Efficient construction of the bicyclo[5.3.0]decenone skeleton based on the Rh(I)-catalyzed allenic Pauson-Khand reaction

Article abstract of DOI:10.1021/jo020649h

A reliable procedure for constructing a bicyclo[5.3.0]deca-1,7-dien-9-one ring system by rhodium-catalyzed Pauson-Khand reaction (PKR) of allenynes with a sulfonyl group has been developed. Investigation of the rhodium-catalyzed PKR on 19 examples of 1,2-nonadien-8-yne derivatives demonstrated that (i) acceptable yields could be consistently achieved through the proper choice of the rhodium catalyst ([RhCl(CO)₂]₂ or [RhCl(CO)dppp]₂) depending on the starting allenyne and that (ii) an ester functionality as well as hydroxy and siloxy groups could be tolerated in this rhodium-catalyzed PKR.

Full text of DOI:10.1021/jo020649h

Efficien t Con str u ction of th e Bicyclo[5.3.0]d ecen on e Sk eleton
Ba sed on th e Rh (I)-Ca ta lyzed Allen ic P a u son -Kh a n d Rea ction
Chisato Mukai,* Izumi Nomura, and Shinji Kitagaki
Faculty of Pharmaceutical Sciences, Kanazawa University,
Takara-machi 13-1, Kanazawa 920-0934, J apan
cmukai@kenroku.kanazawa-u.ac.jp
Received October 14, 2002
A reliable procedure for constructing a bicyclo[5.3.0]deca-1,7-dien-9-one ring system by rhodium-
catalyzed Pauson-Khand reaction (PKR) of allenynes with a sulfonyl group has been developed.
Investigation of the rhodium-catalyzed PKR on 19 examples of 1,2-nonadien-8-yne derivatives
demonstrated that (i) acceptable yields could be consistently achieved through the proper choice of
the rhodium catalyst ([RhCl(CO)2]2 or [RhCl(CO)dppp]2) depending on the starting allenyne and
that (ii) an ester functionality as well as hydroxy and siloxy groups could be tolerated in this
rhodium-catalyzed PKR.
In tr od u ction
When the enyne 1 (n ) 3) was submitted to similar
ring closure conditions, however, none of target bicyclo-
[5.3.0]decenone derivative 2 (n ) 3)3 could be detected
in the reaction mixture. Contrary to our expectations, the
unexpected bicyclo[4.3.0]nonenone compound 3 with a
methyl group R to the carbonyl moiety was produced in
a stereoselective manner. The formation of 3 could
tentatively be rationalized in terms of the intermediacy
of the cobalt complex 43 with the isomerized internal
double bond, which should give rise to the formation of
3. In fact, the application of the Co2(CO)8-mediated
intramolecular PKR of the enynes to the synthesis of the
bicyclo[5.3.0] ring system3,4 has not yet been realized,
except for the preparation of the azabicyclo[5.3.0]-
decenone derivatives5 and medium-sized oxacyclic com-
pounds6,7 from enynes with an aromatic ring as a
template.
On the other hand, the alkyne derivatives 5 with an
allenyl functionality8-11 instead of an olefin group were
found to produce the corresponding bicyclo[5.3.0]deca-
1,7-dien-9-one 6 under Co2(CO)8-mediated PKR condi-
tions,8c although the chemical yields were far from
satisfactory. In addition, Narasaka9 has developed a new
procedure for the synthesis of bicyclo[5.3.0]deca-1,7-dien-
9-one 8 in low yield (15%) from allenyne 7 through an
Fe(CO)4(NMe3)-mediated PKR-type reaction. If a straight-
The Co2(CO)8-mediated Pauson-Khand reaction (PKR)1
is well recognized as a formal [2 + 2 + 1] cyclization of
three components, an alkyne, an alkene, and carbon
monoxide, on the two cobalt atoms of the cluster complex
to produce cyclopentenone derivatives. The intramolecu-
lar version of this intriguing [2 + 2 + 1] cyclization
procedure has emerged as one of the most convenient and
straightforward methods for the construction of the
bicyclo[m.3.0] skeletons (m ) 3, 4) in one operation.
Recent efforts from this laboratory have established an
efficient procedure for the highly stereoselective con-
struction of the optically active bicyclo[3.3.0]octenone 2
(n ) 1)2a,b and bicyclo[4.3.0]nonenone 2 (n ) 2)2c,d
frameworks having a bis(tert-butyldimethylsiloxy) func-
tionality (R ) TBDMS) at both the allyl and homoallyl
positions based on an intramolecular PKR of the optically
active enyne 1 (n ) 1, 2), which was easily derived from
L-tartrate. This scheme would allow us to prepare the
enantiomer of 2 when the commercially available D-
tartrate is employed as a starting material.
* Phone: +81-76-234-4411. Fax: +81-76-234-4410.
(1) For leading reviews, see: (a) Pauson, P. L. In Organometallics
in Organic Synthesis. Aspects of a Modern Interdisciplinary Field; de
Meijere, A., tom Dieck, H., Eds.; Springer: Berlin, 1988; pp 233-246.
(b) Schore, N. E. Chem. Rev. 1988, 88, 1081-1119. (c) Schore, N. E.
Org. React. 1991, 40, 1-90. (d) Schore, N. E. In Comprehensive Organic
Synthesis; Trost, B. M., Ed.; Pergamon: Oxford, 1991; Vol. 5, pp 1037-
1064. (e) Schore, N. E. In Comprehensive Organometallic Chemistry
II; Abel, E. W., Stone, F. G. A., Wilkinson, G., Eds.; Elsevier: New
York, 1995; Vol. 12, pp 703-739. (f) Fru¨hauf, H.-W. Chem. Rev. 1997,
97, 523-596. (g) J eong, N. In Transition Metals in Organic Synthesis;
Beller, H., Bolm, C., Eds; Wiley-VCH: Weinheim, Germany, 1998; Vol.
1, pp 560-577. (h) Geis, O.; Schmalz, H.-G. Angew. Chem., Int. Ed.
1998, 37, 911-914. (i) Chung, Y. K. Coord. Chem. Rev. 1999, 188, 297-
341. (j) Brummond, K. M.; Kent, J . L. Tetrahedron 2000, 56, 3263-
3283.
(3) Mukai, C.; Sonobe, H.; Kim, J . S.; Hanaoka, M. J . Org. Chem.
2000, 65, 6654-6659.
(4) A bicyclo[5.3.0]decenone framework with an oxygen-bridged
structure was synthesized in 29% yield by the zirconocene-mediated
PKR. See: Wender, P. A.; McDonald, F. E. Tetrahedron Lett. 1990,
31, 3691-3694. However, this structure can be regarded as an
oxabicyclo[4.3.0]nonenone skeleton. In addition, attempted Co2(CO)8-
mediated PKR was unsuccessful.
(5) Pe´rez-Serrano, L.; Casarrubios, L.; Dom´ınguez, G.; Pe´rez-
Castells, J . Chem. Commun. 2001, 2602-2603.
(2) (a) Mukai, C.; Uchiyama, M.; Sakamoto, S.; Hanaoka, M.
Tetrahedron Lett. 1995, 36, 5761-5764. (b) Mukai, C.; Kim, J . S.;
Uchiyama, M.; Sakamoto, S.; Hanaoka, M. J . Chem. Soc., Perkin Trans.
1 1998, 2903-2915. (c) Mukai, C.; Kim. J . S.; Uchiyama, M.; Hanaoka,
M. Tetrahedron Lett. 1998, 39, 7909-7912. (d) Mukai, C.; Kim, J . S.;
Sonobe, H.; Hanaoka, M. J . Org. Chem. 1999, 64, 6822-6832.
(6) (a) Krafft, M. E.; Fu, Z.; Bon˜aga, L. V. R. Tetrahedron Lett. 2001,
42, 1427-1431. (b) Lovely, C. J .; Seshadri, H.; Wayland, B. R.; Cordes,
A. W. Org. Lett. 2001, 3, 2607-2610.
(7) Zr-Mediated PKR for the preparation of medium-sized rings with
an aromatic ring was also reported. Barluenga, J .; Sanz, R.; Fan˜ana´s,
F. J . Chem. Eur. J . 1997, 3, 1324-1336.
10.1021/jo020649h CCC: $25.00 © 2003 American Chemical Society
Published on Web 01/25/2003
1376
J . Org. Chem. 2003, 68, 1376-1385

Construction of the Bicyclo[5.3.0]decenone Skeleton
SCHEME 1
forward efficient procedure for the preparation of bicyclo-
[5.3.0]decane ring systems under PKR conditions in an
acceptable yield could be developed, it would become a
useful alternative method for the synthesis of many
bioactive natural products possessing a bicyclo[5.3.0]-
decane skeleton12 as the basic carbon core framework.
In this paper, we describe the efficient rhodium-
catalyzed PKR of allenynes for the construction of
2-phenylsulfonylbicyclo[5.3.0]deca-1,7-dien-9-one deriva-
tives.13,14
Resu lts a n d Discu ssion
P au son -Kh an d Reaction of 3-P h en ylsu lfon ylocta-
1,2-d ien -7-yn e Der iva tives. We have devoted consider-
able attention to allenynes with a sulfinyl or sulfonyl
group as starting materials for this investigation, because
(i) various allenynes could be prepared from the corre-
sponding propargyl alcohols through a [2,3]-sigmatropic
rearrangement by using arenesulfenyl halide15 and (ii)
chemical transformation of the sulfur-containing groups
into other functionalities would be easily achieved. At the
beginning of this program, our first efforts were focused
on the PKR of the octa-1,2-dien-7-yne species 11 and 12
to find efficient and practical conditions for constructing
the bicyclo[4.3.0]nonane and/or bicyclo[3.3.0]octane ring
systems. Thus, the required allenynes 11 and 12 were
easily prepared from 4-pentyn-1-ol (9) via the [2,3]-
sigmatropic rearrangement of the propargyl alcohol 10
as shown in Scheme 3. Introduction of a silyl group at
the triple-bond terminus of 9 was followed by iodination
to give the corresponding iodo derivative, which was
subsequently exposed to the coupling reaction with
3-(tert-butyldiphenylsiloxy)prop-1-yne producing the diyne
SCHEME 2
SCHEME 3 a
(8) For Co-mediated PKR of allenynes, see: (a) Ahmar, M.; Antras,
F.; Cazes, B. Tetrahedron Lett. 1995, 36, 4417-4420. (b) Ahmar, M.;
Chabanis, O.; Gauthier, J .; Cazes, B. Tetrahedron Lett. 1997, 38, 5277-
5280. (c) Ahmar, M.; Locatelli, C.; Colombier, D.; Cazes, B. Tetrahedron
Lett. 1997, 38, 5281-5284. (d) Pagenkopf, B. L.; Belanger, D. B.;
O’Mahony, D. J . R.; Livinghouse, T. Synthesis 2000, 1009-1019. (e)
Antras, F.; Ahmar, M.; Cazes, B. Tetrahedron Lett. 2001, 42, 8153-
8156. (f) Antras, F.; Ahmar, M.; Cazes, B. Tetrahedron Lett. 2001, 42,
8157-8160.
a
Reaction conditions: (a) nBuLi, TMSCl, THF, -78 °C, then 10%
HCl, rt; (b) I2, PPh3, imidazole, CH2Cl2, rt; (c) TBDPSOCH2CtCH,
nBuLi, THF-DMPU, -78 °C; (d) 10% HCl, MeOH, rt, (59%); (e)
(9) For Fe-mediated PKR of allenynes, see: Shibata, T.; Koga, Y.;
Narasaka, K. Bull. Chem. Soc. J pn. 1995, 68, 911-919.
i
TBAF, THF, rt, (72%); (f) PhI, CuI, Pd(PPh3)2Cl2, Pr2NH, THF,
(10) For Mo-mediated PKR of allenynes, see: (a) Kent, J . L.; Wan,
H.; Brummond, K. M. Tetrahedron Lett. 1995, 36, 2407-2410. (b)
Brummond, K. M.; Wan, H. Tetrahedron Lett. 1998, 39, 931-934. (c)
Brummond, K. M.; Wan, H.; Kent, J . L. J . Org. Chem. 1998, 63, 6535-
6545. (d) Brummond, K. M.; Lu, J . J . Am. Chem. Soc. 1999, 121, 5087-
5088. (e) Brummond, K. M.; Lu, J .; Petersen, J . J . Am. Chem. Soc.
2000, 122, 4915-4920. (f) Xiong, H.; Hsung, R. P.; Wei, L.-L.; Berry,
C. R.; Mulder, J . A.; Stockwell, B. Org. Lett. 2000, 2, 2869-2871. (g)
Brummond, K. M.; Kerekes, A. D.; Wan, H. J . Org. Chem. 2002, 67,
5156-5163.
rt, (82%); (g) PhSCl, Et3N, THF, -78 °C, (96%); (h) (i) PhSCl, Et3N,
THF, -78 °C, (ii) mCPBA, CH2Cl2, 0 °C, 12a (85%), 12b (74%),
12c (84%).
derivative. Subsequent removal of the silyl group on the
primary hydroxyl group furnished 10a in 59% overall
yield. The other diynes 10b and 10c16 were obtained from
10a under conventional conditions. Exposure of 10a to
benzenesulfenyl chloride15 in THF at -78 °C in the
presence of Et3N brought about the following transfor-
mation: (i) sulfenic ester formation, and (ii) the [2,3]-
sigmatropic rearrangement resulting in the formation of
the sulfinyl allenyne 11 in 96% yield. However, the
Pauson-Khand reaction of 11 under several conditions
was unsuccessful, presumably due to the sulfinyl moiety
that might act as a weak oxidant leading to the deactiva-
tion of the catalysts employed. Therefore, we next
examined the PKR of the sulfonyl derivatives 12, which
(11) For Zr-mediated PKR of allenynes, see refs 10b, 10c and 10g.
(12) For example, see: (a) Herz, W.; Santhanam, P. S. J . Org. Chem.
1965, 30, 4340-4342. (b) Lansbury, P. T.; Hangauer, D. G., J r.; Vacca,
J . P. J . Am. Chem. Soc. 1980, 102, 3964-3965. (c) Heathcock, C. H.;
DelMar, E. G.; Graham, S. L. J . Am. Chem. Soc. 1982, 104, 1907-
1917. (d) Grieco, P. A.; Majetich, G. F.; Ohfune, Y. J . Am. Chem. Soc.
1982, 104, 4226-4233. (e) Heathcock, C. H.; Tice, C. M.; Germroth, T.
C. J . Am. Chem. Soc. 1982, 104, 6081-6091.
(13) Part of this work was published as a preliminary communica-
tion: Mukai, C.; Nomura, I.; Yamanishi, K.; Hanaoka, M. Org. Lett.
2002, 4, 1755-1758.
(14) Brummond and co-workers very recently reported the [RhCl-
(CO)2]2-catalyzed PKR of allenynes, which includes three examples of
the formation of bicyclo[5.3.0]deca-1,7-dien-9-one derivatives: Brum-
mond, K. M.; Chen, H.; Fisher, K. D.; Kerekes, A. D.; Rickards, B.;
Sill, P. C.; Geib, S. J . Org. Lett. 2002, 4, 1931-1934.
(16) Sonogashira, K.; Tohda, Y.; Hagihara, N. Tetrahedron Lett.
1975, 4467-4470.
(15) Horner, L.; Binder, V. Ann. Chem. 1972, 757, 33-68.
J . Org. Chem, Vol. 68, No. 4, 2003 1377

Mukai et al.
TABLE 1. P a u son -Kh a n d Rea ction of 12a
TABLE 2. P a u son -Kh a n d Rea ction of 12 w ith Rh (I)
Ca ta lyst
yield
(%)
entry
1
condition
product
entry
R
conditiona
product
yield (%)
Co2(CO)8, TMANO, 4 Å MS,
toluene, -10 °C
Co2(CO)8, MeCN, 75 °C
Mo(CO)6, DMSO, toluene, 100 °C
Fe(CO)4(NMe3), THF, hν, -30 °C
Fe2(CO)9, DMSO, toluene, 100 °C
Ru3(CO)12, DMF, 5 atm of CO, 130 °C
13a
52
1
2
3
4
5
6
TMS
H
Ph
TMS
H
Ph
A
A
A
B
B
B
13a
13b
13c
13a
13b
13c
63
56
58
97
85
65
2
3
4
5
6
13a
13a
13a
13a
46
trace
18
18
0
a
Condition A: 2.5 mol % [RhCl(CO)2]2, toluene, 1 atm CO.
Condition B: 2.5 mol % [RhCl(CO)dppp]2, toluene, 1 atm CO.
was easily prepared from 10 by consecutive sulfinylation
and mCPBA oxidation (Scheme 3).
J eong20 and Narasaka21 independently disclosed that
rhodium(I) catalysts are effective in the PKR of enynes.
To develop a high-yielding reliable procedure for prepar-
ing bicyclo[4.3.0]nonadienone as well as bicyclo[5.3.0]-
decadienone derivatives from allenynes by PKR,22 we
applied these rhodium-catalyzed conditions to the ring
closure reaction of 12a . The results are summarized in
Table 2. According to Narasaka’s procedure,21 12a was
treated with a catalytic amount of commercially available
[RhCl(CO)2]2 (2.5 mol %) in refluxing toluene under a
carbon monoxide atmosphere (conditions A)23 for 6 h to
afford 13a in 63% yield as the sole product (entry 1). The
hydrogen and phenyl congeners 12b and 12c also pro-
duced the corresponding bicyclic derivatives 13b and 13c
in 56 and 58% yields, respectively (entries 2 and 3).
[RhCl(CO)dppp]2,24 prepared from [RhCl(cod)]2 and 1,3-
bis(diphenylphosphino)propane (dppp), was found to be
a more powerful catalyst in the transformation of 12 into
13. Thus, on the basis of J eong’s procedure,20 a mixture
of 12a in toluene was refluxed in the presence of 2.5 mol
% [RhCl(CO)dppp]2 for 8 h under an atmosphere of
carbon monoxide (conditions B)23 to give 13a in 97% yield
(entry 4). Similar treatment of 12b and 12c under
conditions B furnished 13b and 13c in 85 and 65% yields,
respectively (entries 5 and 6). The formation of 14 could
not be detected in the reaction mixture in any case. These
observations are in accordance with those reported in
Table 1. Both rhodium(I) catalysts are regarded as
superior catalysts for the construction of bicyclo[4.3.0]-
nona-1,6-dien-8-ones 13 from allenynes 12 in comparison
with other metal catalysts. In particular, [RhCl(CO)-
dppp]2 provided very satisfactory results. Thus, hoping
to develop an efficient method for the synthesis of the
corresponding bicyclo[5.3.0]deca-1,7-dien-9-one deriva-
tives, we turned our attention to the intramolecular PKR
With the required allenynes 12 for the ring closure
reaction in hand, these enynes were then submitted to
the Co2(CO)8-mediated, as well as other metal-catalyzed,
PKR conditions (Table 1). According to the general
procedure for the formation of the alkyne-Co2(CO)6
complex,1 allenyne 12a was treated with Co2(CO)8 in
Et2O at room temperature to give an intractable mixture,
from which the desired cobalt-complexed 12a could not
be isolated. Upon direct exposure to Co2(CO)8 and tri-
methylamine N-oxide (TMANO) in toluene at -10 °C in
the presence of 4 Å molecular sieves,17 12a underwent a
ring closure reaction to provide the bicyclo[4.3.0]nona-
dienone derivative 13a in 52% yield (entry 1). When
directly treated with Co2(CO)8 in acetonitrile at 70-75
°C,18 12a afforded 13a in 46% yield (entry 2). Other
typical Co2(CO)8-mediated PKR conditions were unsuc-
cessful. It should be noted that the Co2(CO)8-mediated
PKR of 12a gave the bicyclo[4.3.0]nonadienone 13a
chemoselectively but not the corresponding bicyclo[3.3.0]-
octenone derivative 14a . We next examined the other
metal-catalyzed PKR of 12a . Mo(CO)6 has recently been
shown by Brummond10 to be effective for the intra-
molecular PKR of allenynes. However, the desired ring-
closed product 13a was obtained only in trace amounts
(entry 3). Narasaka’s procedures with Fe catalysts9
provided 13a in rather lower yields (entries 4 and 5).
19
Ru3(CO)12 was also ineffective in this PKR, resulting
in a mixture of decomposed products (entry 6).
In the case of the Co2(CO)8-mediated PKR of 12a , the
bicyclo[4.3.0]nonadienone framework was chemoselec-
tively formed in moderate yields (entries 1 and 2).
However, these chemical yields are lower compared to
those generally observed in the intramolecular PKR of
alkyne-olefin species (nonenyne derivatives).1 There-
fore, we needed more reliable conditions with higher yield
for the preparation of the bicyclo[4.3.0]nonadienone
skeleton, which would ensure the construction of the
bicyclo[5.3.0]decadienone framework. Recent reports from
(20) (a) J eong, N.; Lee, S.; Sung, B. K. Organometallics 1998, 17,
3642-3644. (b) J eong, N.; Sung, B. K.; Choi, Y. K. J . Am. Chem. Soc.
2000, 122, 6771-6772.
(21) (a) Koga, Y.; Kobayashi, T.; Narasaka, K. Chem. Lett. 1998,
249-250. (b) Kobayashi, T.; Koga, Y.; Narasaka, K. J . Organomet.
Chem. 2001, 624, 73-87.
(22) During this investigation, the [RhCl(CO)2]2-catalyzed PKR of
an allenyne leading to formation of the bicyclo[4.3.0]nona-1,6-dien-8-
one derivative in 61% yield was reported. See ref 21b.
(23) Rh(I)-catalyzed PKR of the sulfoxide 11 was examined under
conditions A and B; however, no reaction took place and the starting
sulfoxide was completely recovered intact.
(17) Pe´rez-Serrano, L.; Casarrubios, L.; Dom´ınguez, G.; Pe´rez-
Castells, J . Org. Lett. 1999, 1, 1187-1188.
(18) (a) Hoye, T. R.; Suriano, J . A. J . Org. Chem. 1993, 58, 1659-
1660. (b) Chung, Y. K.; Lee, B. Y.; J eong, N.; Hudecek, M.; Pauson, P.
L. Organometallics 1993, 12, 220-223.
(19) (a) Morimoto, T.; Chatani, N.; Fukumoto, Y.; Murai, S. J . Org.
Chem. 1997, 62, 3762-3765. (b) Kondo, T.; Suzuki, N.; Okada, T.;
Mitsudo, T. J . Am. Chem. Soc. 1997, 119, 6187-6188.
(24) Sanger, A. R. J . Chem. Soc., Dalton Trans. 1977, 120-129.
1378 J . Org. Chem., Vol. 68, No. 4, 2003

Construction of the Bicyclo[5.3.0]decenone Skeleton
SCHEME 4 a
SCHEME 5 a
a
Reaction conditions: (a) nBuLi, TMSCl, THF, -78 °C, then 10%
HCl, rt; (b) I2, PPh3, imidazole, CH2Cl2, rt; (c) TBDMSOCH2CtCH,
nBuLi, THF-DMPU, -78 °C; (d) 10% HCl, MeOH, rt, (54%); (e)
i
TBAF, THF, rt, (96%); (f) PhI, CuI, Pd(PPh3)2Cl2, Pr2NH, THF,
rt, (68%); (g) (i) PhSCl, Et3N, THF, -78 °C, (ii) mCPBA, CH2Cl2,
0 °C, 17a (78%), 17b (69%), 17c (69%).
TABLE 3. P a u son -Kh a n d Rea ction of 17 w ith Rh (I)
Ca ta lyst
a
Reaction conditions: (a) NaH, THF, ICH2CtCCH2OTBDPS
(21), from 0 °C to rt; (b) TBAF, THF, rt, (80%); (c) PhI, PdCl2(PPh3)2,
i
CuI, Pr2NH, THF, rt, 22b (82%), 25b (95%); (d) (i) PhSCl, Et3N,
THF, -78 °C, (ii) mCPBA, CH2Cl2, 0 °C, 23a (78%), 23b (80%),
26a (77%), 26b (80%); (e) NaH, DMF, ICH2CH2CtCCH2OTHP
(24), from 0 °C to rt; (f) NaH, THF, BrCH2CtCH, from 0 °C to rt;
(g) p-TsOH, MeOH, rt, (56%).
to 5.0 mol % in the same reaction did not improve the
chemical yield (entry 3). The TMS and phenyl congeners
17a and 17c also underwent the [2 + 2 + 1]-type ring
closure reaction to give the corresponding bicyclo[5.3.0]-
deca-1,7-dien-9-ones 18a and 18c in yields of 58 and 55%,
respectively (entries 1 and 4). We could then reproducibly
obtain the bicyclo[5.3.0]deca-1,7-dien-9-one skeleton by
PKR reaction, although the chemical yields were moder-
ate. Furthermore, the transformation of the allenynes 17
into the desired 18 in higher chemical yields was realized
when 17 was exposed to conditions B (entries 5-8). Thus,
we revealed the efficiency for intramolecular rhodium-
catalyzed PKR of the allenynes leading to the construc-
tion of not only the bicyclo[4.3.0]nona-1,6-dien-8-one but
also the bicyclo[5.3.0]deca-1,7-dien-9-one frameworks in
reasonable chemical yields.
The next phase of this program involved the applica-
tion of this newly developed rhodium-catalyzed procedure
to the construction of other bicyclo[5.3.0]deca-1,7-dien-
9-ones. To this end, two types of 1,2-nonadien-8-yne
derivatives 23 and 26 were prepared under conventional
means, as depicted in Scheme 5. Upon exposure to both
conditions A and B, 23a and 23b produced the corre-
sponding bicyclo[5.3.0]deca-1,7-dien-9-one derivatives 27a
and 27b in high yields (Table 4, entries 1-4).27 In one
series of compounds 26, an efficient production of the
cyclized compounds 28a and 28b in high yields was
observed under conditions B (entries 7 and 8). In contrast
to the results in entries 7 and 8, conditions A produced
28a and 28b in lower yields (entries 5 and 6). Table 4
indicates that the rhodium-catalyzed intramolecular PKR
of the 1,2-nonadien-8-yne derivatives with the methoxy-
carbonyl functionality proceeded as anticipated. In par-
ticular, conditions B ([RhCl(CO)dppp]2 catalyst) were
consistently effective for the [2 + 2 + 1] ring closure
reaction of both compounds 23 and 26.
mol %
catalyst
yield
(%)
entry
R
conditiona
product
1
2
3
4
5
6
7
8
TMS
H
A
A
A
A
B
B
B
B
5.0
2.5
5.0
2.5
5.0
2.5
5.0
2.5
18a
18b
18b
18c
18a
18b
18b
18c
45
61
58
55
74
69
75
84
H
Ph
TMS
H
H
Ph
a
Condition A: 2.5 or 5.0 mol % [RhCl(CO)2]2, toluene, 1 atm
CO. Condition B: 2.5 or 5.0 mol % [RhCl(CO)dppp]2, toluene, 1
atm CO.
of the one-carbon-homologated allenynes 17 under the
two rhodium-catalyzed conditions A and B.
Rh od iu m -Ca ta lyzed P a u son -Kh a n d Rea ction of
3-P h en ylsu lfon yln on a -1,2-d ien -8-yn e Der iva tives.
By analogy to the preparation of the octa-1,2-dien-7-yne
derivatives 12, the one-carbon-homologated starting
allenynes 17 for rhodium-catalyzed PKR were prepared
in a straightforward manner from 5-hexyn-1-ol (15), as
shown in Scheme 4. For the initial evaluation of the
rhodium-catalyzed PKR of the allenynes 17, we first
attempted the cyclization of compound 17b under condi-
tions A with 2.5 mol % catalyst to afford the bicyclo[5.3.0]-
deca-1,7-dien-9-one derivative 18b in 61% yield as the
sole isolable product (Table 3, entry 2).25 The other
possible isomer 19b, which would arise from the reaction
of the alkyne moiety with the internal double bond of the
1,2-diene functionality, could never be detected in the
reaction mixture.26 Increasing the amount of the catalyst
(25) Examination of each experiment was carried out several times
to confirm its reproducibility. In some cases, the chemical yields we
reported in the previous paper13 were improved. In particular, we
reported that cyclization of 17a under conditions B gave 18a in 7%
yield along with recovered starting material (45%). It was ultimately
found that the low reactivity of 17a , observed under conditions B, was
due to contamination by impurities. Thus, the purified 17a produced
18a under conditions B in 74% yield (entry 5).
(27) Examination of each experiment was carried out several times
to confirm its reproducibility. In some cases, the chemical yields
reported in our previous paper13 were improved.
(26) A similar behavior was observed by Brummond.14
J . Org. Chem, Vol. 68, No. 4, 2003 1379

Mukai et al.
TABLE 4. P a u son -Kh a n d Rea ction of 23 a n d 26 w ith
Rh (I) Ca ta lyst
TABLE 5. P a u son -Kh a n d Rea ction of 31 a n d 32 w ith
Rh (I) Ca ta lyst
entry
SM
R
conditiona
product
yield (%)
entry
SM
R
conditiona
product
yield (%)
1
2
3
4
5
6
7
8
23a
23b
23a
23b
26a
26b
26a
26b
H
Ph
H
Ph
H
Ph
H
A
A
B
B
A
A
B
B
27a
27b
27a
27b
28a
28b
28a
28b
84
70
80
89
58
40
83
96
1
2
3
4
5
6
7
8
9
31a
31b
31c
31a
31b
31c
32a
32b
32c
32a
32b
32c
TMS
H
Ph
TMS
H
Ph
TMS
H
Ph
TMS
H
Ph
A
A
A
B
B
B
A
A
A
B
B
B
37a
37b
37c
37a
37b
37c
38a
38b
38c
38a
38b
38c
89
49
51
91
66
45
68
46
41
66
83
42
Ph
a
Condition A: 2.5 mol % [RhCl(CO)2]2, toluene, 1 atm CO.
Condition B: 2.5 mol % [RhCl(CO)dppp]2, toluene, 1 atm CO.
10
11
12
SCHEME 6 a
a
Condition A: 2.5 mol % [RhCl(CO)2]2, toluene, 1 atm CO.
Condition B: 2.5 mol % [RhCl(CO)dppp]2, toluene, 1 atm CO.
procedure in Scheme 4, the common starting material,
5-hexyn-1-ol (15), was easily converted into four types of
1,2-nonadien-8-yne derivatives 31, 32, 35, and 36 as
depicted in Scheme 6. The rhodium-catalyzed PKR of 31
and 32 was carried out under the standard conditions A
and B. The results are summarized in Table 5. The
bicyclo[5.3.0]deca-1,7-dien-9-one skeletons 37 and 38
were formed reproducibly, although the chemical yields
vary ranging from 41 to 91%. It should be mentioned that
a significant difference between conditions A and B in
the PKR of 31 and 32 could not be found. This observa-
tion is in contrast to the PKR of the 1,2-nonadien-8-yne
derivatives 17 and 26 (Tables 3 and 4), in which condi-
tions B consistently provided the ring-closed products in
higher yields than conditions A, i.e., conditions B seemed
to be superior to conditions A as long as 17 and 26 were
used as the starting allenyne. A similar tendency (chemi-
cal yields and behavior toward conditions A and B) was
observed when the 1,2-nonadien-8-yne derivative 35 with
a siloxy group at the propargyl position was submitted
to the rhodium-catalyzed PKR resulting in the formation
of 39 in a range of 47-94% yield. The results obtained
are summarized as entries 1-6 in Table 6. In the case of
36 with a free hydroxyl group at the propargyl position,
the corresponding bicyclo[5.3.0]deca-1,7-dien-9-one 40
was produced in moderate to high yield under conditions
B (entries 10-12). When 36b was exposed to conditions
A, however, the desired product 40b was obtained in only
15% yield as the sole isolable product (entry 8). In
addition, the ring closure reaction of 36c proceeded under
conditions A, but the product isolated from the reaction
mixture was the dehydrated compound 8-phenyl-2-
phenylsulfonylbicyclo[5.3.0]deca-1,5,7-trien-9-one (41) in
13% yield, presumably formed from the desired 40c in
the reaction mixture (entry 9). The instability of 41 might
explain the low chemical yield. The behavior of compound
36 toward the rhodium-catalyzed conditions was similar
to that of compounds 17 and 26.
a
Reaction conditions: (a) nBuLi, TMSCl, THF, -78 °C, then
10% HCl, rt; (b) Py‚SO3, DMSO, Et3N, rt; (c) HCtCMgBr, THF,
-20 °C; (d) TBDMSCl, imidazole, DMF, rt, (45%); (e) nBuLi,
(HCHO)n, THF, -78 °C, 30a (73%), 34a (86%) from 33; (f) K2CO3,
MeOH, rt, 30b (95%), 34b (91%); (g) PhI, PdCl2(PPh3)2, CuI,
iPr2NH, THF, rt, 30c (93%), 34c (89%); (h) PhSCl, Et3N, THF,
-78 °C, then mCPBA, CH2Cl2, 0 °C, 31a (94%), 31b (94%), 31c
(85%), 35a (35%), 35b (81%), 35c (70%); (i) 10% HCl, MeOH, rt,
32a (77%), 32b (98%), 32c (85%); (j) nBuLi, TMS-CtCH, THF,
-78°C, 33 (51%) from 15; (k) 10% HCl, THF, rt, 36a (94%), 36b
(98%), 36c (quantitative).
We next investigated some additional examples of the
rhodium-catalyzed PKR of the 1,2-nonadien-8-yne de-
rivatives possessing a hydroxyl or a siloxy group, both of
which might be considered as latent functionalities for
further elaboration. According to the aforementioned
1380 J . Org. Chem., Vol. 68, No. 4, 2003

Construction of the Bicyclo[5.3.0]decenone Skeleton
TABLE 6. P a u son -Kh a n d Rea ction of 35 a n d 36 w ith
11.1 mmol) was added, and the reaction mixture was gradually
warmed to room temperature and stirred for 3 h. Then, 10%
aqueous HCl (6.0 mL) was added to the reaction mixture. After
being stirred for 4 h, the reaction mixture was extracted with
Et2O. The extract was washed with water and brine, dried,
and concentrated to dryness. To the crude alcohol in dry
CH2Cl2 (18 mL) were added PPh3 (1.74 g, 6.64 mmol) and
imidazole (452 mg, 6.64 mmol). Then, I2 (1.69 g, 6.64 mmol)
was added to the reaction mixture. After the mixture was
stirred for 2 h, CH2Cl2 was evaporated off, and the residue
was passed through a short pad of silica gel with 10:1 hexane-
AcOEt to afford the crude iodide. To a solution of 1-(tert-
butyldiphenylsiloxy)-2-propyne (815 mg, 2.77 mmol) in dry
THF (16 mL) was added n-BuLi in hexane (1.41 M, 1.70 mL,
2.40 mmol) at -78 °C. After the mixture was stirred for 30
min, a THF solution of the crude iodide (2.0 mL) was added,
and the reaction mixture was gradually warmed to 50 °C. After
being stirred for 3.5 h, the reaction was quenched by addition
of water, and the mixture was extracted with AcOEt. The
extract was washed with water and brine, dried, and concen-
trated to dryness. To a solution of the crude product in MeOH
(18 mL) was added 10% aqueous HCl (6.0 mL), and the
solution was stirred at room temperature for 12 h. MeOH was
evaporated off, and the residue was extracted with AcOEt. The
extract was washed with water and brine, dried, and concen-
trated to dryness. The residue was chromatographed with 7:1
hexane-AcOEt to afford 10a (211 mg, 59%) as a colorless oil:
Rh (I) Ca ta lyst
entry
SM
R
conditiona
product
yield (%)
1
2
3
4
5
6
7
8
9
35a
35b
35c
35a
35b
35c
36a
36b
36c
36a
36b
36c
TMS
H
Ph
TMS
H
Ph
TMS
H
Ph
TMS
H
Ph
A
A
A
B
B
B
A
A
A
B
B
B
39a
39b
39c
39a
39b
39c
40a
40b
40c
40a
40b
40c
87
47
66
65
53
94
53
15
traceb
93
45
84
10
11
12
a
Condition A: 2.5 mol % [RhCl(CO)2]2, toluene, 1 atm CO.
b
1
IR 3422, 2172 cm-1; H NMR δ 4.23 (t, 2H, J ) 2.4 Hz), 2.32
Condition B: 2.5 mol % [RhCl(CO)dppp]2, toluene, 1 atm CO. 8-
Phenyl-2-phenylsulfonylbicyclo[5.3.0]deca-1,5,7-trien-9-one (41)
was obtained in 13% yield.
(tt, 4H, J ) 7.3, 2.4 Hz), 1.75-1.67 (m, 3H), 0.13 (s, 9H); 13C
NMR δ 106.15, 85.39, 85.20, 78.90, 51.29, 27.60, 18.98, 17.80,
0.08; MS m/z 194 (M+, 2.6); HRMS calcd for C11H18OSi
194.1127, found 194.1113.
1,6-Octa d iyn -8-ol (10b).28 To a solution of 10a (57.0 mg,
0.29 mmol) in dry THF (2.9 mL) was added TBAF in THF (1.0
M, 0.44 mL, 0.44 mmol) at room temperature. After the
mixture was stirred for 4 h, the reaction was quenched by
addition of water, and the mixture was extracted with Et2O.
The extract was washed with water and brine, dried, and
concentrated to dryness. The residue was chromatographed
with 5:1 hexane-AcOEt to afford 10b (25.7 mg, 72%) as a
In summary, we have developed a reliable procedure
for constructing a bicyclo[5.3.0]deca-1,7-dien-9-one ring
system by the rhodium-catalyzed PKR of allenynes with
a sulfonyl group, in which commercially available [RhCl-
(CO)2]2 as well as [RhCl(CO)dppp]2, derived from [RhCl-
(cod)]2, were employed as catalysts. Investigation of the
rhodium-catalyzed PKR on the 19 examples of the 1,2-
nonadien-8-yne derivatives demonstrated (i) that accept-
able yields could be consistently achieved through the
proper choice of the rhodium catalyst depending on the
starting allenyne and (ii) that not only an ester function-
ality but also hydroxyl and siloxy groups can be tolerated
in this rhodium-catalyzed PKR. The application of this
rhodium-catalyzed PKR of allenynes to the construction
of other ring systems as well as to the synthesis of
bioactive compounds is now in progress.
1
colorless oil: IR 3609, 3308 cm-1; H NMR δ 4.22 (t, 2H, J )
2.0 Hz), 2.33 (tt, 2H, J ) 6.8, 2.5 Hz), 2.29 (dt, 2H, J ) 6.8,
2.5 Hz), 1.98 (br s, 1H), 1.95 (t, 1H, J ) 2.5 Hz), 1.75-1.67
(m, 2H); 13C NMR δ 85.05, 83.37, 79.02, 68.95, 51.16, 27.30,
17.67, 17.44.
1-P h en yl-1,6-octa d iyn -8-ol (10c). To a solution of 10b (305
mg, 2.49 mmol), PdCl2(PPh3)2 (17.5 mg, 2.49 × 10-2 mmol),
and CuI (9.50 mg, 4.99 × 10-2 mmol) in dry THF (12 mL) was
added iodobenzene (0.56 mL, 4.99 mmol) at room temperature.
iPr2NH (3.50 mL, 24.9 mmol) was added to the reaction
mixture, which was stirred for 18 h. THF was evaporated off,
and the residue was chromatographed with 6:1 hexane-AcOEt
to afford 10c (402 mg, 82%) as a yellow oil: IR 3609, 3435,
2226 cm-1; 1H NMR δ 7.42-7.36 (m, 2H), 7.30-7.25 (m, 3H),
4.29-4.21 (m, 2H), 2.53 (t, 2H, J ) 6.8 Hz), 2.41 (tt, 2H, J )
6.8, 2.0 Hz), 1.85-1.77 (m, 2H); 13C NMR δ 131.51, 128.16,
127.62, 123.70, 88.97, 85.39, 81.24, 79.00, 51.31, 27.68, 18.53,
17.92; MS m/z 198 (M+, 13); HRMS calcd for C14H14O 198.1044,
found 198.1034.
3-(P h en ylsu lfin yl)-8-(t r im et h ylsilyl)-1,2-oct a d ien -7-
yn e (11). To a solution of 10a (792 mg, 4.00 mmol) in THF
(35 mL) was added Et3N (1.70 mL, 12.2 mmol) at -78 °C. After
the mixture was stirred for 15 min, a solution of PhSCl (1.77
g, 12.2 mmol) in THF (5.0 mL) was added. The reaction
mixture was stirred for 1 h at -78 °C and then gradually
warmed to 0 °C over a period of 1 h. The reaction was quenched
by addition of saturated aqueous NaHCO3, and the mixture
was extracted with Et2O. The extract was washed with water
and brine, dried, and concentrated to dryness. The residual
Exp er im en ta l Section
Melting points are uncorrected. IR spectra were measured
1
in CHCl3. H NMR spectra were taken in CDCl3. CHCl3 (7.26
ppm) for silyl compounds and tetramethylsilane (0.00 ppm)
for compounds without a silyl group were used as internal
standards. 13C NMR spectra were recorded in CDCl3 with
CHCl3 (77.00 ppm) as an internal standard. All reactions were
carried out under a nitrogen atmosphere unless otherwise
stated. Silica gel (silica gel 60, 230-400 mesh) was used for
chromatography. Organic extracts were dried over anhydrous
Na2SO4.
1-(Tr im eth ylsilyl)-1,6-octa d iyn -8-ol (10a ). To a solution
of 4-pentyn-1-ol (155 mg, 1.85 mmol) in dry THF (18 mL) was
added n-BuLi in hexane (1.53 M, 3.60 mL, 5.54 mmol) at -78
°C. After the mixture was stirred for 30 min, TMSCl (1.40 mL,
(28) Carruthers, W.; Pellatt, M. G. J . Chem. Soc. C 1971, 1485-
1488.
J . Org. Chem, Vol. 68, No. 4, 2003 1381

Mukai et al.
oil was chromatographed with 5:1 hexane-AcOEt to afford 11
0.13; MS m/z 208 (M+, 4.0); HRMS calcd for C12H20OSi
208.1284, found 208.1282.
1
(1.19 g, 96%) as a colorless oil: IR 2172, 1969, 1944 cm-1; H
NMR δ 7.67-7.42 (m, 5H), 5.29 (qt, 2H, J ) 11.9, 3.3 Hz),
2.35-2.20 (m, 1H), 2.16 (t, 2H, J ) 6.9 Hz), 2.04-1.87 (m, 1H),
1.69-1.45 (m, 2H), 0.10 (s, 9H); 13C NMR δ 205.28, 143.38,
130.87, 129.00, 124.42, 112.49, 106.06, 85.10, 82.50, 26.35,
21.98, 19.18, 0.06; MS m/z 302 (M+, 0.78); HRMS calcd for
C17H22OSSi 302.1160, found 302.1153.
3-(P h en ylsu lfon yl)-9-(t r im et h ylsilyl)-1,2-n on a d ien -8-
yn e (17a ). According to the procedure described for prepara-
tion of 12a , 17a (259 mg, 78%) was obtained from 16a (207
mg, 0.99 mmol) as a colorless oil: IR 2170, 1969, 1942 cm-1
;
1H NMR δ 7.92-7.87 (m, 2H), 7.65-7.50 (m, 3H), 5.36 (dt,
2H, J ) 8.8, 3.4 Hz), 2.28-2.19 (m, 2H), 2.16 (t, 2H, J ) 6.8
Hz), 1.58-1.36 (m, 4H), 0.12 (s, 9H); 13C NMR δ 207.60, 140.05,
133.42, 129.02, 128.05, 113.08, 106.67, 84.82, 84.51, 27.55,
26.36, 26.02, 19.41, 0.07; MS m/z 332 (M+, 2.0); HRMS calcd
for C18H24O2SSi 332.1266, found 332.1264. Anal. Calcd for
3-(P h en ylsu lfon yl)-8-(t r im et h ylsilyl)-1,2-oct a d ien -7-
yn e (12a ). To a solution of 10a (157 mg, 0.81 mmol) in THF
(6.0 mL), was added Et3N (0.34 mL, 2.43 mmol) at -78 °C.
After the mixture was stirred for 15 min, a solution of PhSCl
(351 mg, 2.43 mmol) in THF (2.0 mL) was added, and the
reaction mixture was stirred for 1.5 h at -78 °C. The reaction
was quenched by addition of water, and the mixture was
extracted with Et2O. The extract was washed with water and
brine, dried, and concentrated to dryness. The residual oil was
passed through a short pad of silica gel with 6:1 hexane-
AcOEt to afford the crude sulfoxide. A solution of mCPBA (209
mg, 1.21 mmol) in CH2Cl2 (2.0 mL) was added to a solution of
the crude sulfoxide in CH2Cl2 (6.0 mL) at 0 °C. After the
reaction mixture was stirred for 1 h, the reaction was quenched
by addition of saturated aqueous NaHCO3, and the mixture
was extracted with CH2Cl2. The extract was washed with
aqueous Na2S2O3 and brine, dried, and concentrated to dry-
ness. The residual oil was chromatographed with 6:1 hexane-
AcOEt to afford 12a (218 mg, 85%) as colorless needles: mp
C
18H24O2SSi: C, 65.01; H, 7.27. Found: C, 64.70; H, 7.33.
4-(ter t-Bu tyld ip h en ylsiloxy)-1-iod o-2-bu tyn e (21). To a
solution of 4-(tert-butyldiphenylsiloxy)-2-butyn-1-ol29 (815 mg,
2.5 mmol) in dry CH2Cl2 (25 mL) were added PPh3 (983 mg,
3.8 mmol) and imidazole (255 mg, 3.8 mmol) at room temper-
ature. Then, I2 (953 mg, 3.8 mmol) was added to the reaction
mixture, which was stirred for 30 min. CH2Cl2 was evaporated
off, and the residue was chromatographed with 30:1 hexane-
1
AcOEt to afford 21 (963 mg, 89%) as a colorless oil; H NMR
δ 7.75-7.66 (m, 4H), 7.49-7.35 (m, 6H), 4.33 (t, 2H, J ) 2.3
Hz), 3.66 (t, 2H, J ) 2.3 Hz), 1.07 (s, 9H); 13C NMR δ 135.60,
132.97, 129.81, 127.73, 83.67, 81.89, 52.89, 26.70, 19.16,
-18.51; MS m/z 434 (M+, 0.2); HRMS calcd for C20H23IOSi
434.0563, found 434.0549. Anal. Calcd for C20H23IOSi: C,
55.30; H, 5.34. Found: C, 54.93; H, 5.41.
5,5-Bis(m eth oxyca r bon yl)-1,7-n on a d iyn -9-ol (22a ). To
a solution of 2030 (378 mg, 2.05 mmol) in THF (20 mL) was
added NaH (60% in mineral oil, 90.4 mg, 2.26 mmol) at 0 °C.
After the mixture was stirred for 30 min, a solution of 21 (985
mg, 2.27 mmol) in THF (5.0 mL) was added, and stirring was
continued for an additional 1 h at 0 °C. The reaction was
quenched by addition of water, and the mixture was extracted
with AcOEt. The extract was washed with water and brine,
dried, and concentrated to dryness. To a solution of the crude
product in THF (20 mL) was added TBAF in THF (1.0 M, 2.10
mL, 2.10 mmol) at room temperature. The reaction mixture
was stirred at room temperature for 30 min and concentrated
to dryness. The residue was passed through a short pad of
silica gel with 2:1 hexane-AcOEt to afford 22a (414 mg, 80%)
as a colorless oil: IR 3524, 3308, 2122, 1732 cm-1; 1H NMR δ
4.21 (t, 2H, J ) 2.0 Hz), 3.74 (s, 6H), 2.88 (t, 2H, J ) 2.0 Hz),
2.37-2.15 (m, 4H), 1.97 (t, 1H, J ) 2.6 Hz); 13C NMR δ 170.22,
82.79, 81.94, 79.91, 69.00, 56.28, 52.85, 51.00, 31.11, 23.34,
13.86; MS m/z 252 (M+, 1.3); HRMS calcd for C13H16O5
252.0998, found 252.1008.
5,5-Bis(m eth oxycar bon yl)-3-(ph en ylsu lfon yl)-1,2-n on a-
d ien -8-yn e (23a ). According to the procedure described for
preparation of 12a , 23a (76.8 mg, 78%) was obtained from 22a
(66.0 mg, 0.26 mmol) as colorless needles: mp 69.5-70.5 °C
(hexane-AcOEt); IR 3308, 1967, 1936, 1734 cm-1; 1H NMR δ
7.93-7.84 (m, 2H), 7.69-7.50 (m, 3H), 5.37 (t, 2H, J ) 3.3
Hz), 3.67 (s, 6H), 2.92 (t, 2H, J ) 3.3 Hz), 2.24-2.02 (m, 4H),
1.91 (t, 1H, J ) 2.6 Hz); 13C NMR δ 208.16, 169.99, 139.68,
133.73, 129.20, 128.21, 108.75, 85.61, 82.71, 68.91, 56.10,
52.69, 30.77, 28.63, 13.84; MS m/z 376 (M+, 1.4); HRMS calcd
for C19H20O6S 376.0981, found 376.0985. Anal. Calcd for
1
74.5-75.5 °C (hexane); IR 2172, 1971, 1938 cm-1; H NMR δ
7.93-7.86 (m, 2H), 7.65-7.50 (m, 3H), 5.38 (t, 2H, J ) 3.4
Hz), 2.38-2.29 (m, 2H), 2.21 (t, 2H, J ) 6.8 Hz), 1.69-1.60
(m, 2H), 0.11 (s, 9H); 13C NMR δ 207.69, 140.14, 133.45, 129.05,
128.06, 112.69, 105.78, 85.44, 84.48, 26.36, 25.85, 19.04, 0.06;
MS m/z 318 (M+, 10); HRMS calcd for C17H22O2SSi 318.1109,
found 318.1112. Anal. Calcd for C17H22O2SSi: C, 64.11; H, 6.96.
Found: C, 64.00; H, 7.05.
1-(Tr im eth ylsilyl)-1,7-n on a d iyn -9-ol (16a ). To a solution
of 15 (2.60 g, 26.5 mmol) in dry THF (130 mL) was added
n-BuLi in hexane (1.43 M, 55.6 mL, 79.5 mmol) at -78 °C.
After the mixture was stirred for 45 min, TMSCl (20.2 mL,
159 mmol) was added, and the reaction mixture was gradually
warmed to room temperature. Then, 10% aqueous HCl (20 mL)
was added to the reaction mixture. After being stirred for 3 h,
the reaction mixture was extracted with Et2O. The extract was
washed with water and brine, dried, and concentrated to
dryness. To the crude alcohol in dry CH2Cl2 (90 mL) were
added PPh3 (20.9 g, 79.5 mmol) and imidazole (5.42 g, 79.5
mmol) at 0 °C. Then I2 (20.2 g, 79.5 mmol) was added to the
reaction mixture, which was gradually warmed to room
temperature. After the mixture was stirred for 12 h, CH2Cl2
was evaporated off, and the residue was passed through a
short pad of silica gel with 10:1 hexane-AcOEt to afford the
crude iodide. To a solution of 1-(tert-butyldimethylsiloxy)-2-
propyne (5.87 g, 34.5 mmol) in dry THF (48 mL) was added
n-BuLi in hexane (1.43 M, 20.4 mL, 29.2 mmol) at -78 °C.
After the mixture was stirred for 30 min, a THF-DMPU
solution of the crude iodide (THF 20 mL, DMPU 13 mL) was
added, and the reaction mixture was stirred at the same
temperature for 1 h and then gradually warmed to room
temperature. After the reaction mixture was stirred for 5 h,
the reaction was quenched by addition of saturated aqueous
NH4Cl, and the mixture was extracted with Et2O. The extract
was washed with water and brine, dried, and concentrated to
dryness. To a solution of the crude product in MeOH (60 mL)
was added 10% aqueous HCl (10 mL), and the mixture was
stirred at room temperature for 12 h. MeOH was evaporated
off, and the residue was extracted with Et2O. The extract was
washed with water and brine, dried, and concentrated to
dryness. The residue was chromatographed with 5:1 hexane-
AcOEt to afford 16a (2.98 g, 54%) as a colorless oil: IR 3609,
C
19H20O6S: C, 60.62; H, 5.36. Found: C, 60.63; H, 5.40.
1-Iodo-5-[(tetr ah ydr o-2H-pyr an -2-yl)oxy]-3-pen tyn e (24).
To a solution of 5-[(tetrahydro-2H-pyran-2-yl)oxy]-3-pentyn-
1-ol31 (800 mg, 4.4 mmol) in dry CH2Cl2 (40 mL) were added
PPh3 (1.4 g, 5.3 mmol) and imidazole (360 mg, 5.3 mmol) at
room temperature. Then, I2 was added to the reaction mixture,
which was stirred for 30 min. CH2Cl2 was evaporated off, and
the residue was chromatographed with 10:1 hexane-AcOEt
to afford 24 (1.0 g, 81%) as a colorless oil: 1H NMR δ 4.82 (t,
1H, J ) 3.4 Hz), 4.23 (qt, 2H, J ) 15.6, 2.0 Hz), 3.87-3.79 (m,
(29) Trost, B. M.; Chulbom, L. J . Am. Chem. Soc. 2001, 123, 12191-
12201.
(30) Laidig, G. J .; Hegedus, L. S. Synthesis 1995, 527-532.
(31) Han, L.; Razdan, R. K. Tetrahedron Lett. 1998, 39, 771-774.
1
3449, 2172 cm-1; H NMR δ 4.25 (t, 2H, J ) 2.4 Hz), 2.30-
2.19 (m, 4H), 1.68-1.58 (m, 4H), 0.14 (s, 9H); 13C NMR δ
106.94, 86.04, 84.76, 78.62, 51.38, 27.66, 27.58, 19.38, 18.28,
1382 J . Org. Chem., Vol. 68, No. 4, 2003

Construction of the Bicyclo[5.3.0]decenone Skeleton
1H), 3.57-3.48 (m, 1H), 3.21 (t, 2H, J ) 7.3 Hz), 2.81 (tt, 2H,
J ) 7.3, 2.0 Hz), 1.88-1.46 (m, 6H); 13C NMR δ 96.55, 84.73,
77.83, 61.89, 54.25, 30.12, 25.23, 23.97, 18.98, 1.24; MS m/z
294 (M+, 5.8); HRMS calcd for C10H15IO2 294.0117, found
bromide in THF (0.50 M, 57.0 mL, 28.5 mmol) at -20 °C. The
reaction mixture was stirred at the same temperature for 2.5
h; the reaction was quenched by addition of saturated aqueous
NH4Cl, and the mixture was 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 6:1 hexane-AcOEt to afford the crude alcohol. The
alcohol was taken up in DMF (20 mL), to which imidazole (3.42
g, 50.3 mmol) and TBDMSCl (3.81 g, 25.2 mmol) were added
at room temperature. The reaction mixture was stirred at room
temperature for 12 h; the reaction was quenched by addition
of water, and the mixture was extracted with Et2O. The extract
was washed with water and brine, dried, and concentrated to
dryness. The residual oil was chromatographed with 40:1
hexane-AcOEt to afford 29 (3.04 g, 45%) as a colorless oil:
IR 3306, 2172 cm-1; 1H NMR δ 4.39 (td, 1H, J ) 6.3, 2.0 Hz),
2.38 (d, 1H, J ) 2.0 Hz), 2.27 (t, 2H, J ) 6.9 Hz) 1.89-1.60
(m, 4H), 0.91 (s, 9H), 0.14 (s, 9H), 0.12 (s, 6H); 13C NMR δ
106.90, 85.19, 84.73, 72.20, 62.32, 37.36, 25.75, 24.08, 19.46,
18.17, 0.13, -4.60, -5.08; MS m/z 308 (M+, 0.7); HRMS calcd
for C17H32OSi2 308.1992, found 308.1979.
6-(ter t-Bu tyldim eth ylsiloxy)-1-(tr im eth ylsilyl)-1,7-n on a-
d iyn -9-ol (30a ). To a solution of 29 (871 mg, 2.82 mmol) in
dry THF (28 mL) was added n-BuLi in hexane (1.36 M, 2.49
mL, 3.39 mmol) at -78 °C. After the mixture was stirred for
40 min, (HCHO)n (425 mg, 14.1 mmol) was added, and the
reaction mixture was stirred at room temperature for 6 h. The
reaction was quenched by addition of aqueous saturated
NH4Cl, and the mixture was extracted with Et2O. The extract
was washed with water and brine, dried, and concentrated to
dryness. The residual oil was chromatographed with 6:1
hexane-AcOEt to afford 30a (699 mg, 73%) as a colorless oil:
IR 3609, 3422, 2170 cm-1; 1H NMR δ 4.43 (tt, 1H, J ) 6.3, 2.0
Hz), 4.29 (dd, 2H, J ) 6.4, 2.0 Hz), 2.26 (t, 2H, J ) 6.8 Hz),
1.81-1.62 (m, 4H), 1.50-1.45 (m, 1H), 0.91 (s, 9H), 0.15 (s,
9H), 0.13 (s, 3H), 0.11 (s, 3H); 13C NMR δ 107.00, 87.26, 84.70,
82.29, 62.53, 51.18, 37.42, 25.79, 24.20, 19.51, 18.22, 0.14,
-4.49; MS m/z 338 (M+, 0.3); HRMS calcd for C18H34O2Si2
338.2097, found 338.2086.
294.0111. Anal. Calcd for
Found: C, 40.76; H, 5.25.
C10H15IO2: C, 40.83; H, 5.14.
4,4-Bis(m eth oxyca r bon yl)-1,7-n on a d iyn -9-ol (25a ). To
a solution of dimethyl malonate (0.20 mL, 1.80 mmol) in dry
DMF (10 mL) was added NaH (60% in mineral oil, 81.0 mg,
2.03 mmol) at 0 °C. After the mixture was stirred for 30 min,
a DMF solution (2.0 mL) of 24 (541 mg, 1.84 mmol) was added,
and the reaction mixture was stirred for 6 h at room temper-
ature. The reaction was quenched by addition of saturated
aqueous NH4Cl, and the mixture was extracted with AcOEt.
The extract was washed with water and brine, dried, and
concentrated to dryness. To a solution of the crude product in
dry THF (10 mL) was added NaH (60% in mineral oil, 81.0
mg, 2.03 mmol) at 0 °C. After the mixture was stirred for 30
min, propargyl bromide (0.14 mL, 1.90 mmol) was added, and
the reaction mixture was stirred at room temperature for 3 h.
The reaction was quenched by addition of saturated aqueous
NH4Cl, and the mixture was extracted with AcOEt. The
extract was washed with water and brine, dried, and concen-
trated to dryness. To a solution of the crude product in MeOH
(10 mL) was added p-TsOH (34.2 mg, 0.18 mmol) at room
temperature. After the mixture was stirred for 12 h, MeOH
was evaporated off, and the residue was extracted with AcOEt.
The extract was washed with water and brine, dried, and
concentrated to dryness. The residue was chromatographed
with 3:1 hexane-AcOEt to afford 25a (249 mg, 56%) as a
colorless oil: IR 3528, 3308, 1734 cm-1; 1H NMR δ 4.24-4.17
(m, 2H), 3.77 (s, 6H), 2.85 (d, 2H, J ) 2.6 Hz), 2.37-2.18 (m,
4H), 2.02 (t, 1H, J ) 2.6 Hz), 1.94 (br s, 1H); 13C NMR δ 170.21,
84.33, 79.28, 78.31, 71.75, 56.14, 52.87, 51.09, 30.82, 22.82,
14.09; MS m/z 252 (M+, 1.0); HRMS calcd for C13H16O5
252.0998, found 252.0998. Anal. Calcd for C13H16O5: C, 61.90;
H, 6.39. Found: C, 61.52; H, 6.48.
6,6-Bis(m eth oxycar bon yl)-3-(ph en ylsu lfon yl)-1,2-n on a-
d ien -8-yn e (26a ). According to the procedure described for
preparation of 12a , 26a (289 mg, 77%) was obtained from 25a
(252 mg, 1.00 mmol) as colorless needles: mp 94-95 °C
(hexane-AcOEt); IR 3308, 1971, 1936, 1734 cm-1; 1H NMR δ
7.91-7.82 (m, 2H), 7.66-7.47 (m, 3H), 5.41 (t, 2H, J ) 3.0
Hz), 3.69 (s, 6H), 2.77 (d, 2H, J ) 3.0 Hz), 2.26-2.08 (m, 4H),
1.95 (t, 1H, J ) 2.6 Hz); 13C NMR δ 207.51, 169.97, 139.95,
133.50, 129.04, 128.03, 112.53, 85.27, 78.10, 71.72, 56.25,
52.87, 30.30, 23.09, 21.75; MS m/z 376 (M+, 8.6); HRMS calcd
for C19H20O6S 376.0981, found 376.0985. Anal. Calcd for
4-(ter t-Bu tyld im eth ylsiloxy)-3-(p h en ylsu lfon yl)-9-(tr i-
m eth ylsilyl)-1,2-n on a d ien -8-yn e (31a ). According to the
procedure described for preparation of 12a , 31a (237 mg, 94%)
was obtained from 30a (184 mg, 0.54 mmol) as a colorless oil:
IR 2172, 1971, 1931 cm-1; 1H NMR δ 7.93-7.87 (m, 2H), 7.65-
7.50 (m, 3H), 5.43-5.33 (m, 2H), 4.49-4.44 (m, 1H), 2.20-
2.15 (m, 2H), 1.91-1.68 (m, 2H), 1.56-1.48 (m, 2H), 0.79 (s,
9H), 0.14 (s, 9H), -0.06 (s, 3H), -0.18 (s, 3H); 13C NMR δ
208.80, 140.88, 133.50, 129.02, 128.10, 117.34, 106.96, 85.21,
84.71, 68.45, 37.07, 25.63, 23.96, 19.55, 18.01, 0.13, -5.17,
-5.34; FABMS m/z 463 (M+ + 1, 2.8); FABHRMS calcd for
C
19H20O6S: C, 60.62; H, 5.36. Found: C, 60.44; H, 5.54.
6-(ter t-Bu tyldim eth ylsiloxy)-1-(tr im eth ylsilyl)-1,7-octa-
C
24H39O3SSi2 463.2158, found 463.2160.
d iyn e (29). To a solution of 5-hexyn-1-ol (15) (2.15 g, 21.9
mmol) in dry THF (65 mL) was added n-BuLi in hexane (1.46
M, 36.0 mL, 52.6 mmol) at -78 °C. After the mixture was
stirred for 1 h, TMSCl (14.0 mL, 110 mmol) was added, and
the reaction mixture was stirred at the same temperature for
30 min and then at room temperature for 12 h. Then, 10%
aqueous HCl (18 mL) was added to the reaction mixture, which
was stirred for 1 h, neutralized with 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 3:1
hexane-AcOEt to afford the C-silylated hexynol. To a solution
of the hexynol, DMSO (5.00 mL, 70.4 mmol), and Et3N (10.0
mL, 71.7 mmol) in dry CH2Cl2 (100 mL) was added SO3‚
pyridine (10.5 g, 66.0 mmol) at 0 °C. After the mixture was
stirred for 6 h at room temperature, the reaction was quenched
by addition of saturated aqueous NH4Cl, and the mixture was
extracted with CH2Cl2. 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 8:1 hexane-
AcOEt to afford the crude aldehyde. To a solution of the crude
aldehyde in dry THF (100 mL) was added ethynylmagnesium
3-(P h en ylsu lfon yl)-9-(t r im et h ylsilyl)-1,2-n on a d ien -8-
yn -4-ol (32a ). To a solution of 31a (160 mg, 0.35 mmol) in
MeOH (3.4 mL) was added 10% aqueous HCl (0.6 mL) at room
temperature. After the mixture was stirred for 14 h, MeOH
was evaporated off, and the residue was extracted with AcOEt.
The extract was washed with water and brine, dried, and
concentrated to dryness. The residual oil was chromatographed
with 7:3 hexane-AcOEt to afford 32a (92.8 mg, 77%) as a
colorless oil: IR 3551, 2172, 1967, 1929 cm-1; 1H NMR δ 7.94-
7.89 (m, 2H), 7.66-7.52 (m, 3H), 5.45 (d, 2H, J ) 1.5 Hz),
4.49-4.43 (m, 1H), 2.93 (d, 1H, J ) 4.4 Hz), 2.18 (td, 2H, J )
6.8, 3.4 Hz), 1.80-1.41 (m, 4H), 0.12 (s, 9H); 13C NMR δ 207.44,
140.35, 133.76, 129.09, 128.06, 115.86, 106.59, 85.46, 85.04,
67.88, 34.16, 24.48, 19.40, 0.10; MS m/z 348 (M+, 0.4); HRMS
calcd for C18H24O3SSi 348.1216, found 348.1219. Anal. Calcd
for C18H24O3SSi: C, 62.03; H, 6.94. Found: C, 61.78; H, 7.02.
1-(Tr im eth ylsilyl)-1,7-octa d iyn -3-ol (33). To a solution
of 5-hexyn-1-ol (15) (1.96 g, 20.0 mmol), DMSO (6.40 mL, 90.0
mmol), and Et3N (12.5 mL, 90.0 mmol) in dry CH2Cl2 (100 mL)
was added SO3‚pyridine (14.3 g, 90.0 mmol) at 0 °C. After the
mixture was stirred for 1 h, the reaction was quenched by
J . Org. Chem, Vol. 68, No. 4, 2003 1383

Mukai et al.
addition of water, and the mixture was extracted with CH2Cl2.
The extract was washed with water and brine, dried, and
concentrated to dryness to afford the crude aldehyde. To a
solution of trimethylsilylacetylene (4.80 mL, 34.0 mmol) in dry
THF (100 mL) was added n-BuLi in hexane (1.43 M, 21.0 mL,
30.0 mmol) at -78 °C. After the mixture was stirred for 1 h,
a THF solution (20 mL) of the crude aldehyde was added, and
the reaction mixture was stirred for 3 h. The reaction was
quenched by addition of water, and the mixture was extracted
with AcOEt. The extract was washed with water and brine,
dried, and concentrated to dryness. The residue was chro-
matographed with 5:1 hexane-AcOEt to afford 33 (1.99 g,
51%) as a pale yellow oil: IR 3601, 3435, 3308, 2172, 2118
113.01, 106.20, 89.70, 84.66, 62.23, 36.48, 26.15, 22.93, -0.20;
MS m/z 348 (M+, 0.8). FABHRMS calcd for C18H25O3SSi
349.1294, found 349.1272.
Rin g Closu r e of 12a w ith Co2(CO)8 a n d TMANO. To a
solution of 12a (42.1 mg, 0.132 mmol), TMANO (99.3 mg, 1.32
mmol), and 4 Å MS (336 mg) in dry toluene (1.32 mL) was
added Co2(CO)8 (49.7 mg, 0.145 mmol) under an Ar atmosphere
at -10 °C. After being stirred for 17 h, the reaction mixture
was passed through a short pad of Celite with AcOEt and
concentrated to dryness. The residue was chromatographed
with 7:1 hexane-AcOEt to afford 2-(phenylsulfonyl)-7-tri-
methylsilylbicyclo[4.3.0]nona-1,6-dien-8-one (13a ) (23.9 mg,
52%) as a yellow oil: IR 1690 cm-1; 1H NMR δ 7.92-7.86 (m,
2H), 7.68-7.61 (m, 1H), 7.59-7.53 (m, 2H), 3.40 (s, 2H), 2.68
(t, 2H, J ) 6.4 Hz), 2.47 (t, 2H, J ) 5.9 Hz), 1.88-1.80 (m,
2H), 0.23 (s, 9H); 13C NMR δ 207.32, 173.76, 145.71, 144.44,
140.07, 134.07, 133.64, 129.35, 127.66, 39.45, 26.72, 25.09,
1
cm-1; H NMR δ 4.38 (t, 1H, J ) 6.8 Hz), 2.24 (td, 2H, J )
6.8, 2.4 Hz), 2.01 (br s, 1H), 1.95 (t, 1H, J ) 2.4 Hz), 1.87-
1.61 (m, 4H), 0.15 (s, 9H); 13C NMR δ 106.38, 89.60, 83.95,
68.68, 62.27, 36.46, 24.01, 18.04, -0.20; FABMS m/z 195 (M+
+ 1, 3.0); FABHRMS calcd for C11H19OSi 195.1205, found
195.1213. Anal. Calcd for C11H18OSi: C, 67.98; H, 9.34.
Found: C, 67.68; H, 9.53.
22.04, -0.80; MS m/z 346 (M+, 47); HRMS calcd for C18H22
-
O3SSi 346.1059, found 346.1058. Rin g Closu r e of 12a w ith
Co2(CO)8 in CH3CN. To a solution of 12a (10 mg, 3.1 × 10-2
mmol) in dry CH3CN (0.3 mL) was added Co2(CO)8 (13 mg,
3.8 × 10-2 mmol) under an Ar atmosphere, and the reaction
mixture was stirred for 20 min at 75 °C. Workup and
chromatography as described above gave 13a (5.0 mg, 46%).
Rin g Closu r e of 12a w ith F e(CO)4(NMe3). To a THF
solution (1.0 mL) of TMANO (61 mg, 0.81 mmol) in a Pyrex
test tube was added Fe(CO)5 (50 µL, 0.37 mmol) under an Ar
atmosphere at -30 °C. After the mixture was stirred for 1 h,
a THF solution of 12a (43 mg, 0.14 mmol, 0.35 mL) was added,
and the reaction mixture was stirred under external photo-
irradiation by a 100 W high-pressure mercury lamp at room
temperature for 18 h. Workup and chromatography as de-
scribed above gave 13a (8.3 mg, 18%). Rin g Closu r e of 12a
w ith F e2(CO)9. To a solution of 12a (30 mg, 0.094 mmol) and
DMSO (70 µL, 0.94 mmol) in dry toluene (1.0 mL) was added
Fe2(CO)9 (51 mg, 0.14 mmol). The reaction mixture was stirred
for 1 h under an Ar atmosphere at 100 °C. Workup and
chromatography as described above gave 13a (5.7 mg, 18%).
3-(ter t-Bu tyldim eth ylsiloxy)-1-(tr im eth ylsilyl)-1,7-n on a-
d iyn -9-ol (34a ). To a solution of 33 (800 mg, 4.12 mmol) in
dry DMF (2.0 mL) were added TBDMSCl (747 mg, 4.94 mmol)
and imidazole (421 mg, 6.19 mmol) at room temperature. After
being stirred at 60 °C for 1 h, the reaction mixture was cooled
to room temperature; the reaction was quenched by addition
of water, and the mixture was extracted with AcOEt. The
extract was washed with water and brine, dried, and concen-
trated to dryness. The residue was passed through a short pad
of silica gel with 20:1 hexane-AcOEt. To a solution of the
crude product in dry THF (40 mL) was added n-BuLi in hexane
(1.43 M, 4.30 mL, 6.14 mmol) at -78 °C. After the mixture
was stirred for 1 h, (HCHO)n (615 mg, 20.5 mmol) was added,
and the reaction mixture was gradually warmed to room
temperature over a period of 2 h. The reaction was quenched
by addition of water, and the mixture was extracted with
AcOEt. The extract was washed with water and brine, dried,
and concentrated to dryness. The residue was chromato-
graphed with 5:1 hexane-AcOEt to afford 34a (1.19 g, 86%)
Gen er a l P r oced u r e for Rin g Closu r e Rea ction w ith
[Rh Cl(CO)2]2: Con d ition A. To a solution of allenyne (0.10
mmol) in dry toluene (1.0 mL) was added 2.5 or 5.0 mol %
[RhCl(CO)2]2. The reaction mixture was refluxed under a CO
atmosphere until the complete disappearance of the starting
material as indicated by TLC. Toluene was evaporated off, and
the residue was chromatographed with hexane-AcOEt to
afford cyclized products. Chemical yields are summarized in
Tables 2-6.
1
as a colorless oil: IR 3609, 3435, 2170 cm-1; H NMR δ 4.35
(t, 1H, J ) 6.3 Hz), 4.24 (t, 2H, J ) 2.5 Hz), 2.25 (tt, 2H, J )
6.8, 2.5 Hz), 1.80-1.54 (m, 5H), 0.90 (s, 9H), 0.15 (s, 9H), 0.13
(s, 3H), 0.11 (s, 3H); 13C NMR δ 107.37, 88.70, 86.02, 78.60,
62.89, 51.30, 37.45, 25.77, 24.35, 18.42, 18.22, -0.21, -4.51,
-4.99; FABMS m/z 339 (M+ + 1, 0.4); FABHRMS calcd for
C
18H35O2Si2 339.2176, found 339.2166. Anal. Calcd for C18H34
-
O2Si2: C, 63.84; H, 10.12. Found: C, 63.48; H, 10.21.
Gen er a l P r oced u r e for Rin g Closu r e Rea ction w ith
[Rh Cl(CO)d p p p ]2: Con d ition B. To a solution of allenyne
(0.10 mmol) in dry toluene (1.0 mL) was added 2.5 or 5.0 mol
% [RhCl(CO)dppp]2. The reaction mixture was refluxed under
a CO atmosphere until the complete disappearance of the
starting material as indicated by TLC. Workup and chroma-
tography as described for condition A afforded cyclized prod-
ucts. Chemical yields are summarized in Tables 2-6.
2-(P h en ylsu lfon yl)-8-(tr im eth ylsilyl)bicyclo[5.3.0]deca-
1,7-d ien -9-on e (18a ): colorless needles, mp 106-106.5 °C
(hexane-AcOEt); IR 1695 cm-1; 1H NMR δ 7.89-7.85 (m, 2H),
7.65-7.52 (m, 3H), 3.49 (s, 2H), 2.79 (t, 2H, J ) 6.8 Hz), 2.72
(t, 2H, J ) 6.4 Hz), 1.81-1.71 (m, 4H), 0.26 (s, 9H); 13C NMR
δ 207.46, 179.13, 148.48, 148.43, 140.50, 137.38, 133.50,
129.33, 127.54, 42.47, 29.02, 26.45, 26.15, 23.44, -0.43; MS
m/z 360 (M+, 78); HRMS calcd for C19H24O3SSi 360.1215, found
360.1218. Anal. Calcd for C19H24O3SSi: C, 63.29; H, 6.71.
Found: C, 63.19; H, 6.82.
7-(ter t-Bu tyld im eth ylsiloxy)-3-(p h en ylsu lfon yl)-9-(tr i-
m eth ylsilyl)-1,2-n on a d ien -8-yn e (35a ). According to the
procedure described for preparation of 12a , 35a (415 mg, 35%)
was obtained from 34a (870 mg, 2.57 mmol) as a colorless oil:
IR 2170, 1971, 1940 cm-1; 1H NMR δ 7.91-7.86 (m, 2H), 7.64-
7.59 (m, 1H), 7.56-7.50 (m, 2H), 5.37 (t, 2H, J ) 3.4 Hz), 4.29-
4.22 (m, 1H), 2.31-2.18 (m, 2H), 1.66-1.48 (m, 4H), 0.86 (s,
9H), 0.13 (s, 9H), 0.09 (s, 3H), 0.06 (s, 3H); 13C NMR δ 207.64,
140.11, 133.42, 129.02, 128.07, 113.23, 107.21, 88.75, 84.57,
62.80, 37.32, 26.11, 25.75, 23.08, 18.19, -0.23, -4.53, -5.03;
FABMS m/z 463 (M+ + 1, 1.0); FABHRMS calcd for C24H39
-
O3SSi2 463.2158, found 463.2151.
3-(P h en ylsu lfon yl)-9-(t r im et h ylsilyl)-1,2-n on a d ien -8-
yn -7-ol (36a ). To a solution of 35a (185 mg, 0.40 mmol) in
THF (6.0 mL) was added 10% aqueous HCl (2.0 mL) at room
temperature. After being stirred for 8 h, the reaction mixture
was neutralized with saturated aqueous NaHCO3 and ex-
tracted with AcOEt. The extract was washed with water and
brine, dried, and concentrated to dryness. The residue was
chromatographed with 3:1 hexane-AcOEt to afford 36a (131
mg, 94%) as a colorless oil: IR 3601, 3510, 2170, 1971, 1940
cm-1; 1H NMR δ 7.91-7.86 (m, 2H), 7.65-7.59 (m, 1H), 7.57-
7.50 (m, 2H), 5.37 (t, 2H, J ) 3.4 Hz), 4.33-4.25 (m, 1H), 2.31-
2.22 (m, 2H), 1.90 (d, 1H, J ) 5.4 Hz), 1.70-1.54 (m, 4H), 0.14
(s, 9H); 13C NMR δ 207.60, 140.00, 133.48, 129.04, 128.05,
4,4-Bis(m eth oxyca r bon yl)-2-(p h en ylsu lfon yl)bicyclo-
[5.3.0]d eca -1,7-d ien -9-on e (27a ): pale yellow needles, mp
164.5-165.5 °C (hexane-AcOEt); IR 1732, 1701 cm-1; 1H NMR
δ 7.91-7.80 (m, 2H), 7.70-7.50 (m, 3H), 6.23 (s, 1H), 3.73 (s,
6H), 3.39 (s, 2H), 3.34 (s, 2H), 2.81-2.67 (m, 2H), 2.49-2.35
(m, 2H); 13C NMR δ 202.10, 171.64, 170.82, 147.91, 140.18,
136.23, 133.80, 133.53, 129.47, 127.75, 57.22, 53.21, 41.44,
1384 J . Org. Chem., Vol. 68, No. 4, 2003

Construction of the Bicyclo[5.3.0]decenone Skeleton
30.82, 29.27, 26.49; MS m/z 404 (M+, 100); HRMS calcd for
Hz), 2.93 (dd, 1H, J ) 16.6, 11.7 Hz), 2.76 (dd, 1H, J ) 17.6,
6.8 Hz), 2.03-1.85 (m, 3H), 1.64-1.52 (m, 1H), 0.76 (s, 9H),
0.26 (s, 9H), 0.02 (s, 3H), -0.14 (s, 3H); 13C NMR δ 207.74,
177.30, 147.28, 144.47, 140.50, 140.09, 133.33, 129.18, 127.66,
70.82, 42.97, 33.78, 28.39, 26.06, 25.54, 17.76, -0.41, -4.69,
-4.81; FABMS m/z 491 (M+ + 1, 1.7); FABHRMS calcd for
C
C
20H20O7S 404.0929, found 404.0931. Anal. Calcd for
20H20O7S: C, 59.40; H, 4.98. Found: C, 59.34; H, 5.02.
5,5-Bis(m eth oxyca r bon yl)-2-(p h en ylsu lfon yl)bicyclo-
[5.3.0]d eca -1,7-d ien -9-on e (28a ): colorless plates, mp 128.5-
1
129 °C (hexane-AcOEt); IR 1732, 1711 (sh) cm-1; H NMR δ
7.91-7.81 (m, 2H), 7.71-7.50 (m, 3H), 6.37 (s, 1H), 3.71 (s,
6H), 3.55 (s, 2H), 3.27 (s, 2H), 2.84-2.71 (m, 2H), 2.32-2.19
(m, 2H); 13C NMR δ 202.41, 170.82, 166.94, 146.18, 139.68,
139.16, 138.96, 133.91, 129.51, 127.66, 55.49, 53.17, 41.62,
34.49, 33.86, 24.96; MS m/z 404 (M+, 100); HRMS calcd for
C
C
25H39O4SSi2 491.2108, found 491.2105. Anal. Calcd for
25H38O4SSi2: C, 61.18; H, 7.80. Found: C, 61.12; H, 8.01.
6-Hydr oxy-2-(ph en ylsu lfon yl)-8-(tr im eth ylsilyl)bicyclo-
[5.3.0]d eca -1,7-d ien -9-on e (40a ): colorless plates, mp 113-
114 °C (hexane-AcOEt); IR 3601, 3503, 1699 cm-1; H NMR
1
C
C
20H20O7S 404.0930, found 404.0926. Anal. Calcd for
20H20O7S: C, 59.40; H, 4.98. Found: C, 59.31; H, 5.07.
3-(t er t -Bu t yld im e t h ylsiloxy)-2-(p h e n ylsu lfon yl)-8-
δ 7.87-7.81 (m, 2H), 7.65-7.58 (m, 1H), 7.57-7.50 (m, 2H),
5.08 (t, 1H, J ) 4.9 Hz), 3.54 (AB-q, 2H, J ) 21.5 Hz), 2.97
(ddd, 1H, J ) 17.1, 10.3, 2.4 Hz), 2.66 (ddd, 1H, J ) 17.1, 7.3,
2.4 Hz), 2.09-1.96 (m, 2H), 1.94-1.78 (m, 2H), 1.71-1.59 (m,
1H), 0.27 (s, 9H); 13C NMR δ 207.20, 177.93, 150.31, 145.27,
140.27, 138.08, 133.53, 129.33, 127.44, 69.29, 42.98, 31.66,
27.91, 24.03, 0.04; MS m/z 376 (M+, 1.8); HRMS calcd for
C19H24O4SSi 376.1164, found 376.1167. Anal. Calcd for C19H24O4-
SSi: C, 60.60; H, 6.42. Found: C, 60.53; H, 6.48.
(tr im eth ylsilyl)bicyclo[5.3.0]deca-1,7-dien -9-on e (37a): col-
orless oil; IR 1697 cm-1; 1H NMR δ 7.88-7.84 (m, 2H), 7.62-
7.49 (m, 3H), 5.16 (dd, 1H, J ) 4.4, 2.4 Hz), 3.34 (AB-q, 2H, J
) 21.5 Hz), 3.36-3.28 (m, 1H), 2.88 (dt, 1H, J ) 15.1, 3.9 Hz),
2.10-1.95 (m, 2H), 1.69-1.54 (m, 2H), 0.84 (s, 9H), 0.24 (s,
9H), 0.14 (s, 3H), 0.01 (s, 3H); 13C NMR δ 206.24, 179.49,
151.63, 149.75, 141.18, 138.83, 133.40, 129.19, 127.40, 67.99,
42.84, 33.10, 29.59, 25.65, 21.33, 18.00, -0.57, -4.90; MS m/z
490 (M+, 0.1); HRMS calcd for C25H38O4SSi2 490.2029, found
490.2015. Anal. Calcd for C25H38O4SSi2: C, 61.18; H, 7.80.
Found: C, 61.55; H, 8.17.
8-P h en yl-2-(p h en ylsu lfon yl)b icyclo[5.3.0]d eca -1,5,7-
tr ien -9-on e (41): colorless oil; IR 1701 cm-1; 1H NMR δ 7.95-
7.88 (m, 2H), 7.69-7.55 (m, 3H), 7.47-7.30 (m, 5H), 6.59 (d,
1H, J ) 11.7 Hz), 6.34 (dt, 1H, J ) 11.7, 5.9 Hz), 3.81 (s, 2H),
2.92-2.82 (m, 2H), 2.54-2.42 (m, 2H); 13C NMR δ 201.15,
156.73, 145.68, 143.81, 141.28, 140.50, 136.95, 133.64, 130.08,
129.43, 129.16, 128.39, 127.49, 124.42, 41.62, 28.48, 28.41;
FABMS m/z 363 (M+ + 1, 31); FABHRMS calcd for C22H19O3S
363.1055, found 363.1048.
3-Hydr oxy-2-(ph en ylsu lfon yl)-8-(tr im eth ylsilyl)bicyclo-
[5.3.0]d eca -1,7-d ien -9-on e (38a ): pale yellow plates, mp
1
147-148 °C (hexane-CH2Cl2); IR 3566, 1699 cm-1; H NMR
δ 7.91-7.87 (m, 2H), 7.65-7.52 (m, 3H), 5.02-4.97 (m, 1H),
3.46 (AB-q, 2H, J ) 21.5 Hz), 3.16 (ddd, 1H, J ) 14.7, 10.7,
5.9 Hz), 2.94-2.87 (m, 2H), 2.22-2.03 (m, 2H), 1.69-1.57 (m,
2H), 0.25 (s, 9H); 13C NMR δ 206.50, 178.06, 152.49, 150.55,
140.18, 138.41, 133.69, 129.46, 127.46, 67.21, 43.21, 31.59,
29.99, 20.76, -0.54; MS m/z 376 (M+, 12); HRMS calcd for
C19H24O4SSi 376.1164, found 376.1164. Anal. Calcd for C19H24O4-
SSi: C, 60.60; H, 6.42. Found: C, 60.38; H, 6.43.
Su p p or t in g In for m a t ion Ava ila b le: 1H and 13C NMR
spectra for compounds 10a ,c, 11, 12b,c, 13a , 16a , 17b,c,
22a ,b, 29, 30a -c, 31a -c, 32b, 35a -c, and 41 and charac-
terization data for compounds 12b,c, 13b,c, 16b,c, 17b,c,
18b,c, 22b, 23b, 25b, 26b, 27b, 28b, 30b,c, 31b,c, 32b,c,
34b,c, 35b,c, 36b,c, 37b,c, 38b,c, 39b,c, and 40b,c. This
material is available free of charge via the Internet at
http://pubs.acs.org.
6-(t er t -Bu t yld im e t h ylsiloxy)-2-(p h e n ylsu lfon yl)-8-
(tr im eth ylsilyl)bicyclo[5.3.0]deca-1,7-dien -9-on e (39a): col-
orless needles, mp 140-141 °C (hexane-AcOEt); IR 1697 cm-1
;
1H NMR δ 7.89-7.81 (m, 2H), 7.63-7.47 (m, 3H), 5.13-5.07
(m, 1H), 3.66 (d, 1H, J ) 21.5 Hz), 3.41 (dd, 1H, J ) 21.5, 2.0
J O020649H
J . Org. Chem, Vol. 68, No. 4, 2003 1385