Stereocomplementary Construction of Optically Active Bicyclo[4.3.0]nonenone Derivatives

Article abstract of DOI:10.1021/jo990819z

Treatment of (5S,6S)-5,6-bis(tert-butyldimethylsiloxy)-8-(substituted)oct-1-en-7-yne derivatives, prepared from diethyl L-tartrate, with Co₂(CO)₈ afforded the corresponding cobalt-complexed enynes, which were subsequently exposed to the typical Pauson-Khand conditions to furnish highly stereoselectively or exclusively (2S,3S,6S)-2,3-bis(tert-butyldimethylsiloxy)-9-(substituted)bicyclo-[4.3.0]non- 1(9)-en-8-ones. On the other hand, (3S,4S)-1-(substituted)oct-7-en-1-yne-3,4-diol congeners produced, on exposure to the Pauson-Khand conditions, (2S,3S,6A)-2,3-dihydroxy-9-(substituted)-bicyclo[4.3.0]-non-1(9)-en-8-one derivatives in a highly stereoselective manner. The newly developed procedure has been shown to be useful for construction of the 2,3-bis(oxygenated)-7-(substituted)-bicyclo[4.3.0]non-6-en-8-one framework in a stereocomplementary as well as stereoselective fashion.

Full text of DOI:10.1021/jo990819z

6822
J . Org. Chem. 1999, 64, 6822-6832
Ster eocom p lem en ta r y Con str u ction of Op tica lly Active
Bicyclo[4.3.0]n on en on e Der iva tives
Chisato Mukai,* J in Sung Kim, Hiroshi Sonobe, and Miyoji Hanaoka*
Faculty of Pharmaceutical Sciences, Kanazawa University, Takara-machi, Kanazawa 920, J apan
Received May 19, 1999
Treatment of (5S,6S)-5,6-bis(tert-butyldimethylsiloxy)-8-(substituted)oct-1-en-7-yne derivatives,
prepared from diethyl L-tartrate, with Co2(CO)8 afforded the corresponding cobalt-complexed enynes,
which were subsequently exposed to the typical Pauson-Khand conditions to furnish highly
stereoselectively or exclusively (2S,3S,6S)-2,3-bis(tert-butyldimethylsiloxy)-9-(substituted)bicyclo-
[4.3.0]non-1(9)-en-8-ones. On the other hand, (3S,4S)-1-(substituted)oct-7-en-1-yne-3,4-diol congeners
produced, on exposure to the Pauson-Khand conditions, (2S,3S,6R)-2,3-dihydroxy-9-(substituted)-
bicyclo[4.3.0]-non-1(9)-en-8-one derivatives in a highly stereoselective manner. The newly developed
procedure has been shown to be useful for construction of the 2,3-bis(oxygenated)-7-(substituted)-
bicyclo[4.3.0]non-6-en-8-one framework in a stereocomplementary as well as stereoselective fashion.
Sch em e 1
In tr od u ction
The optically active bicyclo[m.3.0] ring system has been
found to be a core skeleton of many natural products.
Both linear and angular triquinane sesquiterpenes,1 for
instance, have the bicyclo[3.3.0]octane framework as a
common structural feature. The representative natural
products possessing a bicyclo[4.3.0] skeleton must be
exemplified as the picrotoxanes.2 In addition, the bicyclo-
[5.3.0] and bicyclo[6.3.0] ring systems can be found in
guaianolides3 and ophiobolins,4 respectively. An efficient
and highly stereoselective general method for construc-
tion of the optically active bicyclo[m.3.0] ring system,
therefore, would become a powerful tool for the total
synthesis of these natural products.
the bicyclo[3.3.0]octenone derivatives 2 (n ) 1) possessing
two distinguishable hydroxy functionalities in line with
our synthetic plan.
Our efforts8 were then directed toward application of
the newly developed method to construct the correspond-
ing bicyclo[4.3.0]nonenone derivatives 2 (n ) 2). We
describe here a highly stereoselective as well as stereo-
complementary method for preparation of the bicyclo-
[4.3.0]nonenones.
The intramolecular Pauson-Khand reaction,5 a formal
[2 + 2 + 1] cyclization reaction of three components
(alkyne and olefin moieties and carbon monoxide), has
emerged as one of the most reliable methods for con-
struction of the cyclopentenone-fused bicyclo compounds.
During the course of our program6 directed toward the
development of stereoselective reactions mediated by
alkyne-dicobalt hexacarbonyl complexes, we had envi-
sioned that the optically active enyne derivatives 1
derived from L-tartrate would be versatile starting ma-
terials for the intramolecular Pauson-Khand reaction
leading to the target bicyclo[m.3.0] ring system 2. In the
previous papers,7 we succeeded in development of a new
procedure for the highly stereoselective construction of
Resu lts a n d Discu ssion
In tr a m olecu la r P a u son -Kh a n d Rea ction of (5S,-
6S)-5,6-Bis(oxygen a ted )oct-1-en -7-yn e Der iva tives.
The required optically active enyne derivatives 5, 6, and
7 were easily obtained from diethyl L-tartrate. The known
alcohol 3, derived from diethyl L-tartrate according to
Kotsuki’s procedure,9 was exposed to Corey’s dibromoole-
fination10 to give the dibromo derivative 4 in 72% yield,
which was then treated with n-BuLi10 affording 5a in
78% yield. Hydrolysis of 5a with p-toluenesulfonic acid
(PTSA) in methanol provided the diol 6a in 92% yield.
Introduction of the tert-butyldimethylsilyl (TBDMS) group
on the dihydroxy group of 6a was realized by treatment
with TBDMSCl in DMF to furnish 7a in 99% yield. The
other enynes 5b,c, 6b,c, and 7b,c were obtained from
* To whom correspondence should be addressed. Tel: +81-76-223-
4411. Fax: +81-76-234-4410. E-mail: cmukai@kenroku.kanazawa-
u.ac.jp.
(1) Fraga, B. M. Nat. Prod. Chem. 1992, 9, 217.
(2) Porter, L. A. Chem. Rev. 1967, 67, 441.
(3) Herz, H.; Santhanam, P. S. J . Org. Chem. 1965, 30, 4340.
(4) Nozoe, S.; Morisaki, M.; Tsuda, K.; Iitaka, Y.; Takahashi, N.;
Tamura, S.; Ishibashi, K.; Shirasaka, M. J . Am. Chem. Soc. 1965, 87,
4968.
(5) (a) Schore, N. E. In Comprehensive Organometallic Chemistry
II; Abel, E. W., Stone, F. G., Wilkinson, G., Eds.; Elsevier: New York,
1995; Vol. 12, p 703; (b) Comprehensive Organic Synthesis; Trost, B.
M., Fleming, I., Paquette, L. A., Eds.; Pergamon: Oxford, 1991; Vol.
5, p 1037; (c) Org. React. 1991, 40, 1; (d) Chem. Rev. 1988, 88, 1081.
(e) Pauson P. L. In Organometallics in Organic Synthesis. Aspects of a
Modern Interdisciplinary Field; de Meijere, A., tom Dieck, H., Eds.;
Spring: Berlin, 1988; p 233.
(7) (a) Mukai, C.; Uchiyama, M.; Sakamoto, S.; Hanaoka, M.
Tetrahedron Lett. 1995, 36, 5761. (b) Mukai, C.; Kim, J . S.; Uchiyama,
M.; Sakamoto, S.; Hanaoka, M. J . Chem. Soc., Perkin Trans. 1 1998,
2903.
(8) A part of this work was published in a preliminary communica-
tion: Mukai, C.; Kim, J . S.; Uchiyama, M,; Hanaoka, M. Tetrahedron
Lett. 1998, 39, 7909.
(9) Kotsuki, H.; Miyazaki, A.; Ochi, M.; Sims, J . J . Bull. Chem. Soc.
J pn 1991, 64, 721.
(6) Mukai, C.; Hanaoka, M. Synlett 1996, 11 and references therein.
(10) Corey, E. J .; Fuchs, P. L. Tetrahedron Lett. 1972, 3769.
10.1021/jo990819z CCC: $18.00 © 1999 American Chemical Society
Published on Web 08/18/1999

Construction of Bicyclo[4.3.0]nonenone Derivatives
J . Org. Chem., Vol. 64, No. 18, 1999 6823
Ta ble 1. P a u son -Kh a n d Rea ction of En yn e 7
Sch em e 2a
entry substrate
condition
R
ratioa 8:9
yieldb (%)
1
2
3
4
5
6
7a
7a
7b
7b
7c
7c
A
B
A
B
A
B
H
H
Ph
Ph
TMS
TMS
88:12
88:12
100:0
100:0
100:0
100:0
85
86
99
67c
62d
27e
a
b
Determined by HPLC analysis. Total yield of 8 and 9.
c (1S,2S,3E)-Benzylidene-1,2-bis(tert-butyldimethylsilyloxy)-4-me-
d
thylenecyclohexane (10b) was obtained in 27% yield. The starting
7c was recovered in 16% yield. e The starting 7c was recovered in
44% yield.
5a , 6a , 7a by conventional means (see the Experimental
Section).In the previous papers,7 the highly diastereose-
lective formation of the bicyclo[3.3.0]octenone skeleton
was realized when the starting enynes having the TB-
DMSO group at the propynyl and homopropynyl positions
were exposed to the typical Pauson-Khand conditions.
On the basis of these results, we first investigated the
Pauson-Khand reaction of 7, hoping for highly stereo-
selective construction of the bicyclo[4.3.0]nonenone frame-
work. The Pauson-Khand reaction was carried out under
two conditions, the results of which are summarized in
Table 1. Treatment of 7a with dicobaltoctacarbonyl [(Co2-
(CO)8] in methylene chloride at room temperature gave
the corresponding cobalt-complexed derivative. The com-
plex was then heated in acetonitrile11 at 70-75 °C
(condition A) to afford the cyclized products 8a and 9a
in a ratio of 88:12 in 85% yield. A similar result was
obtained when the cobalt-complexed 7a was exposed to
trimethylamine N-oxide (TMANO)12 in THF (condition
B) at room temperature (Table 1, entry 2). The higher
diastereoselectivity was observed in the case of the
phenyl derivative 7b where exclusive formation of 8b
could be achieved (Table 1, entries 3 and 4). It should be
mentioned that the 1,3-diene derivative13,14 10b was
obtained in 27% yield as a byproduct in the case of 7b
under condition B. The formation of 10b could be
tentatively interpreted by the mechanism proposed by
Krafft14 recently, in which the generally acceptable
metallocyclic intermediate5 would collapse to 10b via
allylic C-H insertion instead of carbonyl insertion lead-
ing to the normal cyclopentenone derivatives. The exclu-
sive formation of 8c in 62 and 27% yields was also
realized under conditions A and B along with the recovery
of the starting enyne 7c in 16 and 44% yields, respec-
tively (Table 1, entries 5 and 6). These results were in
good accordance with the prediction based on the previ-
ous works.7
The structure of 8 and 9 was apparent from spectral
evidence (see the Experimental Section). The stereo-
chemical assignment of the cyclized products 8 and 9 was
made by examination of the 1H NMR spectra. The
1
distinguishing feature of the H NMR spectra of 8a and
9a is the difference in the coupling constants between
H-2 and H-3. The 1H NMR spectrum of 8a revealed a
smaller coupling constant (3.4 Hz) between H-2 and H-3
due to an equatorial-equatorial coupling, while that of
the corresponding 6-epimer 9a showed a rather large
value (8.3 Hz) attributable to a typical axial-axial
coupling. Therefore, it is reasonable to consider that the
preferred conformation of 8a possesses two axial TB-
DMSO groups at the C-2 and the C-3 positions. On the
other hand, 9a must have the preferred conformer in
which two TBDMSO groups should take an equatorial
site. In addition, an NOE experiment with 9a revealed
3.8% enhancement between the H-2 and the H-6 (1,3-
diaxial relationship), but no enhancement between the
H-2 and the H-6 could be observed in the NOE experi-
1
ment with 8a . These information from H NMR analysis
confirmed the stereochemical assignment for both 8a and
9a . The stereochemistry of 1,3-diene derivative 10b, a
byproduct obtained from the reaction of 7b (Table 1, entry
4), was also determined on the basis of an NOE experi-
ment. The fact that irradiation of the Ha produced 11.9%
enhancement of the Hb while no enhancement of the Hc
could be detected in its NOE experiment strongly sup-
ported the structure depicted for 10b.
(11) (a) Chung, Y. K.; Lee, B. Y.; J eong, N.; Hudeced, M.; Pauson,
P. L. Organometallics 1993, 12, 220. (b) Hoye, T. R.; Suriano, J . J .
Org. Chem. 1993, 58, 1659.
(12) J eong, N.; Chung, Y. K.; Lee, B. Y.; Lee, S. H.; Yoo, S. E. Synlett
1991, 204.
(13) Khand, I. U.; Pauson. P. L. J . Chem. Soc., Chem. Commun.
1974, 379.
(14) Ktafft, M. E.; Wilson, A. M.; Dasse, O. A.; Bonaga, L. V. R.;
Cheung, Y. Y.; Fu, Z.; Shao, B,; Scott, I. L. Tetrahedron Lett. 1998, 39,
5911.
We next investigated the Pauson-Khand reaction of
the enynes 6 with two free hydroxy groups at both the
propynyl and homopropynyl positions. The results are

6824 J . Org. Chem., Vol. 64, No. 18, 1999
Ta ble 2. P a u son -Kh a n d Rea ction of En yn e 6
Mukai et al.
Ta ble 3. P a u son -Kh a n d Rea ction of En yn e 5
entry substrate condition
R
ratioa 11:12
yieldb (%)
entry substrate condition
R
ratioa 13:14 yieldb (%)
1
2
3
4
5
6
7
8
9
6a
6a
6b
6b
6c
6c
6a
6b
6c
A
B
A
B
A
B
C
C
C
H
H
17:83
32:68
2:98
15:85
21:79
27:73
5:95
37
72
65
1
2
3
4
5
6
5a
5a
5b
5b
5c
5c
A
B
A
B
A
B
H
H
0:100
0:100
0:100
0:100
0:100
0:100
28
21
56c
32d
8e
Ph
Ph
TMS
TMS
H
88
Ph
Ph
TMS
TMS
22c
30d
88
2f
Ph
TMS
1:99
5:95
94
a
b
54e
Determined by HPLC analysis. Total yield of 13 and 14.
c The starting 5b was recovered in 22% yield. The starting 5b
was recovered in 18% yield. e The starting 5c was recovered in
47% yield. f The starting 5c was recovered in 50% yield.
d
a
b
Determined by HPLC analysis. Total yield of 11 and 12.
c The cobalt-complexed 6c was recovered in 12% yield. The
starting 6c was recovered in 29% yield. e The starting 6c was
recovered in 15% yield.
d
possibility of the hydrogen bonding occurring, the enyne
derivative 5 was used as a substrate for the Pauson-
Khand reaction. The enyne 5 has the trans dioxolane
ring, which might be roughly regarded as a tightly
coordinated model of hydrogen bonding. The Pauson-
Khand reaction of 5a through cobalt complexation was
carried out under conditions A and B to produce 14a
exclusively as expected (Table 3, entries 1 and 2),
although the yield was unsatisfactory. The phenyl con-
gener 5b gave the corresponding 14b exclusively along
with the recovery of the starting 5b (Table 3, entries 3
and 4). In the case of 5c with the terminal TMS group,
exclusive formation of the corresponding 14c was ob-
served. However, decomplexation of the cobalt-complexed
moiety became the major reaction pathway to leave
almost half of the starting 5c (Table 3, entries 5 and 6).
The low chemical yield of the cyclized product 14 from 5
would be attributed to the serious ring strain arising
during the carbon-carbon bond formation process giving
rise to the trans-fused dioxatricyclo[7.3.0.02,6]dodecenone
skeleton. The dioxolane ring in the enyne 5 seems to be
more rigid than the plausible five-membered ring by
hydrogen bonding in 6 because the carbon-oxygen bond
length must be shorter than that of hydrogen bonding.
This would reflect the difference observed in chemical
yield between the series of 5 and 6.
Therefore, it is of great interest to change the dioxolane
ring of 5 into a dialkylated silylene ring because the
silicon-oxygen bond would be more similar to the
plausible hydrogen bonding. Thus, the di-tert-butyl-
silylene derivative 15, prepared from the dihydroxy
compound 6 with di-tert-butylsilyl triflate,17 appeared to
be an attractive substrate to see if 15 would undergo the
Pauson-Khand reaction to provide selectively the cy-
clized product with the same stereochemistry as that of
12 and 14 in rather improved yield. The Pauson-Khand
reaction of 15 was performed under the conditions
according to the case of 5. The resulting cyclized products
with the silylene ring were found to be unstable for
chromatographic separation. Thus, these cyclized prod-
ucts were immediately desilylated with tetra-n-butyl-
summarized in Table 2. Treatment of 6a with Co2(CO)8
provided the corresponding cobalt-complexed 6a , which
was successively heated under the condition A to furnish
a mixture of 11a and 12a in 37% yield (Table 2, entry
1). Although the chemical yield was rather low, the
diastereoselectivity was interestingly in sharp contrast
to that observed in the Pauson-Khand reaction of the
enynes 7 with the sterically bulky TBDMS group on two
hydroxy moieties. The similar preferential formation of
12a over 11a was recognized when the cyclization of 6a
was performed under the condition B (Table 2, entry 2).
The phenyl and the trimethylsilyl (TMS) congeners 6b
and 6c also showed the same bias in which the predomi-
nant formation of 12b,c was constantly recorded (Table
2, entries 3-6). At this stage, we tentatively envisioned
that the vicinal two hydroxy functionalities of 6 would
control the diastereoselectivity resulting in the predomi-
nant production of 12. In other words, we postulated that
the transient five-membered ring possessing the two
carbon appendages in a trans relationship that might be
formed due to intramolecular hydrogen bonding of the
vicinal hydroxy groups governs the stereochemical out-
come. With the above assumption, the enyne 6a was
exposed to the condition with N-methylmorpholine N-
oxide (NMO)15 in methylene chloride (condition C)16
where the hydrogen bonding would be expected to be
more easily achieved compared to conditions A and B.
Thus, treatment of the cobalt-complexed 6a under condi-
tion C afforded 12a in a highly stereoselective fashion
(11a :12a ) 9:95) in 88% yield (Table 2, entry 7) as
anticipated. Similarly the highly stereoselective construc-
tion of 12b and 12c could be attained in the cases of 6b
and 6c as shown in Table 2 (entries 8 and 9).
To obtain further information about the mechanism for
the highly stereoselective construction of the bicyclo-
[4.3.0]nonenone derivative 12, especially anticipating
obtaining some supportive experimental results on the
(15) NMO was employed as an amine N-oxide instead of TMANO‚
2H2O under condition C because of the poor solubility of the latter in
dry methylene chloride.
(16) Shambayati, S.; Crowe, W. E.; Schreiber, S. L. Tetrahedron Lett.
1990, 31, 5289.
(17) Corey, E. J .; Hopkins, P. B. Tetrahedron Lett. 1982, 23, 4871.

Construction of Bicyclo[4.3.0]nonenone Derivatives
J . Org. Chem., Vol. 64, No. 18, 1999 6825
Ta ble 4. P a u son -Kh a n d Rea ction of En yn e 15
Sch em e 4
entry substrate condition
R
ratioa 11:12 yieldb (%)
1
2
3
4
5
6
15a
15a
15b
15b
15c
15c
A
B
A
B
A
B
H
H
Ph
Ph
TMS
TMS
3:97
1:99
4:96
1:99
0:100
33
54
32c
57d
10e
f
a
b
Determined by HPLC analysis. Total yield of 11 and 12.
c The desilylated enyne 6b was recovered in 29% yield. The
desilylated enyne 6b was recovered in 12% yield. e The desilylated
enyne 6c was recovered in 50% yield. f The desilylated enyne 6c
was recovered in 50% yield.
d
Sch em e 3
R1 (TBDMS) group and R2 substituent have a trans
alignment. As a result, the cyclization pathway through
the intermediate 16 would be preferred over that through
17. Unfortunately, these analyses cannot be used to
explain the highly diastereoselective bias observed in the
Pauson-Khand reaction of 6 where the compound 12
having stereochemistry at the C-6 opposite to that of 8
was obtained in a highly stereoselective manner. The
intermediate 17 (R1 ) H) derived from 6 seemed to have
more serious steric repulsion between the R1O and R2
groups than that of 16, resulting in the predominant
formation of 11 over 12. This prediction, however, was
in sharp contrast to the results obtained (Table 2).
Therefore, an alternative explanation will be required to
understand the highly stereoselective and stereocomple-
mentary construction of the bicyclo[4.3.0]nonenones 8
and 12 drawn in Tables 1 and 2.
Irradiation of the H-6 exhibited 6.6% enhancement of
the H-5 in an NOE experiment with 7b, strongly indicat-
ing that these two vicinal protons should preferentially
be oriented in an gauche relationship each other (diequa-
torial-like positions); therefore, the two TBDMSO groups
must have an antiperiplanar relation. Furthermore, the
1H NMR spectrum revealed a coupling constant (4.9 Hz)
that supports the above conformational analysis. Thus,
the preferred conformer for 7b would be described as the
conformer A or A′ shown in Scheme 4. This type of
conformational analysis had already been proposed by
Saito et al.19 for the mechanism in a series of stereose-
lective reactions of compounds with vicinal bis-TBDMSO
groups derived from L-tartrate. On the other hand, an
NOE experiment with the corresponding dihydroxy com-
pound 6b showed a rather smaller enhancement (2.3%)
between the H-5 and the H-6. In addition, enhancement
ammonium fluoride (TBAF) to give the corresponding
dihydroxy derivative 12 in a highly stereoselective man-
ner in a moderate yield as shown in Table 4. Combination
of these results for the almost exclusive formation of 14
and 12 from 5 and 15, respectively, with the fact that
the dihydroxy derivative 6 afforded 12 in a highly
stereoselective fashion strongly indicates the existence
of the conformer with a five-membered ring due to
hydrogen bonding during the conversion of 6 into 12.
In the previous paper,7b we could interpret the stereo-
selective formation of the bicyclo[3.3.0]octenone deriva-
tives possessing the same stereochemistry as that of 8
based on the mechanistic hypothesis for the intramo-
lecular Pauson-Khand reaction proposed by Magnus.18
Highly preferential construction of the bicyclo[4.3.0]-
nonenone 8 over its epimer 9 from the enyne 7 again
might be tentatively explained in terms of the interme-
diacy of similar cobalt-metallocycles (Scheme 3). Two
plausible intermediates 16 and 17 must exist leading to
compounds 8 and its epimer 9, respectively. In the cobalt-
metallocycle 17, the hydroxy functionality (R1 ) TBDMS)
at the propynyl position should have a nonbonding
interaction with the substituent at the acetylenic termi-
nus (R2 group) due to a kind of 1,3-pseudodiaxial rela-
tionship in the sterically congested concave face of the
transient cobaltabicyclo[4.3.0]nonenone skeleton; there-
fore, a seriously unfavorable interaction might occur. This
would not be the case in the intermediate 16 where the
(19) (a) Saito, S.; Hirohara, Y.; Narahara, O.; Moriwake, T. J . Am.
Chem. Soc. 1989, 111, 4533. (b) Saito, S.; Morikawa, Y.; Moriwake, T.
J . Org. Chem. 1990, 55, 5424. (c) Saito, S.; Morikawa, Y.; Moriwake,
T. Synlett 1990, 523. (d) Saito, S.; Narahara, O.; Ishikawa, T.; Asahara,
M.; Moriwake, T.; Gawronski, J .; Kazmierczak, F. J . Org. Chem. 1993,
58, 6292. (e) Saito, S.; Ishikawa, T.; Moriwake, T. Synlett 1994, 279.
(f) Ishikawa, T.; Tajima, Y.; Fukui, M.; Saito, S. Angew. Chem., Int.
Ed. Engl. 1996, 35, 1863.
(18) (a) Magnus, P.; Principe, L. M. Tetrahedron Lett. 1985, 26, 4851.
(b) Magnus, P.; Exon, C.; Albaugh-Robertson, P. Tetrahedron 1985,
41, 5861.

6826 J . Org. Chem., Vol. 64, No. 18, 1999
Mukai et al.
Sch em e 5
of the C-4 methylene protons (3.5%) could be observed
when H-6 was irradiated. This was not the case in an
NOE experiment with 7b in which no enhancement of
the C-4 methylene protons by irradiation of the H-6 could
be recognized. It is noteworthy to mention here that the
coupling constant between the H-5 and the H-6 of 6b was
shown to be the diaxial-like coupling constant (6.4 Hz).
Very similar behavior was recorded in an NOE experi-
ment with the dioxolane derivative 5b. Namely, irradia-
tion of the H-6 effected enhancement of the H-5 (1.1%)
and the C-4 methylene protons (4.1%) as well. Further-
more, the coupling constant between the H-5 and the H-6
(7.8 Hz) is found to be closer to that of 6b than 7b. On
the basis of these observations, we tentatively assumed
that the preferred conformer for 6b should be B or B′.
To obtain further information about the mechanism for
the high stereoselectivity, the NMR spectral analysis
including an NOE experiment of the cobalt-complexed
6b and 7b was attempted several times, but only unclear
and broadening peaks could be recorded presumably due
to partial decomposition of the cobalt complexes that
occurred during the NMR measurement.
yield (Scheme 5). The other enynes 20b-e were obtained
from 20a (see the Experimental Section).
With the required regioisomeric enynes 20 in hand, the
next phase in our research was now the Pauson-Khand
reaction of these enynes. The dihydroxy derivative 20a
was first used as a substrate for the Pauson-Khand
reaction because of anticipation of highly preferential
formation of the bicyclo[4.3.0]nonenone derivative 22a
over its isomer 21a based on the aforementioned results
(see Table 2). Actually, the Pauson-Khand reaction of
20a was carried out under condition C (NMO in meth-
ylene chloride)16 to produce 22a in a highly stereoselec-
tive manner together with its 1-epimer 21a (entry 1; 81%,
21a :22a ) 7:93). The other results were presented in
Table 5. The similar stereoselective formation of 22b was
observed in the case of 20b (Table 5, entry 2). These
results are in good agreement with those recorded in the
Pauson-Khand reaction of the isomeric dihydroxy de-
rivative 6. The di-tert-butylsilylene compound 20e also
provided 22e exclusively when exposed to condition B
(TMANO in THF)12 (Table 5, entry 7). On the other hand,
the enyne 20c possessing a bulky protecting group on
two hydroxy groups has been shown to furnish 21c
stereoselectively as well as stereocomplementarily (Table
5, entries 3 and 4). In addition, the phenyl congener 20d
gave 21d predominantly (Table 5, entries 5 and 6),
although the diastereoselectivity is somewhat lower
compared to the cases of compound 7 (Table 1). It is
noteworthy to state that the 1,3-diene derivative 23d was
obtained as a mixture of (E)- and (Z)-isomers in the
cyclization of the enyne 20d having the phenyl substitu-
ent at the acetylenic terminus and a TBDMS protecting
group on two hydroxy groups (Table 5, entries 5 and 6).
Similar production of the 1,3-diene 10b was already
observed in the Pauson-Khand reaction of 7b with the
same functionalities as those of 20d (see Table 1, entry
4). Thus, it can be roughly concluded that the behavior
of enyne 20 with two hydroxy functionalities at both
allylic and homoallylic positions toward the Pauson-
Khand conditions is as same as that of enynes 5, 6, 7,
and 15 having two hydroxy functionalities at both the
propynyl and homopropynyl positions.
There are two conformers, A and A′, that should be
considered for the precursors of the bicyclo[4.3.0]nonenones
8 and 9, respectively. With the conformer A′ leading to
9, the nonbonding interaction of the olefinic proton
(H-1) with the C3-C4 bond (allylic 1,3-strain), especially
with the axial-like H-4, can be predicted on the basis of
Saito’s mechanistic analysis.19 The conformer A leading
to 8 would suffer from a similar interaction between the
H-2 and the axial-like H-4. However, the latter repulsion
seems to be much less than that of the former judging
from the molecular model considerations. As a result, the
cyclization of 7 would proceed mainly through the
conformer A resulting in the highly stereoselective or
exclusive formation of 8. In the case of 6, a similar
postulation would be applied for understanding the high
diastereoselectivity observed. The conformer B ending up
forming the 11 would possess the unfavorable nonbond-
ing interaction of the olefinic proton (H-1) with the axial-
like H-4. This kind of serious interaction might not be
predicted with the conformer B′, although there is
another weaker repulsion between the H-2 and the axial-
like H-4. Thus, the conformer B′ would become preferred
over the conformer B leading to highly diastereoselective
construction of 12.
In t r a m olecu la r P a u son -Kh a n d R ea ct ion of
(3S,4S)-3,4-Bis(oxygen a ted )oct-1-en -7-yn e Der iva -
tives. The Pauson-Khand reaction of (5S,6S)-bis(oxy-
genated)oct-1-en-7-yne derivatives 6 and 7 have success-
fully provided the corresponding bicyclo[4.3.0]nonenones
in not only a highly stereoselective but also stereo-
complementary manner by changing the protecting group
on two hydroxy groups. These results prompted us to
investigate the Pauson-Khand reaction of the regioiso-
mers of 6 and 7 having two hydroxy functionalities at
both allylic and homoallylic positions. The required
enynes 20 were easily prepared from L-tartrate via the
known alcohol 18.7b Tosylation of 18 was followed by
deketalization with PTSA in methanol to afford the diol
19 in 93% yield. Upon exposure to potassium carbonate,
19 underwent ring closure to provide the corresponding
epoxy derivative, which was subsequently treated with
propargylmagnesium bromide20 producing 20a in 65%
The structure of the cyclized products 21 and 22 was
elucidated by spectral evidence (see the Experimental
Section). The stereochemistry of the newly created ste-
reogenic center of these compounds was determined by
1H NMR spectral considerations. In the H NMR spec-
1
trum of 21b, for instance, the vicinal coupling constant
between the H-1 and the H-2 showed a typical equato-
(20) Huynh, C.; Derguini-Boumechal, F.; Linstrumelle, G. Tetrahe-
dron Lett. 1979, 17, 1503.

Construction of Bicyclo[4.3.0]nonenone Derivatives
J . Org. Chem., Vol. 64, No. 18, 1999 6827
Ta ble 5. P a u son -Kh a n d Rea ction of En yn e 20
Sch em e 6
R1 ) R2
ratioa yieldb
entry substrate condition R1 + R2 R3 21:22
(%)
1
2
3
4
5
6
7
20a
20b
20c
20c
20d
20d
20e
C
C
A
B
A
B
B
H
H
H
Ph
H
7:93
9:91
94:6
93:7
81
97
26
TBDMS
TBDMS
TBDMS
TBDMS
H
63
Ph 85:15
Ph 72:28
Ph
83c
48d
17e
SiBut
1:99
2
a
b
vided by exclusive formation of 22b from the silylene
derivative 20e. On the other hand, the preferred con-
former of the cobalt-complexed 20c,d can be regarded as
D and D′ on the basis of Saitoh’s reports. The weaker
repulsion between the H-2 and the axial-like TBDMSO
group at C-4 might be predicted in the conformer D, while
a very serious nonbonding interaction of the fairly bulky
TBDMSO group at C-4 with the vinyl portion in the
conformer D′ would make the cyclization through the
conformer D a predominant process. Preferential forma-
tion of 21c,d over 22c,d would reflect the difference in
the stability of these two conformers.
Determined by HPLC analysis. Total yield of 21 and 22.
c (1S,2S)-4-Benzylidene-1,2-bis(tert-butyldimethylsilyloxy)-3-me-
thylenecyclohexane (23d ) was obtained in 4% yield as a mixture
of (4E)- and (4Z)-isomers in a ratio of 88:12. The 1,3-diene 23d
was obtained in 39% yield as a mixture of (4E)- and (4Z)-isomers
in a ratio of 84:16. e The desilylated enyne 20b was recovered in
17% yield.
d
rial-equatorial coupling (J ) 3.4 Hz), while that of the
1-epimer 22b was found to have a larger coupling
constant (J ) 9.3 Hz) strongly indicating these two
protons to be axial. NOE experiments confirmed these
assignments. Namely, an NOE experiment with 22b
revealed a 5.6% enhancement between the H-1 and the
H-3 (1,3-diaxial relationship), and no enhancement be-
tween the H-1 and the H-3 could be observed in an NOE
experiment with 21b. The stereochemistry of 23d was
also clarified by an NOE experiment.21
The stereocomplementary formation of the bicyclo-
[4.3.0]nonenones 21 and 22 can be tentatively interpreted
on the basis of the working hypothesis we used to
understand the stereochemical outcome observed in a
series of the Pauson-Khand reaction of enynes 5, 6, 7,
and 15. Hydrogen bonding of the vicinal diol functionality
of the cobalt-complexed enynes 20a ,b would give rise to
two possible conformers, C and C′. With conformer C,
the allylic 1,3-strain between the olefinic proton (H-1) and
the C3-C4 bond would occur; thereby, the H-1 would also
suffer from nonbonding interaction with the axial-like
H-4. The conformer C′, however, might have much less
serious interaction between the H-1 and the axial-like
H-4. The highly stereoselective production of 22a ,b,
therefore, would be rationalized by the above simple
comparison of stability of these two conformers. The
supportive information for this interpretation was pro-
Con clu sion
We have developed a highly stereoselective and ste-
reocomplementary method for construction of the 2,3-bis-
(oxygenated)-9-(substituted)bicyclo[4.3.0]non-1(9)-en-8-
one skeleton by the intramolecular Pauson-Khand
reaction of (5S,6S)-5,6-bis(oxygenated)-8-(substituted)oct-
1-en-7-ynes, easily derived from L-tartrate. This proce-
dure has been found to be successfully applied for a
highly stereoselective and stereocomplementary forma-
tion of 2,3-bis(oxygenated)-7-(substituted)bicyclo[4.3.0]-
non-6-en-8-one framework. This method would provide
useful starting materials with two distinguishable hy-
droxy groups as well as an enone moiety for synthesis of
various kinds of natural products possessing the bicyclo-
[4.3.0]nonane ring system as a core framework. Further
studies on the mechanism for the observed stereoselec-
tivity as well as the stereocomplementarity and its scope
and limitation are now in progress.
Exp er im en ta l Section
Melting points are uncorrected. IR spectra were measured
in CHCl3 unless otherwise mentioned. H NMR spectra were
1
taken in CDCl3 unless otherwise indicated. CHCl3 (7.26 ppm)
was used as an internal standard for silyl compounds. TMS
was employed as an internal standard for other compounds.
13C NMR spectra were recorded in CDCl3 with CHCl3 (77.00
ppm) as an internal standard. CH2Cl2 was freshly distilled
from phosphorus pentoxide, and THF and Et2O from sodium
diphenyl ketyl, prior to use. All reactions were carried out
(21) 6.1% enhancement of Hb by irradiation of Ha in (E)-23d was
observed, while no enhancement between Ha and Hb could be detected
in (Z)-23d .

6828 J . Org. Chem., Vol. 64, No. 18, 1999
Mukai et al.
under nitrogen atmosphere otherwise stated. Silica gel (silica
gel 60, 230-400 mesh, Merck) was used for chromatography.
Organic extracts were dried over anhydrous Na2SO4.
with hexane afforded (-)-7a (469 mg, 99%) as a colorless oil:
1
[R]27 -26.5 (c 0.20, CHCl3); IR 3310, 1645 cm-1; H NMR δ
D
5.83 (ddt, 1H, J ) 17.1, 10.3, 6.8 Hz), 5.03 (dd, 1H, J ) 17.1,
1.5 Hz), 4.95 (dd, 1H, J ) 10.3, 1.5 Hz), 4.34 (dd, 1H, J ) 4.9,
2.0 Hz), 3.60 (ddd, 1H, J ) 8.3, 4.9, 3.4 Hz), 2.32 (d, 1H, J )
2.0 Hz), 2.23 (m, 1H), 2.07 (m, 1H), 1.82 (m, 1H), 1.71 (m, 1H),
0.91 (s, 18H), 0.14 (s, 3H), 0.10 (s, 3H), 0.07 (s, 6H); 13C NMR
138.89, 114.30, 83.06, 74.02, 73.21, 66.85, 30.89, 29.58, 25.82,
25.77, 18.17, 18.08, -4.40, -4.51, -4.67, -4.98; MS m/z 368
(M+, 4.2). Anal. Calcd for C20H40O2Si2: C, 65.15; H, 10.94.
Found: C, 64.80; H, 11.04.
(3S,4S)-1,1-Dibr om o-3,4-(isopr op ylid en edioxy)octa -1,7-
d ien e ((-)-4). A solution of DMSO (3.64 g, 46.6 mmol) in CH2-
Cl2 (20 mL) was added to a solution of oxalyl chloride (2.96 g,
23.3 mmol) in CH2Cl2 (20 mL) at -78 °C over a period of 5
min. After the mixture was stirred for 15 min, a solution of
the alcohol 39 (2.17 g, 11.7 mmol) in CH2Cl2 (20 mL) was added
to the CH2Cl2 solution, and the reaction mixture was stirred
at the same temperature for an additional hour. Et3N (7.07 g,
69.9 mmol) was then added to the reaction mixture, which was
gradually warmed to room temperature and diluted with CH2-
Cl2. The CH2Cl2 solution was washed with water and brine,
dried, and concentrated to leave the crude aldehyde. To a
solution of PPh3 (12.2 g, 46.6 mmol) in CH2Cl2 (30 mL) was
added a solution of CBr4 (7.70 g, 23.3 mmol) in CH2Cl2 (30
mL) at 0 °C, and the reaction mixture was stirred for 10 min.
A solution of the crude aldehyde in CH2Cl2 (20 mL) was then
added to a solution of the ylide in CH2Cl2 solution thus
adjusted at 0 °C, and stirring was continued for 3 h at room
temperature. The reaction mixture was quenched by addition
of saturated aqueous NaHCO3 and extracted with CH2Cl2,
which was washed with water and brine, dried, and concen-
trated to give the residual solids. The solids were washed with
hexane several times, and the filtrate was concentrated to
leave a residual oil, which was chromatographed with hexane-
AcOEt (40:1) to give (-)-4 (2.84 g, 72%) as a pale yellow oil:
(5S,6S)-5,6-(Isop r op ylid en ed ioxy)-8-p h en yloct-1-en -7-
yn e ((-)-5b). To a solution of (-)-5a (1.00 g, 5.55 mmol) and
iodobenzene (1.36 g, 6.66 mmol) in THF (55 mL) were
successively added Pd(PPh3)2Cl2 (117 mg, 0.17 mmol), CuI (63
mg, 0.33 mmol), and diisopropylamine (5.61 g, 55.5 mmol) at
room temperature. The reaction mixture was stirred for 1.5 h
and the precipitates were filtered off. The filtrate was concen-
trated to leave a residual oil, which was chromatographed with
hexane-AcOEt (50:1) to afford (-)-5b (1.37 g, 96%) as a
colorless oil: [R]26D -36.4 (c 0.20, CHCl3); IR 2233, 1642 cm-1
;
1H NMR δ 7.48-7.42 (m, 2H), 7.35-7.28 (m, 3H), 5.87 (ddt,
1H, J ) 17.1, 10.3, 6.8 Hz), 5.09 (dd, 1H, J ) 17.1, 1.5 Hz),
5.01 (dd, 1H, J ) 10.3, 1.5 Hz), 4.47 (d, 1H, J ) 7.8 Hz), 4.13
(td, 1H, J ) 7.8, 5.4 Hz), 2.34-2.19 (m, 2H), 1.85-1.74 (m,
2H), 1.51 (s, 3H), 1.45 (s, 3H); 13C NMR δ 137.63, 131.79,
128.61, 128.25, 122.30, 115.15, 109.76, 86.49, 85.59, 80.97,
71.00, 31.61, 29.76, 27.17, 26.31; MS m/z 256 (M+, 16). Anal.
Calcd for C17H20O2: C, 79.65; H, 7.86. Found: C, 79.36; H,
8.09.
[R]26 -19.7 (c 0.21, CHCl3); IR 1641 cm-1; 1H NMR δ 6.44 (d,
D
1H, J ) 8.3 Hz), 5.82 (ddt, 1H, J ) 17.1, 10.3, 6.8 Hz), 5.05
(dd, 1H, J ) 17.1, 1.5 Hz), 4.99 (dd, 1H, J ) 10.3, 1.5 Hz),
4.30 (t, 1H, J ) 8.3 Hz), 3.79 (dt, 1H, J ) 8.3, 6.4 Hz), 2.24
(m, 1H), 2.16 (m, 1H), 1.76-1.69 (m, 2H), 1.42 (s, 3H), 1.38 (s,
3H); 13C NMR δ 137.63, 135.74, 115.20, 109.40, 93.98, 80.65,
79.19, 31.16, 29.89, 27.21, 26.72; CIMS m/z 343 (M+ + 5, 46),
(3S,4S)-1-P h en yloct-7-en -1-yn e-3,4-d iol ((-)-6b). Accord-
ing to the procedure described for preparation of 6a from 5a ,
(-)-6b (36 mg, 95%) was obtained from compound (-)-5b (45
mg, 0.18 mmol) as a colorless oil: [R]27D -13.9 (c 0.50, CHCl3);
IR 3580, 3421, 2228, 1640 cm-1; 1H NMR δ 7.46-7.41 (m, 2H),
7.35-7.27 (m, 3H), 5.85 (ddt, 1H, J ) 17.1, 10.3, 6.8 Hz), 5.08
(dd, 1H, J ) 17.1, 2.0 Hz), 4.99 (dd, 1H, J ) 10.3, 2.0 Hz),
4.40 (d, 1H, J ) 6.4 Hz), 3.76 (ddd, 1H, J ) 9.3, 6.4, 2.9 Hz),
2.73 (br s, 2H), 2.32 (m, 1H), 2.22 (m, 1H), 1.85 (m, 1H), 1.66
(m, 1H); 13C NMR δ 138.08, 131.72, 128.64, 128.28, 122.10,
115.06, 87.19, 86.42, 74.38, 66.69, 31.66, 29.71; MS m/z 216
(M+, 1.9); HRMS calcd for C14H16O2 216.1150, found 216.1148.
341 (M+ + 3, 100), 339 (M+ + 1, 54). Anal. Calcd for C11H16
Br2O2: C, 38.85; H, 4.74. Found: C, 38.88; H, 4.75.
-
(5S,6S)-5,6-(Isop r op ylid en ed ioxy)oct-1-en -7-yn e ((-)-
5a ). To a solution of (-)-4 (2.84 g, 8.36 mmol) in dry Et2O (80
mL) was added BuLi in hexane (1.40 M, 15 mL, 20.9 mmol)
at 0 °C, and the reaction mixture was stirred for 10 min,
quenched by addition of saturated aqueous NH4Cl, and
extracted with Et2O. The extract was washed with water and
brine, dried, and concentrated to dryness. The residue was
chromatographed with hexanes-Et2O (30:1) to give (-)-5a
(5S,6S)-5,6-Bis(ter t-bu tyld im eth ylsiloxy)-8-p h en yloct-
1-en -7-yn e ((-)-7b). According to the procedure described for
preparation of 7a from 6a , (-)-7b (198 mg, 96%) was obtained
(1.18 g, 78%) as a pale yellow oil: [R]27 -7.3 (c 0.21, CHCl3);
D
from diol (-)-6b (100 mg, 0.46 mmol) as a colorless oil: [R]27
IR 3307, 1641 cm-1; H NMR δ 5.84 (ddt, 1H, J ) 17.1, 10.3,
1
D
-51.9 (c 0.50, CHCl3); IR 1639 cm-1; 1H NMR δ 7.43-7.38 (m,
2H), 7.32-7.27 (m, 3H), 5.85 (ddt, 1H, J ) 17.1, 10.3, 6.8 Hz),
5.04 (dd, 1H, J ) 17.1, 1.5 Hz), 4.96 (dd, 1H, J ) 10.3, 1.5
Hz), 4.56 (d, 1H, J ) 4.9 Hz), 3.69 (ddd, 1H, J ) 8.3, 4.9, 3.4
Hz), 2.25 (m, 1H), 2.11 (m, 1H), 1.86 (m, 1H), 1.76 (m, 1H),
0.93 (s, 9H), 0.92 (s, 9H), 0.19 (s, 3H), 0.14 (s, 3H), 0.10 (s,
3H), 0.09 (s, 3H); 13C NMR δ 139.01, 131.48, 128.18, 127.96,
123.34, 114.27, 88.95, 85.23, 74.47, 67.46, 31.38, 29.60, 25.86,
18.28, 18.10, -4.31, -4.45, -4.78; MS m/z 444 (M+, 49). Anal.
Calcd for C26H44O2Si2: C, 70.21; H, 9.97. Found: C, 69.92; H,
10.12.
6.8 Hz), 5.07 (dd, 1H, J ) 17.1, 2.0 Hz), 5.00 (dd, 1H, J ) 10.3,
2.0 Hz), 4.22 (dd, 1H, J ) 7.3, 2.0 Hz), 4.06 (td, 1H, J ) 7.3,
5.9 Hz), 2.52 (d, 1H, J ) 2.0 Hz), 2.30-2.13 (m, 2H), 1.80-
1.70 (m, 2H), 1.46 (s, 3H), 1.41 (s, 3H); 13C NMR δ 137.48,
115.18, 109.97, 80.85, 80.70, 74.65, 70.15, 31.50, 29.69, 27.06,
26.09; MS m/z 180 (M+, 1.3); HRMS calcd for C11H16O2
180.1151, found 180.1156.
(3S,4S)-Oct-7-en -1-yn e-3,4-d iol ((-)-6a ). A solution of (-)-
5a (700 mg, 3.88 mmol) and PTSA (74 mg, 0.39 mmol) in
MeOH (40 mL) was stirred at 50 °C for 24 h, and MeOH was
evaporated off. The residue was chromatographed with hex-
ane-AcOEt (2:1) to give (-)-6a (503 mg, 92%) as a colorless
(5S,6S)-5,6-(Isop r op ylid en ed ioxy)-8-(t r im et h ylsilyl)-
oct-1-en -7-yn e ((-)-5c). To a solution of (-)-5a (100 mg, 0.56
mmol) in THF (3.7 mL) was added BuLi in hexane (1.54 M;
0.44 mL, 0.68 mmol) at -78 °C. After being stirred at the same
temperature for 10 min, TMSCl (72.7 mg, 0.68 mmol) was
added to the reaction mixture. The mixture was stirred for 30
min at the same temperature, quenched by addition of
saturated aqueous NH4Cl, and extracted with Et2O. The
extract was washed with water and brine, dried, and concen-
trated to dryness. Chromatography of the residue with hexane
oil: [R]26 -11.1 (c 0.21, CHCl3); IR 3610, 3410, 3310, 1645
D
1
cm-1; H NMR δ 5.83 (ddt, 1H, J ) 17.1, 10.3, 6.8 Hz), 5.07
(dd, 1H, J ) 17.1, 2.0 Hz), 4.99 (dd, 1H, J ) 10.3, 2.0 Hz),
4.17 (m, 1H), 3.67 (m, 1H), 3.09 (d, 1H, J ) 5.9 Hz), 2.83 (d,
1H, J ) 3.9 Hz), 2.51 (d, 1H, J ) 2.4 Hz), 2.27 (m, 1H), 2.18
(m, 1H), 1.78 (m, 1H), 1.59 (m, 1H); 13C NMR δ 137.95, 115.10,
82.30, 74.61, 74.12, 65.86, 31.43, 29.60; MS m/z 140 (M+, 1.9);
HRMS calcd for C8H12O2 140.0837, found 140.0836.
(5S ,6S )-5,6-B is (t er t -b u t y ld im e t h y ls ilo x y )o c t -1-e n -
7-yn e ((-)-7a ). To a solution of (-)-6a (180 mg, 1.28 mmol)
and imidazole (525 mg, 7.70 mmol) in DMF (1.2 mL) was added
TBDMSCl (579 mg, 3.84 mmol) at room temperature. The
reaction mixture was heated at 50 °C for 4.5 h, quenched by
addition of saturated aqueous NaHCO3, and extracted with
Et2O. The extract was washed with water and brine, dried,
and concentrated to dryness. Chromatography of the residue
afforded (-)-5c (133 mg, 95%) as a colorless oil: [R]26 -21.2
D
(c 0.50, CHCl3); IR 2178, 1641 cm-1; 1H NMR δ 5.84 (ddt, 1H,
J ) 17.1, 10.3, 6.8 Hz), 5.06 (dd, 1H, J ) 17.1, 2.0 Hz), 4.99
(dd, 1H, J ) 10.3, 2.0 Hz), 4.22 (d, 1H, J ) 7.8 Hz), 4.00 (m,
1H), 2.28-2.13 (m, 2H), 1.78-1.67 (m, 2H), 1.45 (s, 3H), 1.39
(s, 3H), 0.16 (s, 9H); 13C NMR 137.63, 115.06, 109.70, 101.96,
91.72, 80.86, 70.84, 31.56, 29.65, 27.08, 26.22, -0.29; MS m/z

Construction of Bicyclo[4.3.0]nonenone Derivatives
J . Org. Chem., Vol. 64, No. 18, 1999 6829
252 (M+, 0.8). Anal. Calcd for C14H24O2Si: C, 66.61; H, 9.58.
Found: C, 66.39; H, 9.68.
was concentrated to leave the residue, which was taken up in
MeCN (2.0 mL). A solution of the crude cobalt-complexed
enyne in MeCN was heated at 70-75 °C untile complete
disappearance of the starting material (monitored by TLC).
The reaction mixture was passed through a short pad of Celite,
and the filtrate was concentrated to dryness. Chromatography
of the residue with hexane-AcOEt gave cyclized products.
Con d ition B. The crude cobalt-complexed enyne was dissolved
in THF (10 mL) to which TMANO‚2H2O (1.20 mmol) was
added at 0 °C. The reaction mixture was stirred at room
temperature until complete disappearance of the starting
material (monitored by TLC). Workup and chromatography
as described in condition A gave product. Con d ition C. Co2-
(CO)8 (0.24 mmol) was added to a solution of enyne (0.20 mmol)
in CH2Cl2 (10 mL) at room temperature. After the mixture was
stirred for 2 h, NMO (2.00 mmol) was added at 0 °C, and the
mixture was further stirred at 0 °C until complete disappear-
ance of the starting material (monitored by TLC). Workup and
chromatography gave products. Chemical yield and product
ratio obtained under conditions A-C are summarized in Tables
1-4. In the case of enyne 15 (Table 4), the cyclized products
were desilylated as follows: To a solution of the resulting
cyclized products in THF (5.0 mL) was added TBAF in THF
(1.0 M, 0.6 mmol, 0.6 mL) at room temperature. The reaction
mixture was stirred at the same temperature untile complete
disappearance of the cyclized silylene derivatives (monitored
by TLC). The reaction was quenched by addition of MeOH.
The reaction mixture was passed through a short pad of Celite,
and the filtrate was concentrated to dryness. Chromatography
of the residue with hexane-AcOEt gave products.
(3S,4S)-1-(Tr im et h ylsilyl)oct -7-en -1-yn e-3,4-d iol ((-)-
6c). According to the procedure described for preparation 6a
from 5a , (-)-6c (526 mg, 89%) was obtained from (-)-5c (700
mg, 2.77 mmol) as colorless solids: mp 66.0-67.0 °C (cyclo-
hexane); [R]27D -10.3 (c 0.50, CHCl3); IR 3578, 3407, 2174, 1640
1
cm-1; H NMR δ 5.84 (ddt, 1H, J ) 17.1, 10.3, 6.8 Hz), 5.07
(dd, 1H, J ) 17.1, 1.5 Hz), 5.00 (dd, 1H, J ) 10.3, 1.5 Hz),
4.16 (t, 1H, J ) 5.9 Hz), 3.65 (m, 1H), 2.34 (d, 1H, J ) 3.4
Hz), 2.27 (m, 1H), 2.26 (d, 1H, J ) 5.9 Hz), 2.20 (m, 1H), 1.76
(m, 1H), 1.60 (m, 1H), 0.18 (s, 9H); 13C NMR δ 138.08, 114.99,
103.81, 91.54, 74.20, 66.60, 31.52, 29.62, -0.27; CIMS m/z 213
(M+ + 1, 5.4). Anal. Calcd for C11H20O2Si: C, 62.21; H, 9.49.
Found: C, 62.00; H, 9.57.
(5S,6S)-5,6-Bis(ter t-bu tyld im eth ylsiloxy)-8-(tr im eth yl-
silyl)oct-1-en -7-yn e ((-)-7c). According to the procedure
described for preparation of 5c from 5a , (-)-7c (1.64 g, 96%)
was obtained from (-)-7a (1.43 g, 3.88 mmol) as a colorless
oil: [R]27 -1.7 (c 0.20, CHCl3); IR 1645 cm-1; 1H NMR δ 5.83
D
(ddt, 1H, J ) 17.1, 10.3, 6.8 Hz), 5.02 (dd, 1H, J ) 17.1, 2.0
Hz), 4.95 (dd, 1H, J ) 10.3, 2.0 Hz), 4.31 (d, 1H, J ) 5.4 Hz),
3.59 (m, 1H), 2.19 (m, 1H), 2.09 (m, 1H), 1.76 (m, 1H), 1.69
(m, 1H), 0.90 (s, 9H), 0.89 (s, 9H), 0.14 (s, 9H), 0.13 (s, 3H),
0.10 (s, 3H), 0.06 (s, 3H), 0.05 (s, 3H); 13C NMR 139.07, 114.18,
105.48, 90.03, 74.23, 67.35, 31.39, 29.47, 25.86, 18.28, 18.08,
-0.21, -4.33, -4.47, -4.51, -4.74; MS m/z 440 (M+, 1.8);
HRMS calcd for C23H48O2Si3 440.2962, found 440.2962.
(5S,6S)-5,6-(Di-ter t-b u t ylsilylen ed ioxy)oct -1-en -7-yn e
((-)-15a ). To a solution of (-)-6a (80.1 mg, 0.57 mmol) and
2,6-lutidine (367 mg, 1.32 mmol) in CH2Cl2 (1.10 mL) was
added di-tert-butylsilyl ditriflate (0.44 mL, 1.32 mmol) at 0 °C.
The reaction mixture was stirred for 6 h at room temperature
and concentrated to leave residual oil, chromatography of
which with hexane-AcOEt (40:1) was carried out by using 1%
Et3N containing solvent pre-eluting silica gel with to afford
(2S,3S,6S)- a n d (2S,3S,6R)-2,3-Bis(ter t-bu tyld im eth yl-
siloxy)bicyclo[4.3.0]n on -1(9)-en -8-on es ((-)-8a a n d (+)-
9a ). A mixture of (-)-8a and (+)-9a was obtained in a ratio of
88:12 (entry 1 in Table 1). The ratio was determined by HPLC
analysis (hexane/2-propanol ) 30:1; 1.0 mL/min; retention time
of (-)-8a was recorded as 4.1 min and that of (+)-9a as 5.2
min). Compound (-)-8a was obtained as a colorless oil: [R]D25
(-)-15a (140 mg, 87%) as a colorless oil: [R]26 -13.9 (c 0.51,
D
CHCl3); IR 3310, 1645 cm-1; 1H NMR 5.85 (ddt, 1H, J ) 17.1,
10.3, 6.8 Hz), 5.07 (dd, 1H, J ) 17.1, 1.5 Hz), 4.99 (dd, 1H, J
) 10.3, 1.5 Hz), 4.25 (dd, 1H, J ) 8.3, 2.0 Hz), 3.97 (td, 1H, J
) 8.3, 4.4 Hz), 2.50 (d, 1H, J ) 2.0 Hz), 2.30 (m, 1H), 2.22 (m,
1H), 1.74 (m, 1H), 1.63 (m, 1H), 1.07 (s, 9H), 1.03 (s, 9H); 13C
NMR δ 137.93, 114.93, 82.09, 80.25, 74.00, 70.28, 33.69, 29.76,
26.90, 26.85, 20.97, 20.69; MS m/z 280 (M+, 4.4). Anal. Calcd
for C16H28O2Si: C, 68.52; H, 10.06. Found: C, 68.55; H, 10.50.
(5S,6S)-5,6-(Di-ter t-bu tylsilylen ed ioxy)-8-p h en yloct-1-
en -7-yn e ((-)-15b). According to the procedure described for
preparation of 15a from 6a , (-)-15b (153 mg, 93%) was
1
-118.7 (c 0.21, CHCl3); IR 1704, 1631 cm-1; H NMR δ 5.89
(m, 1H), 4.33 (d, 1H, J ) 3.4 Hz), 3.90 (m, 1H), 2.98 (m, 1H),
2.54 (dd, 1H, J ) 19.0, 6.3 Hz), 2.03 (m, 1H), 1.97 (dd, 1H, J
) 19.0, 2.0 Hz), 1.84 (m, 1H), 1.54 (m, 1H), 1.49 (m, 1H), 0.87
(s, 9H), 0.82 (s, 9H), 0.06 (s, 3H), 0.03 (s, 3H), 0.02 (s, 3H),
0.00 (s, 3H); 13C NMR δ 209.43, 182.16, 129.15, 72.49, 70.66,
42.21, 37.13, 28.92, 27.26, 25.61, 17.97, 17.88, -4.81, -4.92,
-4.98, -5.05; MS m/z 396 (M+, 2.8). Anal. Calcd for C21H40O3-
Si2: C, 63.58; H, 10.16. Found: C, 63.20; H, 10.33. Compound
(+)-9a was obtained as colorless solids: mp 64.0-65.0 °C
(MeOH); [R +171.2 (c 0.22, CHCl3); IR 1704, 1622 cm-1 1H
;
obtained from (-)-6b (100 mg, 0.46 mmol) as a colorless oil:
NMR δ 6.11 (t, 1H, J ) 1.5 Hz), 4.14 (dd, 1H, J ) 8.3, 1.5 Hz),
3.50 (ddd, 1H, J ) 11.2, 8.3, 4.4 Hz), 2.71 (m, 1H), 2.61 (dd,
1H, J ) 19.0, 6.8 Hz), 2.06 (m, 1H), 2.02 (dd, 1H, J ) 19.0, 1.5
Hz), 1.97 (m, 1H), 1.54 (m, 1H), 1.04 (m, 1H), 0.93 (s, 9H),
0.89 (s, 9H), 0.11 (s, 3H), 0.08 (s, 3H), 0.07 (s, 3H), 0.00 (s,
3H); 13C NMR δ 208.00, 184.69, 127.39, 77.49, 76.53, 42.07,
40.52, 33.52, 31.00, 26.04, 18.19, 18.10, -3.66, -4.27, -4.80;
MS m/z 396 (M+, 0.3); HRMS calcd for C21H40O3Si2 396.2516,
found 396.2520.
1
[R]26 -28.3 (c 0.19, CHCl3); IR 2232, 1640 cm-1; H NMR δ
D
7.48-7.42 (m, 2H), 7.34-7.28 (m, 3H), 5.88 (ddt, 1H, J ) 17.1,
10.3, 6.8 Hz), 5.08 (dd, 1H, J ) 17.1, 1.5 Hz), 5.00 (dd, 1H, J
) 10.3, 1.5 Hz), 4.50 (d, 1H, J ) 8.8 Hz), 4.06 (m, 1H), 2.34
(m, 1H), 2.26 (m, 1H), 1.80 (m, 1H), 1.70 (m, 1H), 1.10 (s, 9H),
1.06 (s, 9H); 13C NMR δ 138.06, 131.84, 128.46, 128.21, 114.86,
87.17, 85.90, 80.50, 71.03, 33.89, 29.80, 26.97, 26.92, 21.04,
20.74; MS m/z 356 (M+, 46); HRMS calcd for C22H32O2Si
356.2172, found 356.2166.
(2S,3S,6S)-2,3-Bis(ter t-b u t yld im et h ylsiloxy)-9-p h en -
ylbicyclo[4.3.0]n on -1(9)-en -8-on e ((-)-8b). Compound (-)-
8b was obtained as a colorless oil: [R]26D -94.7 (c 0.50, CHCl3);
(5S,6S)-5,6-(Di-ter t-b u t ylsilylen ed ioxy)-8-(t r im et h yl-
silyl)oct-1-en -7-yn e ((-)-15c). According to the procedure
described for preparation of 15a from 6a , (-)-15c (154 mg,
92%) was obtained from (-)-6c (100 mg, 0.47 mmol) as a
IR 1695, 1646 cm-1 1H NMR δ 7.40-7.29 (m, 5H), 4.66 (d,
;
colorless oil: [R]27D -14.6 (c 0.50, CHCl3); IR 2181, 1639 cm-1
;
1H, J ) 3.4 Hz), 4.01 (m, 1H), 3.09 (m, 1H), 2.72 (dd, 1H, J )
19.0, 6.8 Hz), 2.13 (dd, 1H, J ) 19.0, 2.0 Hz), 2.12 (m, 1H),
1.94 (m, 1H), 1.67-1.52 (m, 2H), 0.87 (s, 9H), 0.81 (s, 9H), 0.06
(s, 3H), 0.05 (s, 3H), -0.19 (s, 3H), -0.22 (s, 3H); 13C NMR δ
207.37, 174.61, 139.84, 130.93, 129.27, 127.89, 127.76, 73.17,
67.85, 41.71, 35.51, 28.90, 27.60, 25.84, 25.57, 18.10, 17.83,
-4.76, -4.99, -5.23; MS m/z 472 (M+, 4.5). Anal. Calcd for
C27H44O3Si2: C, 68.59; H, 9.38. Found: C, 68.24; H, 9.47.
1H NMR δ 5.86 (ddt, 1H, J ) 17.1, 10.3, 6.8 Hz), 5.07 (dd, 1H,
J ) 17.1, 1.5 Hz), 4.99 (dd, 1H, J ) 10.3, 1.5 Hz), 4.26 (d, 1H,
J ) 8.8 Hz), 3.95 (m, 1H), 2.27 (m, 1H), 2.22 (m, 1H), 1.73 (m,
1H), 1.65 (m, 1H), 1.07 (s, 9H), 1.02 (s, 9H), 0.17 (s, 9H); 13C
NMR δ 138.04, 114.79, 103.61, 90.89, 80.40, 70.89, 33.82,
29.69, 26.94, 26.88, 20.95, 20.69, -0.21; MS m/z 352 (M+, 25).
Anal. Calcd for C19H36O2Si2: C, 64.71; H, 10.29. Found: C,
64.35; H, 10.51.
(2S,3S,6S)-2,3-Bis(t er t -b u t yld im e t h ylsiloxy)-9-(t r i-
m eth ylsilyl)bicyclo[4.3.0]n on -1(9)-en -8-on e ((-)-8c). Com-
pound (-)-8c was obtained as colorless solids: mp 72.0-73.0
Gen er a l P r oced u r e for P a u son -Kh a n d Rea ction of
En yn es 5-7 a n d 15. Con d ition A. Co2(CO)8 (0.24 mmol) was
added to a solution of enyne (0.20 mmol) in Et2O (2.0 mL) at
room temperature. After being stirred for 1 h, the Et2O solution
°C (MeOH); [R]26 -92.2 (c 0.20, CHCl3); IR 1680, 1599 cm-1
;
D
1H NMR δ 4.65 (d, 1H, J ) 3.9 Hz), 3.91 (m, 1H), 3.05 (m,

6830 J . Org. Chem., Vol. 64, No. 18, 1999
Mukai et al.
1H), 2.48 (dd, 1H, J ) 19.0, 6.8 Hz), 2.07 (m, 1H), 1.90 (dd,
1H, J ) 19.0, 2.4 Hz), 1.84 (m, 1H), 1.53 (m, 1H), 1.46 (m,
1H), 0.89 (s, 9H), 0.85 (s, 9H), 0.23 (s, 9H), 0.10 (s, 3H), 0.06
(s, 3H), 0.05 (s, 3H), 0.02 (s, 3H); 13C NMR δ 214.16, 187.94,
139.46, 73.21, 69.69, 42.39, 38.76, 29.56, 27.32, 25.82, 25.64,
17.97, -0.34, -4.35, -4.62, -4.69, -4.96; MS m/z 468 (M+,
35). Anal. Calcd for C24H48O3Si3: C, 61.48; H, 10.32. Found:
C, 61.19; H, 10.53.
H, 8.39. Found: C, 59.57; H, 8.45. Compound (+)-12c was
obtained as colorless solids: mp 133-134 °C (hexane-AcOEt);
[R]24D +130.7 (c 0.20, MeOH); IR (KBr) 3476, 3372, 1667, 1570
cm-1; 1H NMR δ (CD3OD) 4.20 (d, 1H, J ) 8.8 Hz), 3.41 (ddd,
1H, J ) 11.2, 8.8, 4.4 Hz), 2.71 (m, 1H), 2.54 (dd, 1H, J )
18.6, 6.8 Hz), 2.09 (m, 1H), 2.01 (m, 1H), 1.94 (dd, 1H, J )
18.6, 2.4 Hz), 1.57 (m, 1H), 1.04 (m, 1H), 0.22 (s, 9H); 13C NMR
δ (CD3OD) 215.25, 193.60, 137.43, 79.28, 77.28, 43.52, 42.91,
32.97, 32.49, 1.99; MS m/z 240 (M+, 0.4). Anal. Calcd for
(2S,3S,6S)- a n d (2S,3S,6R)-2,3-Dih yd r oxybicyclo[4.3.0]-
n on -1(9)-en -8-on es ((-)-11a a n d (+)-12a ). A mixture of
stereoisomers (-)-11a and (+)-12a was obtained in the ratio
of 17 to 83 (entry 1 in Table 2). The ratio was determined by
HPLC analysis (hexane/2-propanol ) 1:1; 0.5 mL/min; reten-
tion time of (-)-11a was recorded as 9.4 min and taht of (+)-
12a as 10.1 min). Compound (-)-11a was obtained as colorless
solids: mp 121-122 °C (AcOEt); [R]2D4 -287.6 (c 0.20, MeOH);
C
12H20O3Si: C, 59.96; H, 8.39. Found: C, 59.63; H, 8.55.
(2S,3S,6R)-2,3-(Isop r op ylid en ed ioxy)bicyclo[4.3.0]n on -
1(9)-en -8-on e (14a ). Compound 14a was obtained as a labile
1
colorless oil: IR 1706, 1647 cm-1; H NMR δ 6.60 (t, 1H, J )
1.5 Hz), 4.16 (dd, 1H, J ) 9.3, 1.5 Hz), 3.45 (ddd, 1H, J ) 11.7,
9.3, 3.4 Hz), 2.78 (m, 1H), 2.63 (dd, 1H, J ) 19.0, 6.8 Hz), 2.32-
2.22 (m, 2H), 2.02 (dd, 1H, J ) 19.0, 2.4 Hz), 1.72 (m, 1H),
1.51 (s, 3H), 1.48 (s, 3H), 1.21 (m, 1H). High-resolution mass
spectral analysis and combustion analysis could not be per-
formed due to its instability.
IR (KBr) 3425, 3335, 1660, 1623 cm-1 1H NMR δ (CD3OD)
;
6.01 (d, 1H, J ) 1.5 Hz), 4.48 (d, 1H, J ) 3.4 Hz), 4.01 (m,
1H), 3.10 (m, 1H), 2.58 (dd, 1H, J ) 19.0, 6.4 Hz), 2.09 (m,
1H), 1.98 (dd, 1H, J ) 19.0, 2.0 Hz), 1.92 (m, 1H), 1.70 (m,
1H), 1.50 (m, 1H); 13C NMR δ (CD3OD) 212.25, 184.94, 130.67,
72.34, 70.47, 43.20, 38.56, 29.85, 27.53; MS m/z 168 (M+, 100).
Anal. Calcd for C9H12O3: C, 64.27; H, 7.19. Found: C, 63.90;
H, 7.23. Compound (+)-12a was obtained as colorless solids:
(2S,3S,6R)-2,3-(Isop r op ylid en ed ioxy)-9-p h en ylbicyclo-
[4.3.0]n on -1(9)-en -8-on e (14b). Compound 14b was obtained
as a labile colorless oil: IR 1704, 1662 cm-1; 1H NMR δ 7.41-
7.21 (m, 5H), 4.30 (d, 1H, J ) 9.3 Hz), 3.65 (ddd, 1H, J ) 11.2,
9.3, 3.4 Hz), 2.82-2.72 (m, 2H), 2.38-2.27 (m, 2H), 2.16 (m,
1H), 1.76 (m, 1H), 1.41 (s, 3H), 1.35 (s, 3H), 1.29 (m, 1H). High-
resolution mass spectral analysis and combustion analysis
could not be performed due to its instability.
mp 152-153 °C (AcOEt); [R]26 +234.3 (c 0.20, MeOH); IR
D
(KBr) 3428, 3301, 1685, 1670, 1619 cm-1; 1H NMR δ (CD3OD)
6.06 (t, 1H, J ) 1.5 Hz), 4.17 (br d, 1H, J ) 8.8 Hz), 3.41 (ddd,
1H, J ) 11.2, 8.8, 4.4 Hz), 2.84 (m, 1H), 2.62 (dd, 1H, J )
19.1, 6.3 Hz), 2.11 (m, 1H), 2.04 (dd, 1H, J ) 19.1, 2.0 Hz),
2.01 (m, 1H), 1.57 (m, 1H), 1.10 (m, 1H); 13C NMR δ (CD3OD)
211.33, 187.67, 126.43, 77.43, 76.74, 42.94, 41.83, 32.90, 31.80;
MS m/z 168 (M+, 100). Anal. Calcd for C9H12O3: C, 64.27; H,
7.19. Found: C, 63.94; H, 7.26.
(2S,3S,6R)-2,3-(Isopr opyliden edioxy)-9-(tr im eth ylsilyl)-
bicyclo-[4.3.0]n on -1(9)-en -8-on e ((+)-14c). Compound (+)-
14c was obtained as colorless oil: [R]27D +169.5 (c 0.20, CHCl3);
1
IR 1692, 1605 cm-1; H NMR δ 4.21 (d, 1H, J ) 9.3 Hz), 3.45
(ddd, 1H, J ) 11.2, 9.3, 3.4 Hz), 2.66 (m, 1H), 2.57 (dd, 1H, J
) 18.6, 7.3 Hz), 2.27-2.19 (m, 2H), 1.96 (dd, 1H, J ) 18.6, 2.9
Hz), 1.70 (m, 1H), 1.48 (s, 3H), 1.47 (s, 3H), 1.16 (m, 1H), 0.25
(s, 9H); 13C NMR δ 211.71, 182.55, 135.62, 110.37, 81.92, 80.41,
41.71, 41.08, 31.36, 27.71, 27.05, 26.78, 0.36; MS m/z 280 (M+,
2.2); HRMS calcd for C15H24O3Si 280.1495, found 280.1495.
(1S,2S,3E)-3-Ben zylid en e-1,2-b is(ter t-b u t yld im et h yl-
siloxy)-4-m et h ylid en ecycloh exa n e ((-)-10b ). Compound
(2S,3S,6S)- a n d (2S,3S,6R)-2,3-Dih yd r oxy-9-p h en yl-
bicyclo[4.3.0]-n on -1(9)-en -8-on es ((-)-11b a n d (+)-12b). A
mixture of stereoisomers (-)-11b and (+)-12b was obtained
in a ratio of 15:85 (entry 4 in Table 2). The ratio was
determined by HPLC analysis (CH2Cl2/2-propanol ) 10:1; 1.0
mL/min; retention time of (-)-11b was recorded as 6.0 min
and that of (+)-12b as 4.4 min). Compound (-)-11b was
(-)-10b was obtained as a colorless oil: [R]27 -45.1 (c 0.20,
D
CHCl3); IR 1636 cm-1; H NMR δ 7.37-7.13 (m, 5H), 6.33 (s,
1
obtained as colorless solids: mp 245-246 °C (AcOEt); [R]27
D
1H), 4.86 (s, 1H), 4.61 (s, 1H), 3.94 (d, 1H, J ) 5.4 Hz), 3.77
(td, 1H, J ) 5.4, 2.9 Hz), 2.57 (m, 1H), 2.19 (m, 1H), 2.07 (m,
1H), 1.59 (m, 1H), 0.91 (s, 9H), 0.87 (s, 9H), 0.11 (s, 3H), 0.09
(s, 3H), 0.07 (s, 3H), 0.07 (s, 3H); 13C NMR δ 144.17, 142.52,
137.52, 128.82, 127.82, 126.31, 125.59, 113.05, 79.64, 73.46,
31.29, 30.91, 25.91, 25.82, 18.21, 18.04, -4.40, -4.45, -4.63,
-4.81; MS m/z 444 (M+, 92). Anal. Calcd for C26H44O2Si2: C,
70.21; H, 9.97. Found: C, 70.01; H, 10.15.
-133.1 (c 0.19, MeOH); IR (KBr) 3418, 3357, 1679, 1651 cm-1
;
1H NMR δ (CD3OD) 7.42-7.29 (m, 5H), 4.65 (d, 1H, J ) 3.3),
4.02 (m, 1H), 3.16 (m, 1H), 2.71 (dd, 1H, J ) 19.1, 6.6 Hz),
2.17 (m, 1H), 2.12 (dd, 1H, J ) 19.1, 2.0 Hz), 1.98 (m, 1H),
1.74 (m, 1H), 1.60 (m, 1H); 13C NMR δ (CD3OD) 209.89, 176.98,
142.04, 132.25, 130.54, 129.12, 128.98, 72.49, 68.51, 42.84,
36.98, 29.76, 27.74; MS m/z 244 (M+, 100); HRMS calcd for
C15H16O3 244.1099, found 244.1096. Compound (+)-12b was
obtained as colorless solids: mp 96-97 °C (hexane-AcOEt);
[R]26D +120.3 (c 0.21, MeOH); IR (KBr) 3441, 3264, 1720, 1705,
1654, 1633 cm-1; 1H NMR δ (CD3OD) 7.30-7.21 (m, 3H), 7.20-
7.17 (m, 2H), 4.33 (d, 1H, J ) 9.3 Hz), 3.55 (ddd, 1H, J ) 11.2,
9.3, 4.4 Hz), 2.84 (m, 1H), 2.71 (dd, 1H, J ) 19.0, 6.4 Hz), 2.16
(m, 1H), 2.13 (dd, 1H, J ) 19.0, 1.5 Hz), 2.08 (m, 1H), 1.62 (m,
1H), 1.22 (m, 1H); 13C NMR δ (CD3OD) 210.06, 177.37, 139.85,
133.80, 131.39, 128.08, 127.99, 78.88, 76.60, 42.08, 40.84,
33.01, 32.07; MS m/z 244 (M+, 100). Anal. Calcd for C15H16O3:
C, 73.75; H, 6.60. Found: C, 73.45; H, 6.75.
(2S,3S)-1-p-Tolu en esu lfon yl-4-bu ten -1,2,3-tr iol ((-)-19).
p-TsCl (3.69 g, 19.4 mmol) was added to a solution of the
known alcohol 18 (2.05 g, 12.9 mmol), Et3N (3.93 g, 38.8 mmol),
and DMAP (131 mg, 1.29 mmol) in CH2Cl2 (25 mL) at -20 °C.
After being stirred for 2 h, the reaction mixture was quenched
by addition of water and extracted with CH2Cl2. The extract
was washed with water and brine, dried, and concentrated to
leave the crude tosylate. According to the procedure described
for preparation of compound 6a from 5a , the crude tosylate
was treated with PTSA (245 mg, 1.29 mmol) in MeOH (130
mL) to give (-)-19 (3.27 g, 93%) as colorless solids: mp 52.0-
53.0 °C (hexanes-Et2O); [R]26D -11.5 (c 0.50, CHCl3); IR 3563,
3416, 1646 cm-1; 1H NMR δ 7.80 (d, 2H, J ) 8.3 Hz), 7.36 (d,
2H, J ) 8.3 Hz), 5.85 (ddd, 1H, J ) 17.1, 10.3, 6.4 Hz), 5.36
(d, 1H, J ) 17.1 Hz), 5.27(d, 1H, J ) 10.3 Hz), 4.15 (dd, 1H, J
) 10.3, 4.4 Hz), 4.15 (m, 1H), 4.05 (dd, 1H, J ) 10.3, 6.4 Hz),
3.78 (m, 1H), 2.49 (d, 1H, J ) 5.4 Hz), 2.46 (s, 3H), 2.19 (d,
1H, J ) 4.9 Hz); 13C NMR δ 145.16, 136.15, 132.45, 129.94,
127.96, 118.08, 72.24, 71.81, 70.55, 21.62; FABMS m/z 273 (M+
+ 1, 17). Anal. Calcd for C12H16O5S: C, 52.93; H, 5.92. Found:
C, 52.80; H, 5.97.
(2S,3S,6S)- a n d (2S,3S,6R)-2,3-Dih yd r oxy-9-(tr im eth yl-
silyl)bicyclo[4.3.0]n on -1(9)-en -8-on es ((-)-11c a n d (+)-
12c). A mixture of stereoisomers (-)-11c and (+)-12c was
obtained in a ratio of 21:79 (entry 5 in Table 2). The ratio was
determined by HPLC analysis (CH2Cl2/2-propanol ) 10:1; 1.0
mL/min; retention time of (-)-11c was recorded as 6.0 min
and that of (+)-12c as 4.5 min). Compound (-)-11c was
obtained as colorless solids: mp 118-119 °C (hexane-AcOEt);
[R]23D -193.7 (c 0.20, MeOH); IR (KBr) 3422, 3288, 1681, 1591
1
cm-1; H NMR δ (CD3OD) 4.72 (d, 1H, J ) 3.4 Hz), 4.01 (m,
1H), 3.09 (m, 1H), 2.50 (dd, 1H, J ) 19.0, 6.8 Hz), 2.11 (m,
1H), 1.91 (dd, 1H, J ) 19.0, 2.4 Hz), 1.90 (m, 1H), 1.67 (m,
1H), 1.48 (m, 1H), 0.23 (s, 9H); 13C NMR δ (CD3OD) 216.42,
191.12, 141.95, 72.65, 69.92, 43.56, 40.03, 30.15, 27.62, -0.22;
MS m/z 240 (M+, 69). Anal. Calcd for C12H20O3Si: C, 59.96;
(3S,4S)-Oct-1-en -7-yn e-3,4-d iol ((-)-20a ). To a solution
of (-)-19 (1.05 g, 3.84 mmol) in MeOH (40 mL) was added K2-
CO3 (1.33 g, 9.60 mmol) at room temperature, and the reaction
mixture was stirred for 10 min. MeOH was evaporated off,
and the residue was diluted with water and extracted with

Construction of Bicyclo[4.3.0]nonenone Derivatives
J . Org. Chem., Vol. 64, No. 18, 1999 6831
AcOEt. The extract was dried and concentrated to dryness.
The residue was passed through a short pad of silica gel wih
hexanes-Et2O (1:1) to give the crude epoxy derivative. To a
suspension of CuI (658 mg, 3.46 mmol) in Et2O (60 mL) was
added a solution of propargylmagnesium bromide in Et2O (0.58
M; 19.9 mL; 11.5 mmol) at -78 °C. After the mixture was
stirred for 5 min, a solution of crude epoxide obtained from
(-)-19 in Et2O (60 mL) was added, and the reaction mixture
was further stirred for 30 min at the same temperature. The
reaction mixture was quenched with saturated aqueous NH4-
Cl, filtered through Celite, and extracted with AcOEt. The
extract was washed with brine, dried, and concentrated to
dryness. Chromatography of the residual oil with hexane-
AcOEt (2:1) gave (-)-20a (350 mg, 65%) as a colorless oil:
5.39 (d, 1H, J ) 17.1 Hz), 5.23 (d, 1H, J ) 10.3 Hz), 4.08 (m,
1H), 3.80 (td, 1H, J ) 8.8, 2.9 Hz), 2.67 (m, 1H), 2.57 (m, 1H),
1.88 (m, 1H), 1.75 (m, 1H), 1.07 (s, 9H), 1.07 (s, 9H); 13C NMR
δ 136.95, 131.50, 128.18, 127.53, 123.92, 117.32, 89.65, 81.74,
80.79, 78.96, 33.14, 27.03, 26.97, 20.95, 20.74, 16.25; MS m/z
356 (M+, 30). Anal. Calcd for C22H32O2Si: C, 74.10; H, 9.05.
Found: C, 73.87; H, 9.14.
Gen er a l P r oced u r e for P a u son -Kh a n d Rea ction of
En yn es 20. According to the procedure described for the
Pauson-Khand reaction of enynes 5-7 and 15, enynes 20
were exposed to three conditions (conditions A-C). In the cases
of cyclization of enyne 20e, desilylation was carried out before
chromatographic isolation. Chemical yield and the product
ratio of 21/22 are summarized in Table 5.
[R]27 -34.5 (c 0.20, CHCl3); IR 3567, 3422, 3307, 2118, 1644
(1S,2S,3S)- a n d (1R,2S,3S)-2,3-Dih yd r oxybicyclo[4.3.0]-
n on -6-en -8-on es ((-)-21a a n d (+)-22a ). A mixture of (-)-
21a and (+)-22a was obtained in a ratio of 7:93 (entry 1 in
Table 5). The ratio was determined by HPLC analysis (CH2-
Cl2/2-propanol ) 5:1; 1.0 mL/min; retention time of (-)-21a
was recorded as 8.3 min and that of (+)-22a as 5.9 min).
Compound (-)-21a was obtained as colorless solids: mp 181-
D
1
cm-1; H NMR δ 5.87 (ddd, 1H, J ) 17.1, 10.3, 6.4 Hz), 5.37
(d, 1H, J ) 17.1 Hz), 5.27 (d, 1H, J ) 10.3 Hz), 3.96 (m, 1H),
3.66 (ddd, 1H, J ) 9.3, 5.9, 3.4 Hz), 2.37 (m, 2H), 2.20 (br s,
2H), 1.97 (t, 1H, J ) 2.4 Hz), 1.75 (m, 1H), 1.68 (m, 1H); 13C
NMR δ 137.23, 117.68, 83.94, 76.07, 72.90, 68.81, 31.45, 14.79;
MS m/z 140 (M+, 1.3); HRMS calcd for C8H12O2 140.0837, found
140.0840.
183 °C (from AcOEt); [R]25 -182.3 (c 0.21, MeOH); IR (KBr)
D
(3S,4S)-3,4-Bis(t er t -b u t yld im e t h ylsiloxy)oct -1-e n -7-
yn e ((-)-20c). According to the procedure described for
preparation of 7a from 6a , (-)-20c (574 mg, 98%) was obtained
3420, 3381, 1639, 1607 cm-1; 1H NMR δ (CD3OD) 5.86 (m, 1H),
3.95-3.88 (m, 2H), 3.28 (m, 1H), 2.68 (br td, 1H, J ) 13.7, 5.9
Hz), 2.60 (ddd, 1H, J ) 13.7, 4.9, 2.0 Hz), 2.41 (dd, 1H, J )
18.6, 2.0 Hz), 2.34 (dd, 1H, J ) 18.6, 6.4 Hz), 1.96 (tdd, 1H, J
13.7, 4.9, 2.4 Hz), 1.87 (m, 1H); 13C NMR δ (CD3OD) 213.09,
185.60, 128.71, 72.88, 70.11, 42.86, 37.81, 28.44, 25.89; MS
m/z 168 (M+, 61). Anal. Calcd for C9H12O3: C, 64.27; H, 7.19.
Found: C, 63.88; H, 7.22. Compound (+)-22a was obtained as
from (-)-20a (223 mg, 1.59 mmol) as a colorless oil: [R]27
D
-79.2 (c 0.50, CHCl3); IR 3308, 2116, 1642 cm-1; H NMR δ
1
5.97 (ddd, 1H, J ) 17.1, 10.7, 3.9 Hz), 5.28 (d, 1H, J ) 17.1
Hz), 5.15 (d, 1H, J ) 10.7 Hz), 4.18 (m, 1H), 3.77 (ddd, 1H, J
) 8.8, 4.9, 3.4 Hz), 2.28 (m, 1H), 2.17 (m, 1H), 1.92 (t, 1H, J )
2.4 Hz), 1.80 (m, 1H), 1.42 (m, 1H), 0.91 (s, 9H), 0.90 (s, 9H),
0.10 (s, 3H), 0.10 (s, 3H), 0.07 (s, 3H), 0.05 (s, 3H); 13C NMR
δ 136.51, 114.88, 84.62, 74.86, 73.46, 68.32, 29.71, 25.84, 18.21,
17.99, 14.97, -4.29, -4.74, -4.80, -4.90; MS m/z 368 (M+,
0.5); HRMS calcd for C20H40O2Si2 368.2567, found 368.2566.
(3S,4S)-3,4-Bis(ter t-bu tyld im eth ylsiloxy)-8-p h en yloct-
1-en -7-yn e ((-)-20d ). According to the procedure described
for preparation of 5b from 5a , (-)-20d (540 mg, 88%) was
colorless solids: mp 134-135 °C (from AcOEt); [R]27 +52.6
D
(c 0.20, MeOH); IR (KBr) 3468, 3339, 1695, 1679, 1622 cm-1
;
1H NMR δ (CD3OD) 5.89 (m, 1H), 3.59 (ddd, 1H, J ) 11.2, 9.3,
4.4 Hz), 3.00 (dd, 1H, J ) 10.3, 9.3 Hz), 2.81 (ddd, 1H, J )
14.2, 4.4, 2.4 Hz), 2.76 (m, 1H), 2.59 (dd, 1H, J ) 19.0, 6.4
Hz), 2.41 (br td, 1H, J ) 14.2, 5.4 Hz), 2.31 (dd, 1H, J ) 19.0,
1.5 Hz), 2.15 (m, 1H), (m, 1H); 13C NMR δ (CD3OD) 212.02,
183.57, 128.71, 81.56, 74.35, 48.87, 41.33, 32.92, 28.88; MS
m/z 168 (M+, 63). Anal. Calcd for C9H12O3 requires C, 64.27;
H, 7.19. Found: C, 63.87; H, 7.26.
obtained from (-)-20c (508 mg, 1.38 mmol) as a colorless oil:
1
[R]27 -53.3 (c 0.50, CHCl3); IR 1640 cm-1; H NMR δ 7.39-
D
7.35 (m, 2H), 7.30-7.24 (m, 3H), 6.00 (ddd, 1H, J ) 17.6, 10.7,
3.9 Hz), 5.30 (d, 1H, J ) 17.6 Hz), 5.16 (d, J ) 10.7 Hz), 4.21
(m, 1H), 3.87 (ddd, 1H, J ) 9.8, 4.9, 2.9 Hz), 2.51 (ddd, 1H, J
) 16.6, 6.8, 4.9 Hz), 2.40 (ddd, 1H, J ) 16.6, 9.8, 6.8 Hz), 1.88
(dddd, 1H, J ) 16.6, 9.8, 6.8, 2.9 Hz), 1.48 (dddd, 1H, J ) 16.6,
9.8, 6.8, 4.9 Hz), 0.92 (s, 9H), 0.90 (s, 9H), 0.14 (s, 3H), 0.11 (s,
3H), 0.06 (s, 3H), 0.05 (s, 3H); 13C NMR δ 136.59, 131.48,
128.10, 127.39, 124.15, 114.83, 90.26, 80.92, 74.93, 73.50,
29.78, 25.86, 25.81, 18.19, 18.03, 15.89, -4.27, -4.69, -4.80,
-4.90; MS m/z 444 (M+, 14). Anal. Calcd for C26H44O2Si2: C,
70.21; H, 9.97. Found: C, 69.83; H, 10.06.
(1S,2S,3S)- a n d (1R,2S,3S)-2,3-Dih yd r oxy-7-p h en ylbi-
cyclo[4.3.0]n on -6-en - 8-on es ((+)-21b a n d (-)-22b). A
mixture of (+)-21b and (-)-22b was obtained in a ratio of 9:91
(entry 2 in Table 5). The ratio was determined by HPLC
analysis (AcOEt; 1.0 mL/min; retention time of (+)-21b was
recorded as 7.2 min and that of (-)-22b as 8.8 min). Compound
(+)-21b was obtained as colorless solids: mp 157-158 °C (from
AcOEt); [R]26 +33.4 (c 0.20, MeOH); IR (KBr) 3451, 3382,
D
1693, 1682, 1670, 1636, 1600 cm-1; H NMR δ 7.43-7.38 (m,
1
2H), 7.34-7.28 (m, 3H), 4.14 (m, 1H), 4.09 (m, 1H), 3.42 (m,
1H), 2.86 (ddd, 1H, J ) 14.2, 4.9, 2.0 Hz), 2.70 (td, 1H, J )
14.2, 6.4 Hz), 2.59-2.56 (m, 2H), 1.99 (tdd, 1H, J ) 14.2, 4.9,
2.4 Hz), 1.91 (m, 1H), 1.73 (br s, 2H); (CD3OD) 7.40-7.35 (m,
2H), 7.32-7.24 (m, 3H), 4.00-3.94 (m, 2H), 3.36 (m, 1H), 2.75-
2.63 (m, 2H), 2.55 (dd, 1H, J ) 18.6, 2.4 Hz), 2.48 (dd, 1H, J
) 18.6, 6.8 Hz), 1.95 (m, 1H), 1.85 (m, 1H); (D2O; sodium
3-(trimethylsilyl)propanesulfonate was used as an internal
standard) 7.52-7.41 (m, 3H), 7.32-7.28 (m, 2H), 4.14 (t, 1H,
J ) 3.4 Hz), 4.09 (m, 1H), 3.41 (m, 1H), 2.76 (m, 1H), 2.66
(dd, 1H, J ) 19.1, 6.4 Hz), 2.65 (m, 1H), 2.56 (dd, 1H, J )
19.1, 1.5 Hz), 1.98-1.84 (m, 2H); 13C NMR δ (CD3OD) 210.17,
177.97, 139.94, 132.88, 130.36, 129.18, 128.62, 73.12, 70.28,
41.18, 37.43, 28.26, 24.27; MS m/z 244 (M+, 100). Anal. Calcd
for C15H16O3: C, 73.75; H, 6.60. Found: C, 73.37; H, 6.70.
Compound (-)-22b was obtained as colorless solids: mp 131-
(3S,4S)-8-P h en yloct-1-en -7-yn e-3,4-d iol ((-)-20b). To a
solution of (-)-20d (447 mg, 1.00 mmol) in THF (10 mL) was
added TBAF in THF (1.0 M; 2,10 mL, 2.10 mmol) at room
temperature. After being stirred for 2 h at the same temper-
ature, the reaction mixture was quenched by addition of
saturated aqueous NH4Cl solution and extracted with AcOEt.
The extract was washed with water and brine, dried, and
concentrated to dryness. Chromatography of the residue with
hexane-AcOEt (2:1) afforded (-)-20b (214 mg, 99%) as
colorless solids: mp 45.0-46.0 °C (from hexanes-Et2O); [R]26
D
-24.5 (c 0.50, CHCl3); IR 3574, 3421, 1645 cm-1; H NMR δ
1
7.41-7.36 (m, 2H), 7.31-7.25 (m, 3H), 5.91 (ddd, 1H, J ) 17.1,
10.3, 6.4 Hz), 5.38 (d, J ) 17.1 Hz), 5.28 (d, 1H, J ) 10.3 Hz),
4.01 (m, 1H), 3.73 (ddd, 1H, J ) 9.3, 5.9, 3.4 Hz), 2.65-2.54
(m, 2H), 2.10 (br s, 2H), 1.85 (m, 1H), 1.76 (m, 1H); 13C NMR
δ 137.30, 131.48, 128.16, 127.62, 123.61, 117.65, 89.38, 81.12,
76.07, 73.19, 31.79, 15.80; MS m/z 216 (M+, 3.5). Anal. Calcd
for C14H16O2: C, 77.75; H, 7.46. Found: C, 77.50; H, 7.53.
(3S,4S)-3,4-(Di-ter t-bu tylsilylen ed ioxy)-8-p h en yloct-1-
en -7-yn e ((-)-20e). According to the procedure described for
preparation 15a from 6a , (-)-20e (243 mg, 87%) was obtained
132 °C (from hexane-AcOEt); [R]22 - 82.8 (c 0.20, MeOH);
D
IR (KBr) 3400, 3344, 3274, 1677, 1628 cm-1; 1H NMR δ 7.44-
7.32 (m, 3H), 7.29-7.26 (m, 2H), 3.78 (ddd, 1H, J ) 13.2, 8.8,
4.4 Hz), 3.50 (br s, 1H), 3.24 (dd, 1H, J ) 10.3, 8.8 Hz), 3.05
(ddd, 1H, J ) 14.7, 4.4, 2.4 Hz), 2.86-2.77 (m, 2H), 2.60 (br s,
1H), 2.49 (m, 1H), 2.38 (td, 1H, J ) 14.7, 5.4 Hz), 2.20 (m,
1H), 1.48 (m, 1H); (CD3OD) 7.41-7.29 (m, 3H), 7.26-7.20 (m,
2H), 3.67 (ddd, 1H, J ) 11.2, 8.8, 4.4 Hz), 3.08 (dd, 1H, J )
9.8, 8.8 Hz), 2.90 (m, 1H), 2.82 (m, 1H), 2.71 (dd, 1H, J ) 19.0,
6.4 Hz), 2.45 (d, 1H, J ) 19.0 Hz), 2.42 (td, 1H, J ) 14.7, 5.9
from (-)-20b (170 mg, 0.78 mmol) as a colorless oil: [R]26
D
-41.7 (c 0.50, CHCl3); IR 1645 cm-1; 1H NMR δ 7.40-7.36 (m,
2H), 7.29-7.25 (m, 3H), 5.84 (ddd, 1H, J ) 17.1, 10.3, 6.4 Hz),

6832 J . Org. Chem., Vol. 64, No. 18, 1999
Mukai et al.
Hz), 2.12 (m, 1H), 1.37 (m, 1H); (D2O; sodium 3-(trimethyl-
silyl)propanesulfonate was used as an internal standard)
7.51-7.41 (m, 3H), 7.28-7.23 (m, 2H), 3.79 (ddd, 1H, J ) 11.2,
9.3, 4.4 Hz), 3.24 (dd, 1H, J ) 10.3, 9.3 Hz), 2.91 (m, 1H), 2.86
(m, 1H), 2.80 (dd, 1H, J ) 19.1, 6.4 Hz), 2.52 (d, 1H, J ) 19.1
Hz), 2.43 (td, 1H, J ) 14.2, 5.4 Hz), 2.14 (m, 1H), 1.39 (m,
1H); 13C NMR δ (CD3OD) 209.20, 175.92, 139.69, 132.45,
130.29, 129.27, 128.93, 81.63, 74.55, 47.15, 40.66, 32.77, 27.29;
MS m/z 244 (M+, 100); HRMS calcd for C15H16O3 244.1100,
found 244.1100.
22d ). A mixture of 21d and 22d was obtained in a ratio of
85:15 (entry 5 in Table 5) as a colorless oil. The ratio was
determined by HPLC analysis (hexane/2-propanol ) 100:1; 0.5
mL/min; retention time of 21d was recorded as 9.5 min and
that of 22d as 8.8 min): IR 1691, 1642 cm-1; selected data for
1H NMR δ 7.42-7.22 (m, 5H), 3.88 (m, 72/100 × 2H), 3.78 (ddd,
28/100H, J ) 11.2, 7.8, 3.9 Hz), 3.36-3.31 (m, 1H), 0.95 (s,
72/100H × 9H), 0.92 (s, 28/100H × 9H), 0.90 (s, 28/100H ×
9H), 0.83 (s, 72/100H × 9H); MS m/z 472 (M+, 0.7). Anal. Calcd
for C27H44O3Si2: C, 68.59; H, 9.38. Found: C, 68.50; H, 9.51.
(1S,2S,3S)- a n d (1R,2S,3S)-2,3-Bis(ter t-bu tyld im eth yl-
siloxy)bicyclo-[4.3.0]n on -6-en -8-on es ((-)-21c a n d 22c). A
mixture of (-)-21c and 22c was obtained in a ratio of 94:6
(entry 3 in Table 5). The ratio was determined by HPLC
analysis (hexane/AcOEt ) 5:1; 1.0 mL/min; retention time of
(-)-21c was recorded as 4.7 min and that of 22c as 6.0 min).
Compound (-)-21c was obtained as colorless solids: mp 80.0-
(1S,2S,3E)- a n d (1S,2S,3Z)-4-Ben zylid en e-1,2-bis(ter t-
bu tyld i-m eth ylsiloxy)-3-m eth ylid en ecycloh exa n es ((E)-
23d a n d (Z)-23d ). A mixture of regioisomers (E)-23d and (Z)-
23d was obtained in a ratio of 84:16 (entry 6 in Table 5) as a
colorless oil. The ratio was determined by HPLC analysis
(hexane; 1.0 mL/min; retention time of (E)-23d was recorded
as 8.3 min and that of (Z)-23d as 9.9 min): IR 1636 cm-1
;
81.0 °C (from MeOH); [R]26 -86.7 (c 0.20, CHCl3); IR 1692,
selected data for 1H NMR δ 7.42-7.09 (m, 5H), 6.48 (s, 84/
100H), 6.27 (s, 16/100H), 5.14 (d, 84/100H, J ) 2.4 Hz), 5.01
(m, 16/100H), 4.29 (m, 84/100H), 4.81 (d, 16/100H, J ) 2.4 Hz),
4.02-3.98 (m, 1H), 3.77 (td, 84/100H, J ) 4.9, 2.9 Hz), 3.71
(d, 16/100H, J ) 5.4, 2.9 Hz), 0.93 (s, 16/100 × 9H), 0.89 (s,
84/100 × 9H); MS m/z 444 (M+, 100). Anal. Calcd for C26H44O2-
Si2: C, 70.21; H, 9.97. Found: C, 70.05; H, 10.23.
D
1624 cm-1; 1H NMR δ 5.85 (m, 1H), 3.86 (m, 1H), 3.80 (t, 1H,
J ) 3.4 Hz), 3.22 (m, 1H), 2.62 (br td, 1H, J ) 13.2, 5.9), 2.53
(ddd, 1H, J ) 13.2, 4.9, 2.0 Hz), 2.31 (dd, 1H, J ) 18.6, 6.4
Hz), 2.22 (dd, 1H, J ) 18.6, 2.4 Hz), 1.92 (tdd, 1H, J ) 13.2,
4.9, 2.4 Hz), 1.73 (m, 1H), 0.92 (s, 9H), 0.81 (s, 9H), 0.09 (s,
3H), 0.09 (s, 3H), 0.04 (s, 3H), 0.02 (s, 3H); 13C NMR δ 209.41,
181.51, 128.09, 73.46, 69.85, 41.60, 37.04, 28.11, 25.72, 25.61,
24.93, 17.94, 17.85, -4.31, -4.90, -5.19; MS m/z 396 (M+, 0.5).
Anal. Calcd for C21H40O3Si2: C, 63.58; H, 10.16. Found: C,
63.29; H, 10.35. Compound 22c was obtained as a labile
colorless oil: IR 1706, 1626 cm-1; 1H NMR δ 5.86 (m, 1H), 3.70
(ddd, 1H, J ) 11.2, 7.8, 3.9 Hz), 3.26 (dd, 1H, J ) 8.8, 7.8 Hz),
2.73 (m, 1H), 2.59 (dd, 1H, J ) 18.6, 6.4 Hz), 2.51 (m, 1H),
2.29 (m, 1H), 2.27 (dd, 1H, J ) 18.6, 2.5 Hz), 2.11 (m, 1H),
1.44 (m, 1H), 0.91 (s, 9H), 0.89 (s, 9H), 0.12 (s, 3H), 0.10 (s,
3H), 0.10 (s, 3H), 0.08 (s, 3H). High-resolution mass spectral
analysis and combustion analysis could not be performed due
to its instability.
Ack n ow led gm en t. This work was supported in part
by Grant-in-Aid for Scientific Research from the Min-
istry of Education, Science and Culture of J apan, to
which the authors' thanks are due.
Su p p or t in g In for m a t ion Ava ila b le: 1H and 13C NMR
spectra for compounds 5a , 6a ,b, 7c, 9a , 11b, 14c, 15b, 20a ,c,
and 22b and 1H spectra for compounds 14a ,b and 22c. This
material is available free of charge via the Internet at
http://pubs.acs.org.
(1S,2S,3S)- a n d (1R,2S,3S)-2,3-Bis(ter t-bu tyld im eth yl-
siloxy)-8-p h en ylb icyclo[4.3.0]n on -6-en -8-on es (21d a n d
J O990819Z