed PKR
of allenynes can be applicable for constructing medium-
sized bicyclo[6.3.0] frameworks. In fact, the bicylo[6.3.0]
undecadienones as well as their benzo and furo derivatives
could be formed in reasonable yields. In addition, the
[RhCl(CO)2]2-catalyzed [2,3]-sigmatropic rearrangement of
the sulfinic ester species of propargyl alcohols was
developed. This procedure proceeds at room temperature
to afford the allenyl sulfone derivatives in high yield. Thus,
it would become a useful method when the thermal [2,3]-
sigmatropic rearrangement of the sulfinic ester species of
propargyl alcohols is troublesome.
1967, 1936, 1732, 1308, 1153 cmK1 1H NMR d 7.93–
;
7.84 (m, 2H), 7.66–7.47 (m, 3H), 7.31–7.23 (m, 5H), 5.32 (t,
2H, JZ3.3 Hz), 3.65 (s, 6H), 2.93 (t, 2H, JZ3.3 Hz), 2.32
(t, 2H, JZ6.9 Hz), 2.12–2.01 (m, 2H), 1.43–1.20 (m, 2H);
13C NMR d 208.1, 170.4, 139.7, 133.6, 131.5, 129.1, 128.2,
127.6, 123.8, 108.9, 89.1, 85.5, 81.1, 56.6, 52.6, 31.1, 28.5,
23.4, 19.4; MS m/z 466 (MC, 1.9); HRMS calcd for
C26H26O6S 466.1450, found 466.1445.
4.1.3. 1-(But-3-ynyl)-2-[2-(phenylsulfonyl)buta-2,3-di-
enyl]benzene (22). A colorless oil: IR 3308, 2118, 1967,
1
1935, 1308, 1151 cmK1; H NMR d 7.92–7.82 (m, 2H),
4. Experimental
7.66–7.57 (m, 1H), 7.56–7.47 (m, 2H), 7.19–6.99 (m, 4H),
5.17 (t, 2H, JZ3.6 Hz), 3.62 (t, 2H, JZ3.6 Hz), 2.62 (t, 2H,
JZ7.6 Hz), 2.28 (td, 2H, JZ7.6, 2.6 Hz), 1.94 (t, 1H, JZ
2.6 Hz); 13C NMR d 208.3, 139.9, 138.5, 133.8, 133.5,
130.4, 129.2, 129.0, 127.9, 127.3, 126.5, 113.2, 84.7, 83.3,
69.1, 31.0, 30.8, 19.6; MS m/z 322 (MC, 0.5). Anal. Calcd
for C20H18O2S: C, 74.50; H, 5.63. Found: C, 74.30; H,
5.65.
Melting points are uncorrected. Infrared spectra were
measured in CHCl3. 1H NMR spectra were taken in
chloroform-d (CDCl3). CHCl3 (7.26 ppm) for silyl com-
pounds and tetramethylsilane (0.00 ppm) for compounds
without a silyl group was used as an internal standard. 13C
NMR spectra were recorded in CDCl3 with CDCl3
(77.0 ppm) as an internal standard. All reactions were
carried out under N2 atmosphere unless otherwise stated.
Silica gel (Silica gel 60, 40–50 mm) was used for
chromatography. Organic extracts were dried over
anhydrous Na2SO4.
4.1.4. 1-(4-Phenylbut-3-ynyl)-2-[2-(phenylsulfonyl)buta-
2,3-dienyl]benzene (23). A colorless oil: IR 1967, 1935,
1308, 1151 cmK1; 1H NMR d 7.92–7.84 (m, 2H), 7.62–7.44
(m, 3H), 7.38–7.00 (m, 9H), 5.18 (t, 2H, JZ4.0 Hz), 3.67 (t,
2H, JZ4.0 Hz), 2.69 (t, 2H, JZ7.3 Hz), 2.50 (t, 2H, JZ
7.3 Hz); 13C NMR d 208.4, 140.1, 138.9, 133.9, 133.5,
131.4, 130.5, 129.6, 129.1, 128.2, 128.1, 127.7, 127.3,
126.6, 123.7, 113.4, 89.1, 84.7, 81.5, 31.4, 30.9, 20.8; MS
m/z 399 (MC, 0.3). Anal. Calcd for C26H22O2S: C, 78.36; H,
5.56. Found: C, 78.02; H, 5.60.
4.1. General procedure for preparation of allenyl
sulfones with PhSCl and mCPBA
To a solution of propargyl alcohol in THF (0.1 M) were
added successively Et3N (3.0 equiv) and PhSCl (1.5 equiv)
at K78 8C. The reaction mixture was stirred until complete

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4.2. General procedure for preparation of propargyl
sulphinates
MS m/z 322 (MC, 0.4); HRMS calcd for C20H18O2S
322.1027, found 322.1023.
To a solution of propargyl alcohol in THF (0.1 M) were
added successively iPr2NEt (3.0 equiv) and PhSOCl
(1.5 equiv) at K78 8C. After stirring for 1.5 h, the reaction
mixture was quenched by addition of water and extracted
with AcOEt. The extract was washed with water and brine,
dried and concentrated to dryness. The residue was
chromatographed with hexane–AcOEt to afford propargyl
sulfinate. Chemical yields were summarized in Schemes.
4.2.6. 1-(5-Phenylpent-4-ynyl)-2-[3-(phenylsulfinyloxy)
prop-1-ynyl]benzene (36). A colorless oil: IR 2224 cmK1
;
1H NMR d 7.78–7.75 (m, 2H), 7.55–7.51 (m, 3H), 7.41–
7.36 (m, 3H), 7.31–7.22 (m, 5H), 7.19–7.12 (m, 1H), 4.85,
4.58 (AB-q, 2H, JZ16 Hz), 2.90 (t, 2H, JZ7.6 Hz), 2.41 (t,
2H, JZ7.3 Hz), 1.92 (quin, 2H, JZ7.3 Hz); 13C NMR d
144.3, 144.0, 132.7, 132.4, 131.5, 129.1, 129.0, 128.2,
127.6, 125.9, 125.3, 123.9, 121.4, 89.8, 86.7, 86.3, 81.1,
53.0, 33.5, 29.4, 19.0; FABMS m/z 399 (MCC1, 3.3);
FABHRMS calcd for C26H23O2S 399.1419, found
399.1428.
4.2.1. 5-Phenylpent-2-yn-1-yl benzenesulfinate (41). A
colorless oil: H NMR d 7.74–7.71 (m, 2H), 7.56–7.53 (m,
1
3H), 7.31–7.17 (m, 5H), 4.62 (dt, 1H, JZ15, 2.2 Hz), 4.33
(dt, 1H, JZ15, 2.2 Hz), 2.79 (t, 2H, JZ7.6 Hz), 2.48 (tt, 2H,
JZ7.6, 2.2 Hz); 13C NMR d 144.4, 140.3, 132.3, 129.0,
128.4, 128.3, 126.3, 125.3, 88.5, 74.6, 52.9, 34.6, 20.9; MS
m/z 284 (MC, 3.6); HRMS calcd for C17H16O2S 284.0871,
found 284.0870.
4.2.7. 1-[3-(Phenylsulfinyloxy)prop-1-ynyl]-2-[5-(tri-
methylsilyl)pent-4-ynyl]benzene (37). A pale yellow oil:
IR 2224, 2172 cmK1; 1H NMR d 7.81–7.77 (m, 2H), 7.59–
7.53 (m, 3H), 7.38–7.35 (m, 1H), 7.29–7.11 (m, 3H), 4.89,
4.62 (AB-q, 2H, JZ16 Hz), 2.82 (t, 2H, JZ7.3 Hz), 2.23 (t,
2H, JZ7.3 Hz), 1.83 (quin, 2H, JZ7.3 Hz), 0.15 (s, 9H);
13C NMR d 144.3, 144.0, 132.7, 132.4, 129.1, 129.0, 125.9,
125.3, 121.3, 107.0, 86.7, 86.3, 84.9, 52.9, 33.4, 29.3, 19.4,
0.1; FABMS m/z 395 (MCC1, 2.2); FABHRMS calcd for
C23H27O2SiS 395.1501, found 395.1509.
4.2.2. 6-Phenylhex-3-yn-2-yl benzenesulfinate (42). As a
mixture of diastereomers. Compound 42 was a colorless oil:
1
IR 2245 cmK1; H NMR for one isomer d 7.72–7.69 (m,
2H), 7.55–7.49 (m, 3H), 7.32–7.20 (m, 5H), 5.04 (qt, 1H,
JZ6.6, 2.0 Hz), 2.86 (t, 2H, JZ7.6 Hz), 2.56 (td, 2H, JZ
7.6, 2.0 Hz), 1.49 (d, 3H, JZ6.6 Hz); 13C NMR for one
isomer d 145.6, 140.3, 132.1, 128.9, 128.5, 128.4, 126.4,
4.2.8. 3-[1-(Methoxymethoxy)-5-phenylpent-4-ynyl]-2-
[3-(phenylsulfinyloxy)prop-1-ynyl]furan (58). As a
mixture of diastereomers. Compound 58 was a colorless
1
125.1, 87.5, 79.4, 65.4, 34.7, 23.3, 20.9; H NMR data for
1
oil: IR 2230 cmK1; H NMR d 7.75–7.71 (m, 2H), 7.55–
the other isomer d 7.74–7.71 (m, 2H), 7.54–7.47 (m, 3H),
7.31–7.15 (m, 5H), 5.00 (qt, 1H, JZ6.6, 2.0 Hz), 2.71 (t,
2H, JZ7.6 Hz), 2.37 (td, 2H, JZ7.6, 2.0 Hz), 1.55 (d, 3H,
JZ6.6 Hz); 13C NMR data for the other isomer d 144.8,
140.4, 132.0, 128.8, 128.4, 128.3, 126.3, 125.4, 86.9, 79.2,
63.3, 34.6, 24.1, 20.8; MS m/z 298 (MC, 2.7); HRMS calcd
for C18H18O2S 298.1027, found 298.1025.
7.49 (m, 3H), 7.41–7.35 (m, 2H), 7.33 (d, 1H, JZ2.0 Hz),
7.28–7.23 (m, 3H), 6.42 (d, 1H, JZ2.0 Hz), 4.92–4.86 (m,
1H), 4.80–4.74 (m, 1H), 4.59–4.45 (m, 3H), 3.37 (m, 3H),
2.59–2.43 (m, 2H), 2.18–2.09 (m, 1H), 1.96–1.87 (m, 1H);
13C NMR d 144.3, 144.1, 144.1, 133.8, 133.7, 132.4, 131.7,
131.7, 131.4, 129.0, 128.2, 127.6, 125.3, 125.2, 123.7,
109.7, 94.2, 90.4, 88.9, 88.9, 81.2, 76.7, 68.6, 55.6, 52.3,
52.3, 35.0, 35.0, 15.8, 15.8; FABMS m/z 449 (MCC1,
13.7); FABHRMS calcd for C26H25O5S 449.1422, found
449.1415.
4.2.3. 2-Methyl-6-phenylhex-3-yn-2-yl benzenesulfinate
(43). A colorless oil: IR 2241 cmK1; 1H NMR d 7.70–7.65
(m, 2H), 7.52–7.48 (m, 3H), 7.35–7.17 (m, 5H), 2.88 (t, 2H,
JZ7.4 Hz), 2.60 (t, 2H, JZ7.4 Hz), 1.74 (s, 3H), 1.62 (s,
3H); 13C NMR d 146.6, 140.3, 131.5, 128.8, 128.5, 128.3,
126.3, 125.0, 88.0, 82.0, 76.4, 34.7, 31.2, 31.0, 20.9; MS m/z
312 (MC, 11.3); HRMS calcd for C19H20O2S 312.1184,
found 312.1190.
4.3. General procedure for Rh(I)-catalyzed synthesis of
allenyl sulfones from propargyl sulfinates
To a solution of sulfinates (0.1 mmol) in toluene (1 mL) was
added 5 mol% of [RhCl(CO)2]2. Then the reaction mixture
was stirred at room temperature for several hours. The
solvent was evaporated off, and the residue was chromato-
graphed to afford allenyl sulfones. Chemical yields were
summarized in Schemes.
4.2.4. 3-Phenylprop-2-ynyl benzenesulfinate (47). A
colorless oil: IR 2228 cmK1 1H NMR d 7.83–7.76 (m,
;
2H), 7.62–7.53 (m, 3H), 7.42–7.26 (m, 5H), 4.84, 4.58 (AB-
q, 2H, JZ5.6 Hz); 13C NMR d 144.2, 144.1, 132.4, 131.8,
129.1, 128.8, 128.2, 125.3, 87.9, 82.8, 52.5; MS m/z 256
(MC, 1.2); HRMS calcd for C15H12O2S 256.0558, found
256.0565.
4.3.1. 5-Phenyl-3-(phenylsulfonyl)penta-1,2-diene (44). A
colorless oil: IR 1969, 1940, 1317, 1150 cmK1; 1H NMR d
7.89–7.86 (m, 2H), 7.63–7.50 (m, 3H), 7.26–7.06 (m, 5H),
5.31 (t, 2H, JZ3.3 Hz), 2.74 (t, 2H, JZ7.2 Hz), 2.58–2.50
(m, 2H); 13C NMR d 208.0, 140.2, 140.1, 133.4, 129.1,
128.4, 128.3, 128.1, 126.2, 112.4, 84.5, 33.6, 28.4; MS m/z
284 (MC, 8.3); FABHRMS calcd for C17H17O2S 285.0949,
found 285.0952 (MCC1).
4.2.5. 1-(Pent-4-ynyl)-2-[3-(phenylsulfinyloxy)prop-1-
ynyl]benzene (35). A pale yellow oil: IR 3308, 2224,
1
2116 cmK1; H NMR d 7.81–7.77 (m, 2H), 7.59–7.53 (m,
3H), 7.38–7.11 (m, 4H), 4.89, 4.61 (AB-q, 2H, JZ16 Hz),
2.85 (t, 2H, JZ7.6 Hz), 2.20 (td, 2H, JZ6.9, 2.6 Hz), 1.97
(t, 1H, JZ2.6 Hz), 1.83 (quin, 2H, JZ6.9 Hz); 13C NMR d
144.0, 132.7, 132.4, 129.1, 129.0, 128.9, 125.9, 125.4,
125.3, 121.4, 86.6, 86.3, 84.2, 68.7, 52.9, 33.3, 29.3, 18.0;
4.3.2. 6-Phenyl-4-(phenylsulfonyl)hexa-2,3-diene (45). A
colorless oil: IR 1963, 1315, 1148 cmK1; 1H NMR d 7.87–
7.84 (m, 2H), 7.61–7.51 (m, 3H), 7.26–7.05 (m, 5H), 5.66

C. Mukai et al. / Tetrahedron 61 (2005) 10983–10994
10989
(qt, 1H, JZ7.4, 2.8 Hz), 2.76–2.71 (m, 2H), 2.58 (qd, 2H,
JZ8.1, 2.8 Hz), 1.60 (d, 3H, JZ7.4 Hz); 13C NMR d 204.8,
140.3, 140.1, 133.2, 129.0, 128.4, 128.3, 128.0, 126.1,
111.9, 96.4, 33.5, 28.3, 13.2; MS m/z 298 (MC, 5.3);
FABHRMS calcd for C18H19O2S 299.1106, found 299.1104
(MCC1).
4.28 (AB-q, 2H, JZ6.9 Hz), 3.33 (s, 3H), 2.54–2.33 (m,
2H), 1.99–1.87 (m, 1H), 1.60–1.50 (m, 1H); 13C NMR d
209.4, 144.3, 140.2, 138.0, 133.6, 131.4, 128.9, 128.3,
128.2, 127.7, 127.3, 123.7, 109.9, 106.5, 93.6, 89.1, 84.4,
81.2, 67.2, 55.5, 34.9, 15.8; MS m/z 448 (MC, 22.1);
FABHRMS calcd for C26H25O5S 449.1422, found 449.1435
(MCC1).
4.3.3. 2-Methyl-6-phenyl-4-(phenylsulfonyl)hexa-2,3-
diene (46). A colorless oil: IR 1963, 1313, 1148 cmK1
;
4.4. General procedure for Rh(I)-catalyzed PKR
1H NMR d 7.86–7.82 (m, 2H), 7.62–7.47 (m, 3H),
7.26–7.06 (m, 5H), 2.75 (t, 2H, JZ6.9 Hz), 2.61 (t, 2H,
JZ6.9 Hz), 1.58 (s, 6H); 13C NMR d 202.2, 140.6, 140.3,
133.0, 128.9, 128.3, 128.2, 127.9, 126.0, 110.2, 107.3, 33.6,
28.1, 19.5; MS m/z 312 (MC, 10.8); FABHRMS calcd for
C19H21O2S 313.1262, found 313.1264 (MCC1).
To a solution of allenylalkyne (0.1 mmol) in solvent (1 mL)
was added Rh(I) catalyst (5, 10 or 20 mol%). Then the
reaction mixture was warmed to the temperature shown in
text under CO atmosphere until complete disappearance of
the starting material monitored by TLC. The solvent was
evaporated off, and the residue was chromatographed to
afford cyclized products. Chemical yields were summarized
in Schemes.
4.3.4. 1-Phenyl-1-(phenylsulfonyl)propa-1,2-diene (48).
A colorless oil: IR 1963, 1927, 1321, 1153 cmK1; 1H NMR
d 7.82–7.79 (m, 2H), 7.56–7.26 (m, 8H), 5.55 (s, 2H); 13C
NMR d 209.1, 140.3, 140.2, 133.4, 128.9, 128.8, 128.6,
128.5, 128.2, 115.2, 83.9; MS m/z 256 (MC, 7.2);
FABHRMS calcd for C15H13O2S 257.0637, found
257.0657 (MCC1).
4.4.1. 9-Phenyl-2-(phenylsulfonyl)bicyclo[6.3.0]undeca-
1,8-dien-10-one (8). Colorless needles: mp 184.5–187 8C
1
(CHCl3–hexane); IR 1707, 1306, 1150 cmK1; H NMR d
7.93–7.89 (m, 2H), 7.64 (t, 1H, JZ7.3 Hz), 7.57 (t, 2H, JZ
7.3 Hz), 7.46–7.35 (m, 3H), 7.25–7.19 (m, 2H), 3.79 (s, 2H),
3.07 (t, 2H, JZ6.8 Hz), 2.93 (t, 2H, JZ7.1 Hz), 1.78 (quin,
2H, JZ7.1 Hz), 1.66–1.49 (m, 4H); 13C NMR d 201.6,
164.9, 148.6, 147.0, 140.7, 134.7, 133.5, 130.6, 129.3,
129.1, 128.8, 128.4, 127.6, 40.9, 28.3, 27.6, 27.4, 26.1, 21.5;
MS m/z 378 (MC, 64.5); HRMS calcd for C23H22O3S
378.1289, found 378.1288.
4.3.5. 1-(Pent-4-ynyl)-2-[1-(phenylsulfonyl)propa-1,2-
dienyl]benzene (32). A pale yellow oil: IR 3308, 1967,
1931, 1321, 1153 cmK1; 1H NMR d 7.71–7.12 (m, 9H), 5.47
(s, 2H), 2.45 (t, 2H, JZ7.9 Hz), 2.10 (td, 2H, JZ6.9,
2.6 Hz), 1.98 (t, 1H, JZ2.6 Hz), 1.57 (quin, 2H, JZ6.9 Hz);
13C NMR d 208.2, 141.7, 139.6, 133.5, 131.1, 129.6, 129.4,
128.8, 128.7, 127.5, 125.9, 112.5, 84.0, 82.9, 68.8, 31.8,
29.5, 18.3; MS m/z 322 (MC, 0.4); HRMS calcd for
C20H18O2S 322.1028, found 322.1024.
4.4.2. 4,4-Bis(methoxycarbonyl)-9-phenyl-2-(phenyl-
sulfonyl)bicyclo[6.3.0]undeca-1,8-dien-10-one (12).
Colorless powders: mp 254–256 8C (CHCl3–hexane); IR
1
4.3.6. 1-(5-Phenylpent-4-ynyl)-2-[1-(phenylsulfonyl)
propa-1,2-dienyl]benzene (33). A colorless oil: IR 2232,
1730, 1709, 1308, 1150 cmK1; H NMR d 7.94–7.86 (m,
2H), 7.69–7.52 (m, 3H), 7.46–7.34 (m, 3H), 7.22–7.14 (m,
2H), 3.94–3.71 (m, 8H), 3.61 (d, 1H, JZ17 Hz), 3.34 (d,
1H, JZ22 Hz), 3.00–2.70 (m, 2H), 2.36–2.12 (m, 2H),
1.85–1.60 (m, 2H); 13C NMR d 200.6, 171.3, 170.8, 163.2,
149.7, 149.2, 141.1, 133.6, 133.4, 130.2, 129.5, 129.1,
128.5, 127.6, 56.7, 53.1, 40.8, 32.2, 27.5, 26.8, 24.0; MS m/z
494 (MC, 16.3); FABHRMS calcd for C27H27O7S
495.1477, found 495.1488 (MCC1).
1
1967, 1931, 1321, 1153 cmK1; H NMR d 7.68–7.66 (m,
2H), 7.58–7.54 (m, 1H), 7.44–7.34 (m, 4H), 7.32–7.28 (m,
4H), 7.26–7.15 (m, 3H), 5.46 (s, 2H), 2.51 (t, 2H, JZ
7.9 Hz), 2.33 (t, 2H, JZ6.9 Hz), 1.64 (quin, 2H, JZ6.9 Hz);
13C NMR d 208.1, 141.9, 139.4, 133.5, 131.5, 131.1, 129.6,
129.4, 128.8, 128.6, 128.3, 127.7, 127.5, 125.9, 123.7,
112.4, 89.6, 82.9, 81.2, 32.0, 29.8, 19.2; MS m/z 398 (MC,
24.9); HRMS calcd for C26H22O2S 398.1341, found
398.1342.
4.4.3. 11-(Phenylsulfonyl)-1,4,5,10-tetrahydro-2H-
benzo[g]cyclopentacycloocten-2-one (24). Colorless
powders: mp 155–157 8C (hexane–AcOEt); IR 1701,
4.3.7. 1-[1-(Phenylsulfonyl)propa-1,2-dienyl]-2-[5-(tri-
methylsilyl)pent-4-ynyl]benzene (34). A pale yellow oil:
1
1308, 1150 cmK1; H NMR d 7.81–7.75 (m, 2H), 7.66–
1
IR 2170, 1967, 1931, 1321, 1153 cmK1; H NMR d 7.70–
7.57 (m, 1H), 7.55–7.45 (m, 2H), 7.17–6.98 (m, 4H), 6.33
(s, 1H), 4.23 (br s, 2H), 3.45–3.14 (m, 6H); 13C NMR d
202.2, 171.7, 146.4, 140.6, 138.8, 137.9, 136.2, 135.6,
133.6, 131.5, 131.3, 129.3, 127.7, 127.2, 126.6, 41.9, 34.0,
32.6, 29.7; MS m/z 350 (MC, 43.3); HRMS calcd for
C21H18O3S 350.0977, found 350.0975.
7.56 (m, 3H), 7.47–7.41 (m, 2H), 7.30–7.14 (m, 4H), 5.50
(s, 2H), 2.44 (t, 2H, JZ7.9 Hz), 2.14 (t, 2H, JZ6.9 Hz),
1.55 (quin, 2H, JZ6.9 Hz), 0.18 (s, 9H); 13C NMR d 208.2,
141.9, 139.6, 133.5, 131.0, 129.6, 129.4, 128.8, 128.6,
127.5, 125.9, 112.4, 106.9, 85.1, 82.9, 32.0, 29.7, 19.7, 0.2;
MS m/z 394 (MC, 1.6). Anal. Calcd for C23H26OSSi: C,
70.01; H, 6.64. Found: C, 69.99; H, 6.96.
4.4.4. 3-Phenyl-11-(phenylsulfonyl)-1,4,5,10-tetrahydro-
2H-benzo[g]cyclopentacycloocten-2-one (25). Pale yellow
powders: mp 227–229 8C (CHCl3–hexane); IR 1709, 1308,
4.3.8. 3-[1-(Methoxymethoxy)-5-phenylpent-4-ynyl]-2-
[1-(phenylsulfonyl)propa-1,2-dienyl]furan (59). A color-
less oil: IR 1965, 1917, 1325, 1153 cmK1; 1H NMR d 7.86
(d, 2H, JZ7.3 Hz), 7.58 (t, 1H, JZ7.3 Hz), 7.50–7.43 (m,
3H), 7.42–7.38 (m, 2H), 7.34–7.28 (m, 3H), 6.40 (d, 1H, JZ
1.7 Hz), 5.56 (s, 2H), 4.69 (dd, 1H, JZ9.3, 4.4 Hz), 4.34,
1
1148 cmK1; H NMR d 7.87–7.79 (m, 2H), 7.67–7.37 (m,
6H), 7.33–7.24 (m, 2H), 7.15–7.01 (m, 3H), 6.96–6.89 (m,
1H), 4.25 (br s, 2H), 3.59 (br s, 2H), 3.24 (s, 4H); 13C NMR
d 200.8, 164.7, 148.8, 146.8, 140.7, 136.9, 136.6, 136.6,
133.5, 130.9, 130.8, 130.3, 129.3, 129.3, 129.2, 128.5,

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C. Mukai et al. / Tetrahedron 61 (2005) 10983–10994
127.8, 127.3, 127.0, 41.8, 34.8, 33.0, 28.3; MS m/z 426
(MC, 29.6); FABHRMS calcd for C27H23O3S 427.1368,
found 427.1368 (MCC1).
8.40 mL, 11.6 mmol) at K78 8C. After stirring for 30 min, a
solution of 3 (2.28 g, 7.73 mmol) in THF–DMPU (5/1,
10 mL) was gradually added to the reaction mixture, which
was stirred at room temperature for 14 h. The reaction
mixture was quenched by addition of saturated aqueous
NH4Cl and extracted with AcOEt. The extract was washed
with water and brine, dried, and concentrated to dryness.
The residue was chromatographed with hexane–AcOEt
(10/1) to afford 4 (2.33 g, 51%) as a colorless oil: IR
4.4.5. 11-(Phenylsulfonyl)-1,4,5,6-tetrahydro-2H-benzo-
[f]cyclopentacycloocten-2-one (49). Colorless powders:
mp 126–129 8C (CHCl3–hexane); IR 1701, 1321,
1
1150 cmK1; H NMR d 7.79–7.72 (m, 1H), 7.48–7.45 (m,
3H), 7.33–7.25 (m, 4H), 6.96–6.95 (m, 1H), 6.27 (s, 1H),
3.85, 3.80 (AB-q, 2H, JZ22 Hz), 2.46–2.38 (m, 2H), 2.26
(td, 1H, JZ13, 5.9 Hz), 1.85–1.70 (m, 2H), 1.66–1.57 (m,
1H); 13C NMR d 202.7, 171.9, 146.3, 139.9, 139.7, 138.2,
138.1, 135.3, 133.2, 131.2, 131.0, 130.3, 128.6, 127.8,
125.9, 41.6, 31.2, 30.2, 27.2; MS m/z 350 (MC, 100);
HRMS calcd for C21H18O3S 350.0977, found 350.0979.
1
2170 cmK1; H NMR d 7.78–7.69 (m, 4H), 7.46–7.34 (m,
6H), 4.32 (t, 2H, JZ2.0 Hz), 2.27–2.10 (m, 4H), 1.60–1.37
(m, 6H), 1.07 (s, 9H), 0.16 (s, 9H); 13C NMR d 135.6, 133.4,
129.7, 127.6, 107.4, 85.5, 84.4, 78.6, 53.0, 28.2, 28.0, 27.9,
26.7, 19.8, 19.2, 18.7, 0.2; FABMS m/z 461 (MCC1, 3.3).
Anal. Calcd for C29H40OSi: C, 75.59; H, 8.75. Found: C,
75.67; H, 8.75.
4.4.6. 3-Phenyl-11-(phenylsulfonyl)-1,4,5,6-tetrahydro-
2H-benzo[f]cyclopentacycloocten-2-one (50). Pale yellow
plates: mp 219–221.5 8C (CHCl3–hexane); IR 1707, 1321,
4.5.2. Deca-2,9-diyn-1-ol (5). To a solution of 4 (2.33 g,
5.06 mmol) in THF (50 mL) was added TBAF (1.0 M in
THF solution, 12 mL, 12 mmol) at room temperature. After
stirring for 30 min, THF was evaporated off, and the residue
was chromatographed with hexane–AcOEt (5/1) to afford 5
1
1150 cmK1; H NMR d 7.76–7.74 (m, 1H), 7.52–7.20 (m,
12H), 6.97–6.95 (m, 1H), 4.01, 3.92 (AB-q, 2H, JZ22 Hz),
2.63–2.58 (m, 1H), 2.49–2.41 (m, 1H), 2.37 (td, 1H, JZ13,
4.9 Hz), 1.80–1.75 (m, 2H), 1.60–1.56 (m, 1H); 13C NMR d
201.2, 164.9, 147.7, 146.1, 140.2, 140.0, 135.0, 133.1,
131.4, 131.2, 130.5, 130.3, 129.1, 128.8, 128.6, 128.4,
127.8, 127.6, 125.9, 40.8, 31.3, 30.4, 24.2; MS m/z 426
(MC, 60.1); FABHRMS calcd for C27H23O3S 427.1368,
found 427.1357 (MCC1).
(0.710 g, 93%) as a colorless oil: IR 3609, 3441, 2226 cmK1
;
1H NMR d 4.23 (t, 2H, JZ2.3 Hz), 2.28–2.13 (m, 4H), 1.94
(t, 1H, JZ2.6 Hz), 1.72 (br s, 1H), 1.59–1.42 (m, 6H); 13C
NMR d 86.3, 84.4, 78.5, 68.3, 51.4, 28.0, 27.9, 27.9, 18.6,
18.3; MS m/z 150 (MC, 3.6); HRMS calcd for C10H14O
150.1044, found 150.1053.
4.4.7. 11-(Phenylsulfonyl)-3-(trimethylsilyl)-1,4,5,6-
tetrahydro-2H-benzo[f]cyclopentacycloocten-2-one
(51). Pale yellow needles: mp 153.5–156 8C (hexane–THF);
IR 1695, 1317, 1148 cmK1; 1H NMR d 7.75–7.68 (m, 1H),
7.50–7.42 (m, 3H), 7.35–7.20 (m, 4H), 6.98–6.90 (m, 1H),
3.81, 3.70(AB-q, 2H, JZ22 Hz), 2.61(dt, 1H, JZ13, 2.8 Hz),
2.45–2.34 (m, 1H), 2.27 (td, 1H, JZ13, 5.9 Hz), 1.82 (td, 1H,
JZ13, 4.6 Hz), 1.75–1.50 (m, 2H), 0.23 (s, 9H); 13C NMR d
207.2, 177.4, 150.6, 147.7, 140.2, 140.1, 134.0, 133.5, 131.2,
131.1, 130.2, 128.6, 127.8, 127.6, 125.8, 42.0, 31.6, 30.3, 26.4,
K0.3; MS m/z 422 (MC, 1.9). Anal. Calcd for C24H26O3SSi:
C, 68.21; H, 6.20. Found: C, 68.25; H, 6.49.
4.5.3. 10-Phenyldeca-2,9-diyn-1-ol (6). To a solution of 5
(580 mg, 3.83 mmol) in THF (38 mL) were added
Pd(PPh3)2Cl2 (26.9 mg, 3.83!10K2 mmol) and CuI
(14.6 mg, 7.66!10K2 mmol) at room temperature. Iodo-
benzene (0.85 mL, 7.7 mmol) and iPr2NH (5.02 mL,
38.3 mmol) were then added dropwise to the reaction
mixture. After being stirred for 24 h, the reaction mixture
was filtered by suction. The filtrate was concentrated, and
the residue was chromatographed with hexane–AcOEt (5/1)
to afford 6 (688 mg, 79%) as a colorless oil: IR 3609, 3445,
2253, 2226 cmK1; 1H NMR d 7.42–7.36 (m, 2H), 7.30–7.24
(m, 3H), 4.23 (s, 2H), 2.41 (t, 2H, JZ6.8 Hz), 2.28–2.20 (m,
2H), 1.70 (br s, 1H), 1.66–1.52 (m, 6H); 13C NMR d 131.5,
128.1, 127.5, 124.0, 90.0, 86.2, 80.8, 78.5, 51.3, 28.2, 28.1,
28.0, 19.2, 18.6; MS m/z 226 (MC, 4.3); HRMS calcd for
C16H18O 226.1358, found 226.1354.
4.4.8.
4-(Methoxymethoxy)-7-phenyl-10-(phenyl-
sulfonyl)-4,5,6,9-tetrahydro-8H-cyclopentacycloocta[5,
6-b]furan-8-one (60). Pale yellow powders: mp 219–
1
221 8C (CHCl3–hexane); IR 1710, 1310, 1151 cmK1; H
NMR d 7.89 (d, 2H, JZ7.6 Hz), 7.56–7.38 (m, 7H), 7.30–
7.20 (m, 2H), 6.39 (d, 1H, JZ1.7 Hz), 4.59 (dd, 1H, JZ12,
6.1 Hz), 4.51, 4.39 (AB-q, 2H, JZ6.8 Hz), 3.97, 3.85 (AB-
q, 2H, JZ23 Hz), 3.33 (s, 3H), 2.76 (d, 1H, JZ13 Hz),
2.22–2.10 (m, 1H), 1.91 (td, 1H, JZ13, 5.1 Hz), 1.86–1.76
(m, 1H); 13C NMR d 200.7, 163.2, 149.6, 141.7, 141.0,
133.4, 130.4, 129.4, 129.1, 129.0, 128.9, 128.6, 127.5,
127.0, 108.6, 94.9, 69.3, 55.8, 40.5, 37.2, 25.0; MS m/z 476
(MC, 37.9); FABHRMS calcd for C27H25O6S 477.1372,
found 477.1371 (MCC1).
4.5.4. 5,5-Bis(methoxycarbonyl)deca-2,9-diyn-1-ol (9).
To a solution of dimethyl malonate (1.14 mL, 10.0 mmol)
in THF (70 mL) was added NaH (60% in mineral oil,
520 mg, 13.0 mmol) at 0 8C. After stirring for 30 min, a
solution of 5-iodopent-1-yne (3.19 g, 12.0 mmol) in THF
(30 mL) was gradually added to the reaction mixture, which
was stirred at room temperature for 36 h. The reaction
mixture was quenched by addition of saturated aqueous
NH4Cl and extracted with AcOEt. The extract was washed
with water and brine, dried, and concentrated to dryness.
The residue was passed through a short pad of silica gel with
hexane–AcOEt (4/1) to afford the crude alkyne. To a
solution of the crude alkyne in THF (70 mL) was added
NaH (60% in mineral oil, 416 mg, 10.4 mmol) at 0 8C. After
stirring for 10 min, a solution of 4-iodo-1-(tert-butyldiphe-
nylsiloxy)but-2-yne (3.16 g, 7.27 mmol) in THF (17 mL)
was gradually added to the reaction mixture, which was
4.5. Preparation of propargyl alcohol derivatives
4.5.1. 10-(tert-Butyldiphenylsiloxy)-1-(trimethylsilyl)
deca-1,8-diyne (4). To a solution of 3-(tert-butyldiphenyl-
siloxy)prop-1-yne (2.96 g, 10.0 mmol) in THF–DMPU (5/1,
90 mL) was added nBuLi (1.38 M in hexane solution,

C. Mukai et al. / Tetrahedron 61 (2005) 10983–10994
10991
stirred at room temperature for 1.5 h. The reaction mixture
was quenched by addition of saturated aqueous NH4Cl and
extracted with AcOEt. The extract was washed with water
and brine, dried, and concentrated to dryness. The residue
was passed through a short pad of silica gel with hexane–
AcOEt (6/1) to afford the crude diyne. To a solution of the
crude diyne in THF (44 mL) was added TBAF (1.0 M in
THF solution, 4.9 mL, 4.9 mmol) at room temperature.
After stirring for 1.5 h, THF was evaporated off, and the
residue was chromatographed with hexane–AcOEt (3/1) to
afford 9 (1.17 g, 44%) as a colorless oil: IR 3607, 3508,
3308, 2118, 1726 cmK1; 1H NMR d 4.19 (br s, 2H), 3.73 (s,
6H), 2.84 (t, 2H, JZ2.0 Hz), 2.21 (td, 2H, JZ6.9, 2.6 Hz),
2.17–2.07 (m, 2H), 1.96 (t, 1H, JZ2.6 Hz), 1.93 (br s, 1H),
1.50–1.33 (m, 2H); 13C NMR d 170.5, 83.3, 81.7, 79.6, 68.7,
56.5, 52.6, 50.5, 31.2, 23.1, 23.0, 18.3; MS m/z 266 (MC,
0.7); HRMS calcd for C14H18O5 266.1155, found 266.1161.
CH2Cl2 (15 mL) were added PPh3 (637 mg, 3.00 mmol) and
CBr4 (746 mg, 2.25 mmol) at 0 8C, and the reaction mixture
was stirred at room temperature for 1 h. CH2Cl2 was
evaporated off, and the residue was chromatographed with
hexane–AcOEt (30/1) to afford 17 (438 mg, 99%) as a
colorless oil: IR 2172 cmK1; 1H NMR d 7.38–7.15 (m, 4H),
4.59 (s, 2H), 2.98 (t, 2H, JZ7.6 Hz), 2.59 (t, 2H, JZ
7.6 Hz), 0.15 (s, 9H); 13C NMR d 139.4, 135.7, 130.5, 130.1,
129.0, 127.0, 106.1, 85.7, 31.6, 31.1, 21.4, 0.0; MS m/z 294
(MC, 1.2), 296 (MC, 1.2). Anal. Calcd for C14H19BrSi: C,
56.94; H, 6.49. Found: C, 56.77; H, 6.56.
4.5.8. 2-(But-3-ynyl)-1-(4-hydroxybut-2-ynyl)benzene
(20). Lithium acetylide, prepared from 1-(tert-butyl-
dimethylsiloxy)prop-2-yne (766 mg, 4.50 mmol) and
nBuLi (1.42 M in hexane, 3.24 mL, 4.60 mmol), in THF
(1.3 mL) was added to a suspension of InCl3 (354 mg,
1.60 mmol) in THF (10 mL) at K78 8C. After being stirred
for 30 min, the resulting solution was then added to a
solution of 17 (809 mg, 2.74 mmol) and Pd(dppf)Cl2
(CH2Cl2 complex, 22.4 mg, 2.70!10K2 mmol) in THF
(12 mL). The reaction mixture was refluxed for 18.5 h,
quenched by addition of MeOH and 10% aqueous HCl, and
extracted with Et2O. The extract was washed with water and
brine, dried, and concentrated to dryness. The residue was
passed through a short pad of silica gel with hexane–AcOEt
(50/1) to afford the crude diyne 19. To a solution of the
crude 19 in THF (23 mL) was added TBAF (1.0 M in THF
solution, 7.0 mL, 7.0 mmol) at 0 8C, and the reaction
mixture was stirred for 1 h. THF was evaporated off, and
the residue was chromatographed with hexane–AcOEt (4/1)
to afford 20 (354 mg, 65%) as a colorless oil: IR 3606, 3439,
3306, 2118 cmK1; 1H NMR d 7.42–7.36 (m, 1H), 7.22–7.16
(m, 3H), 4.25 (t, 2H, JZ2.4 Hz), 3.61 (t, 2H, JZ2.4 Hz),
2.89 (t, 2H, JZ7.8 Hz), 2.48 (td, 2H, JZ7.8, 2.4 Hz), 2.10
(br s, 1H), 1.99 (t, 1H, JZ2.4 Hz); 13C NMR d 138.1, 134.4,
129.2, 129.0, 127.1, 126.8, 83.7, 83.6, 80.6, 69.1, 51.2, 31.3,
22.8, 19.6; MS m/z 198 (MC, 2.4); HRMS calcd for
C14H14O 198.1044, found 198.1042.
4.5.5. 5,5-Bis(methoxycarbonyl)-10-phenyldeca-2,9-
diyn-1-ol (10). According to the procedure for preparation
of 6 from 5, 10 (530 mg, 77%) was obtained from 9
(532 mg, 2.00 mmol) as a colorless oil: IR 3607, 3471,
1
1732 cmK1; H NMR d 7.43–7.33 (m, 2H), 7.31–7.24 (m,
3H), 4.20–4.10 (m, 2H), 3.74 (s, 6H), 2.88 (t, 2H, JZ
2.3 Hz), 2.44 (t, 2H, JZ7.3 Hz), 2.26–2.16 (m, 2H), 1.95–
1.81 (m, 1H), 1.60–1.42 (m, 2H); 13C NMR d 170.7, 131.5,
128.2, 127.6, 123.8, 89.2, 81.7, 81.2, 80.3, 56.9, 52.7, 51.0,
31.5, 23.6, 23.3, 19.5; MS m/z 342 (MC, 2.4); HRMS calcd
for C20H22O5 342.1467, found 342.1465.
4.5.6. 2-(Hydroxymethyl)-1-[4-(trimethylsilyl)but-3-
ynyl]benzene (16). To a suspension of zinc powder
(1.31 g, 20.0 mmol) in DMA (8.0 mL) was added I2
(254 mg, 1.00 mmol) at room temperature. The reaction
mixture was stirred until the red color of I2 disappeared.
Then a solution of 4-bromo-1-(trimethylsilyl)but-1-yne
(2.05 g, 10.0 mmol) in DMA (2.0 mL) was added and the
reaction mixture was warmed to 80 8C. After stirring for 3 h,
a solution of 13 (1.76 g, 5.05 mmol) in DMA (1.0 mL) and
Pd(PPh3)4 (289 mg, 0.250 mmol) were added to the reaction
mixture, which was stirred at 80 8C for 1 h. The reaction
mixture was filtered through a Celite pad, and the filtrate
was diluted with 10% aqueous HCl and extracted with Et2O.
The extract was washed with water and brine, dried and
concentrated to dryness. The residue was passed through a
short pad of silica gel with hexane–AcOEt (20/1) to afford
the crude 15. To a solution of the crude 15 in THF (50 mL)
was added TsOH–H2O (476 mg, 2.50 mmol) at room
temperature. After being stirred for 13 h, the reaction
mixture was quenched by addition of saturated aqueous
NaHCO3 and extracted with AcOEt. The extract was
washed with water and brine, dried, and concentrated to
dryness. The residue was chromatographed with hexane–
AcOEt (4/1) to afford 16 (727 mg, 62%) as a colorless oil:
IR 3609, 3503, 2170 cmK1; 1H NMR d 7.40–7.20 (m, 4H),
4.74 (s, 2H), 2.94 (t, 2H, JZ7.6 Hz), 2.55 (t, 2H, JZ
7.6 Hz), 1.71 (s, 1H), 0.14 (s, 9H); 13C NMR d 138.8, 138.5,
129.7, 128.6, 128.0, 126.7, 106.7, 85.6, 63.1, 31.1, 21.9, 0.0;
MS m/z 232 (MC, 4.5). Anal. Calcd for C14H20OSi: C,
72.36; H, 8.67. Found: C, 72.11; H, 8.95.
4.5.9. 1-(4-Hydroxybut-2-ynyl)-2-(4-phenylbut-3-ynyl)
benzene (21). According to the procedure for preparation
of 6 from 5, 21 (301 mg, 73%) was obtained from 20
(297 mg, 1.50 mmol) as a colorless oil: IR 3607, 3383,
1
2226 cmK1; H NMR d 7.44–7.34 (m, 3H), 7.30–7.18 (m,
6H), 4.26 (t, 2H, JZ2.0 Hz), 3.66 (t, 2H, JZ2.0 Hz), 2.97
(t, 2H, JZ7.8 Hz), 2.70 (t, 2H, JZ7.8 Hz), 1.83 (br s, 1H);
13C NMR d 138.3, 134.5, 131.5, 129.4, 129.0, 128.2, 127.7,
127.2, 126.8, 123.6, 89.3, 83.8, 81.4, 80.6, 51.3, 31.7, 22.9,
20.8; MS m/z 274 (MC, 2.1); HRMS calcd for C20H18O
274.1357, found 274.1349.
4.5.10. 1-Bromo-2-[3-(tert-butyldimethylsiloxy)prop-1-
ynyl]benzene (27). According to the procedure for
preparation of 6 from 5, 27 (552 mg, 85%) was obtained
from 26 (0.25 mL, 2.00 mmol) as a colorless oil: 1H NMR d
7.57 (dd, 1H, JZ7.9, 1.3 Hz), 7.46 (dd, 1H, JZ7.9, 1.7 Hz),
7.25 (td, 1H, JZ7.6, 1.3 Hz), 7.15 (td, 1H, JZ7.6, 1.7 Hz),
4.59 (s, 2H), 0.94 (s, 9H), 0.18 (s, 6H); 13C NMR d 133.6,
132.4, 129.4, 126.9, 125.4, 125.1, 92.5, 83.2, 52.3, 25.8,
18.3, K5.0; MS m/z 323 (MC, 2.5), 325 (MC, 2.6). Anal.
Calcd for C15H21OBrSi: C, 55.38; H, 6.51. Found: C, 55.06;
H, 6.45.
4.5.7. 2-(Bromomethyl)-1-[4-(trimethylsilyl)but-3-ynyl]
benzene (17). To a solution 16 (349 mg, 1.50 mmol) in

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C. Mukai et al. / Tetrahedron 61 (2005) 10983–10994
4.5.11. 1-(3-Hydroxyprop-1-ynyl)-2-(pent-4-ynyl)ben-
zene (29). According to the procedure for preparation of
15 from 13, the crude 28 was obtained from 27 (975 mg,
3.00 mmol). To a solution of the crude 28 in THF (20 mL)
was added TBAF (1.0 M in THF solution, 5.0 mL,
5.0 mmol) at 0 8C. After stirring for 10 min, THF was
evaporated off, and the residue was chromatographed with
hexane–AcOEt (4/1) to afford 29 (438 mg, 74%) as a
128.3, 128.2, 126.3, 87.9, 85.6, 51.2, 34.9, 20.8; MS m/z 160
(MC, 3.7); FABHRMS calcd for C11H12ONa 183.0786,
found 183.0794 (MCC23).
4.5.15. 6-Phenylhex-3-yn-2-ol (39). To a solution of
4-phenylbut-1-yne (421 mg, 3.23 mmol) in THF (32 mL)
was added nBuLi (1.47 M in hexane solution, 3.30 mL,
4.85 mmol) at K78 8C. After stirring for 1 h, CH3CHO
(0.91 mL, 16 mmol) was added to the reaction mixture,
which was stirred for 1 h. The reaction mixture was
quenched by addition of saturated aqueous NH4Cl and
extracted with AcOEt. The extract was washed with water
and brine, dried and concentrated to dryness. The residue
was chromatographed with hexane–AcOEt (5/1) to afford
39 (529 mg, 94%) as a colorless oil: IR 3603, 3420,
1
colorless oil: IR 3607, 3431, 3306, 2233, 2116 cmK1; H
NMR d 7.43–7.40 (m, 1H), 7.29–7.13 (m, 3H), 4.53 (d, 2H,
JZ6.0 Hz), 2.90 (t, 2H, JZ7.6 Hz), 2.24 (td, 2H, JZ6.9,
2.6 Hz), 2.01 (t, 1H, JZ2.6 Hz), 1.87 (quin, 2H, JZ7.0 Hz),
1.71 (t, 1H, JZ6.0 Hz); 13C NMR d 143.7, 132.4, 129.0,
128.6, 126.0, 122.0, 90.8, 84.5, 84.3, 68.6, 51.8, 33.3, 29.2,
18.1; MS m/z 198 (MC, 2.5); FABHRMS calcd for
C14H14ONa 221.0943, found 221.0954 (MCC23).
1
2241 cmK1; H NMR d 7.33–7.20 (m, 5H), 4.64–4.55 (m,
1H), 2.82 (t, 2H, JZ7.6 Hz), 2.49 (td, 2H, JZ7.6, 1.8 Hz),
1.70 (d, 1H, JZ5.1 Hz), 1.41 (d, 3H, JZ6.4 Hz); 13C NMR
d 140.6, 128.4, 128.3, 126.3, 83.9, 83.1, 58.5, 35.0, 24.6,
20.8; MS m/z 174 (MC, 2.8); FABHRMS calcd for
C12H14ONa 197.0942, found 197.0951 (MCC23).
4.5.12. 1-(3-Hydroxyprop-1-ynyl)-2-(5-phenylpent-4-
ynyl)benzene (30). According to the procedure for
preparation of 6 from 5, 30 (120 mg, 73%) was obtained
from 29 (118 mg, 0.600 mmol) as a colorless oil: IR 3607,
3425, 2232 cmK1; 1H NMR d 7.44–7.39 (m, 3H), 7.31–7.13
(m, 6H), 4.46 (d, 2H, JZ6.3 Hz), 2.96 (t, 2H, JZ7.9 Hz),
2.46 (t, 2H, JZ6.9 Hz), 1.96 (quin, 2H, JZ6.9 Hz), 1.63 (t,
1H, JZ6.3 Hz); 13C NMR d 143.8, 132.5, 131.5, 129.0,
128.6, 128.3, 127.7, 125.9, 123.9, 122.0, 90.8, 90.0, 84.3,
81.1, 51.7, 33.5, 29.4, 19.1; MS m/z 274 (MC, 4.7);
FABHRMS calcd for C20H18ONa 297.1256, found
297.1246 (MCC23).
4.5.16. 2-Methyl-6-phenylhex-3-yn-2-ol (40).19 According
to the procedure for preparation of 39, 40 (495 mg, 79%)
was obtained from 4-phenylbut-1-yne (435 mg, 3.34 mmol)
and CH3COCH3 (1.20 mL, 16.7 mmol) as a colorless oil: IR
3599, 3431, 2235 cmK1; 1H NMR d 7.33–7.20 (m, 5H), 2.81
(t, 2H, JZ7.6 Hz), 2.47 (t, 2H, JZ7.6 Hz), 1.84 (s, 1H),
1.47 (s, 6H).
4.5.13. 1-(3-Hydroxyprop-1-ynyl)-2-[5-(trimethylsilyl)
pent-4-ynyl]benzene (31). According to the procedure for
preparation of 15 from 13, the crude 28 was obtained from
27 (846 mg, 2.60 mmol). To a solution of the crude 28 in
THF (20 mL) was added 10% aqueous HCl (5.0 mL) at
room temperature. After being stirred for 1 h, the reaction
mixture was quenched by addition of saturated aqueous
NaHCO3 and extracted with AcOEt. The extract was
washed with water and brine, dried and concentrated to
dryness. The residue was chromatographed with hexane–
AcOEt (3/1) to afford 31 (557 mg, 78%) as a colorless oil:
IR 3607, 3454, 2233, 2170 cmK1; 1H NMR d 7.42–7.39 (m,
1H), 7.28–7.11 (m, 3H), 4.52 (s, 2H), 2.87 (t, 2H, JZ
7.6 Hz), 2.27 (t, 2H, JZ7.3 Hz), 1.95 (s, 1H), 1.87 (quin,
2H, JZ7.3 Hz), 0.17 (s, 9H); 13C NMR d 143.7, 132.4,
129.0, 128.6, 125.9, 122.0, 107.3, 90.8, 85.0, 84.3, 51.6,
33.5, 29.2, 19.5, 0.2; MS m/z 270 (MC, 0.2). Anal. Calcd for
C17H22OSi: C, 75.50; H, 8.20. Found: C, 75.23; H, 8.58.
4.5.17. 2-[3-(tert-Butyldiphenylsiloxy)prop-1-ynyl]-3-(2,
5-dioxolanyl)furan (52). To a solution of N,N,N0-trimethyl-
ethylenediamine (3.40 mL, 26.0 mmol) in THF (40 mL)
was added nBuLi (1.46 M in hexane solution, 16.8 mL,
24.0 mmol) at K78 8C. After stirring for 10 min, 3-fur-
aldehyde (1.73 mL, 20.0 mmol) was gradually added, and
n
the reaction mixture was stirred for 20 min. Then BuLi
(35.0 mL, 50.0 mmol) was added dropwise to the reaction
mixture, which was stirred for 2 h. A solution of I2 (25.4 g,
100 mmol) in THF (10 mL) was added to the reaction
mixture. After being stirred for 1 h, the reaction mixture was
quenched by addition of saturated aqueous Na2S2O3 and
extracted with AcOEt. The extract was washed with water
and brine, dried and concentrated to dryness. The residue
was passed through a short pad of silica gel with hexane–
AcOEt (5/1) to afford the crude iodide. To a solution of the
crude iodide in benzene (31 mL) were added ethylene
glycol (2.09 mL, 37.5 mmol) and TsOH–H2O (476 mg,
2.50 mmol), and the reaction mixture was refluxed for 1.5 h
under azeotropic removal of water. The reaction mixture
was quenched by addition of Et3N and extracted with
AcOEt. The extract was washed with water and brine, dried
and concentrated to dryness. The residue was passed
through a short pad of silica gel with hexane–AcOEt (5/1)
to afford the crude acetal. According to the procedure for
preparation of 6 from 5, 52 (4.49 g, 52%) was obtained from
the crude acetal as a pale yellow oil: 1H NMR d 7.76–7.68
(m, 4H), 7.48–7.35 (m, 6H), 7.32 (d, 1H, JZ2.0 Hz), 6.47
(d, 1H, JZ2.0 Hz), 5.79 (s, 1H), 4.56 (s, 2H), 4.18–3.91 (m,
4H), 1.07 (s, 9H); 13C NMR d 143.4, 135.7, 135.5, 132.8,
129.8, 127.7, 109.1, 97.8, 94.9, 73.6, 65.1, 53.0, 26.6, 19.1;
MS m/z 432 (MC, 2.2). Anal. Calcd for C26H28O4Si: C,
72.19; H, 6.52. Found: C, 71.95; H, 6.58.
4.5.14. 5-Phenylpent-2-yn-1-ol (38). To a solution of
4-phenylbut-1-yne (1.36 g, 10.5 mmol) in THF (100 mL)
was added nBuLi (1.47 M in hexane solution, 10.7 mL,
15.8 mmol) at K78 8C. After stirring for 1 h, (HCHO)n
(1.58 g, 52.5 mmol) was added to the reaction mixture,
which was stirred for 2 h. The reaction mixture was
quenched by addition of saturated aqueous NH4Cl and
extracted with AcOEt. The extract was washed with water
and brine, dried and concentrated to dryness. The residue
was chromatographed with hexane–AcOEt (2/1) to afford
38 (1.64 g, 97%) as a colorless oil: IR 3609, 3427,
1
2222 cmK1; H NMR d 7.33–7.20 (m, 5H), 4.23 (dt, 2H,
JZ5.9, 2.1 Hz), 2.83 (t, 2H, JZ7.6 Hz), 2.51 (tt, 2H, JZ
7.6, 2.1 Hz), 1.53 (t, 1H, JZ5.9 Hz); 13C NMR d 140.5,

C. Mukai et al. / Tetrahedron 61 (2005) 10983–10994
10993
4.5.18. 2-[3-(tert-Butyldiphenylsiloxy)prop-1-ynyl]-3-[1-
hydroxy-5-(trimethylsilyl)pent-4-ynyl]furan (54). To a
solution of 52 (433 mg, 1.00 mmol) in THF (10 mL) was
added 10% aqueous HCl (3.0 mL) at room temperature.
After being stirred for 1 h, the reaction mixture was
quenched by addition of saturated aqueous NaHCO3, and
extracted with AcOEt. The extract was washed with water
and brine, dried and concentrated to dryness. The residue
was passed through a short pad of silica gel with hexane–
AcOEt (10/1) to afford the crude aldehyde. To a solution of
53 (1.0 M in Et2O solution, 9.9 mL, 9.9 mmol) was added
crude aldehyde in Et2O (10 mL) at 0 8C, and the reaction
mixture was stirred at room temperature for 1 h. The
reaction mixture was quenched by addition of 10% aqueous
HCl and extracted with AcOEt. The extract was washed
with water and brine, dried and concentrated to dryness. The
residue was chromatographed with hexane–AcOEt (8/1) to
afford 54 (868 mg, 85%) as a pale yellow oil: IR 3599, 3524,
4.5.21.
2-(3-Hydroxyprop-1-ynyl)-3-[1-(methoxy-
methoxy)-5-phenylpent-4-ynyl]furan (57). According to
the procedure for preparation of 6 from 5, 57 (369 mg, 91%)
was obtained from 56 (310 mg, 1.25 mmol) as a pale yellow
oil: IR 3601, 3422, 2230 cmK1; H NMR d 7.43–7.39 (m,
1
2H), 7.33 (d, 1H, JZ2.0 Hz), 7.31–7.24 (m, 3H), 6.42 (d,
1H, JZ2.0 Hz), 4.95 (dd, 1H, JZ8.3, 5.6 Hz), 4.63, 4.53
(AB-q, 2H, JZ6.8 Hz), 4.37 (s, 2H), 3.41 (s, 3H), 2.65–2.42
(m, 3H), 2.22–2.12 (m, 1H), 1.99–1.89 (m, 1H); 13C NMR d
143.9, 134.8, 131.4, 130.3, 128.2, 127.7, 123.8, 109.5, 95.1,
93.8, 89.0, 81.3, 74.5, 68.2, 55.6, 51.2, 34.7, 16.0; MS m/z
324 (MC, 0.5). Anal. Calcd for C20H20O4: C, 74.06; H, 6.21.
Found: C, 73.85; H, 6.52.
Acknowledgements
This work was supported in part by a Grant-in Aid for
Scientific Research from the Ministry of Education, Culture,
Sports Science and Technology, Japan, for which we are
thankful.
1
2172 cmK1; H NMR d 7.75–7.71 (m, 4H), 7.48–7.37 (m,
6H), 7.31 (d, 1H, JZ2.0 Hz), 6.44 (d, 1H, JZ2.0 Hz), 4.78
(dd, 1H, JZ7.8, 5.1 Hz), 4.57 (s, 2H), 2.32 (td, 2H, JZ7.3,
1.0 Hz), 2.05 (br s, 1H), 2.04–1.94 (m, 1H), 1.92–1.83 (m,
1H), 1.08 (s, 9H), 0.14 (s, 9H); 13C NMR d 143.6, 135.6,
133.2, 132.9, 132.9, 129.8, 127.7, 109.3, 106.5, 95.2, 85.3,
74.1, 65.9, 53.1, 36.1, 26.7, 19.2, 16.4, 0.1; MS m/z 514
(MC, 0.8). Anal. Calcd for C31H38O3Si2: C, 72.33; H, 7.44.
Found: C, 71.97; H, 7.46.
References and notes
1. For leading reviews, see: (a) Pauson, P. L. In Aspects of a
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4.5.19. 2-[3-(tert-Butyldiphenylsiloxy)prop-1-ynyl]-3-[1-
(methoxymethoxy)-5-(trimethylsilyl)pent-4-ynyl]furan
(55). To a solution of 54 (419 mg, 0.814 mmol) in CH2Cl2
i
(8.1 mL) were added Pr2NEt (0.28 mL, 1.6 mmol) and
MOMCl (0.12 mL, 1.63 mmol) at 0 8C, and the reaction
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was chromatographed with hexane–AcOEt (8/1) to afford
1
55 (432 mg, 95%) as a pale yellow oil: IR 2172 cmK1; H
NMR d 7.79–7.74 (m, 4H), 7.49–7.41 (m, 6H), 7.33 (d, 1H,
JZ2.0 Hz), 6.41 (d, 1H, JZ2.0 Hz), 4.78 (dd, 1H, JZ8.1,
5.4 Hz), 4.62–4.56 (m, 3H), 4.53 (d, 1H, JZ6.6 Hz), 3.38
(s, 3H), 2.36 (td, 2H, JZ7.8, 2.0 Hz), 2.13–2.04 (m, 1H),
1.95–1.86 (m, 1H), 1.12 (s, 9H), 0.17 (s, 9H); 13C NMR d
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109.7, 106.4, 94.9, 94.3, 84.9, 73.9, 68.9, 55.6, 53.1, 35.2,
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7.72.
2. For attempts at constructing the bicyclo[5.3.0]decenone
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´
of enynes with an aromatic ring as a template, see: (a) Perez-
4.5.20.
2-(3-Hydroxyprop-1-ynyl)-3-[1-(methoxy-
´
´
methoxy)pent-4-ynyl]furan (56). According to the pro-
cedure for preparation of 5 from 4, 56 (28.5 mg, 90%) was
obtained from 55 (71.4 mg, 0.128 mmol) as a colorless oil:
Serrano, L.; Casarrubios, L.; Domınguez, G.; Perez-Castells, J.
Chem. Commun. 2001, 2602–2603. (b) Krafft, M. E.; Fu, Z.;
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1
IR 3603, 3420, 3308, 2118 cmK1; H NMR d 7.33 (d, 1H,
JZ2.0 Hz), 6.40 (d, 1H, JZ2.0 Hz), 4.83 (dd, 1H, JZ8.3,
5.9 Hz), 4.64–4.46 (m, 4H), 3.39 (s, 3H), 2.61 (br s, 1H),
2.37–2.25 (m, 2H), 2.17–2.01 (m, 1H), 1.99 (t, 1H, JZ
2.6 Hz), 1.95–1.79 (m, 1H); 13C NMR d 143.9, 134.7, 130.4,
109.5, 95.1, 93.9, 83.5, 74.7, 68.8, 68.2, 55.7, 51.4, 34.6,
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C. Mukai et al. / Tetrahedron 61 (2005) 10983–10994
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