Synthesis and reactivity of cross-conjugated polyenones with a planar chirality

Article abstract of DOI:10.1021/jo9603643

The complexes 6 are the first examples of a novel class of cross conjugated polyenones bearing a planar chirality introduced by an organometallic moiety. Their synthesis is described using, as a key intermediate, the easily accessible new phosphorane 9. The free double bond of the selectively protected polyenes 6 reacts efficiently, although with low diastereoselectivities, in Diels-Alder or 1,3 dipolar cycloaddition reactions or with nucleophiles. Cyclopentyl radical also adds to 6, and this is the first example of a radical reaction in the presence of carbonyliron complexes. Decomplexation of the various adducts leads, in good yields, to the corresponding polyfunctionalized free dienes, which can be of further synthetic use.

Full text of DOI:10.1021/jo9603643

J . Org. Chem. 1996, 61, 5063-5072
5063
Syn th esis a n d Rea ctivity of Cr oss-Con ju ga ted P olyen on es w ith a
P la n a r Ch ir a lity
Nathalie J . Marchand, Danielle M. Gre´e, J acques T. Martelli, and Rene´ L. Gre´e*
Laboratoire de Synthe`ses et Activations de Biomole´cules, CNRS URA 1467,
Ecole Nationale Supe´rieure de Chimie de Rennes, Avenue du Ge´ne´ral Leclerc, 35700 Rennes, France
Lo¨ıc J . Toupet
Groupe Matie`re Condense´e et Mate´riaux, CNRS URA 804, Universite´ de Rennes,
Avenue du Ge´ne´ral Leclerc, 35042 Rennes Cedex, France
Received February 21, 1996X
The complexes 6 are the first examples of a novel class of cross conjugated polyenones bearing a
planar chirality introduced by an organometallic moiety. Their synthesis is described using, as a
key intermediate, the easily accessible new phosphorane 9. The free double bond of the selectively
protected polyenes 6 reacts efficiently, although with low diastereoselectivities, in Diels-Alder or
1,3 dipolar cycloaddition reactions or with nucleophiles. Cyclopentyl radical also adds to 6, and
this is the first example of a radical reaction in the presence of carbonyliron complexes.
Decomplexation of the various adducts leads, in good yields, to the corresponding polyfunctionalized
free dienes, which can be of further synthetic use.
Cross-conjugated polyenones are very interesting de-
rivatives from several viewpoints. Some of them have
been isolated as bioactive compounds: clavuridenone (1)1
and ptilodene (2),2 for instance, are marine polyunsatu-
rated fatty acid metabolites with antiinflammatory activ-
ity; melodienone (3) shows significant toxicity against
human tumor cell lines.3 Others, like damascenone (4)
and â-damascone (5) are odoriferous compounds isolated
from Bulgarian rose oil,4 and they are very useful in
perfumery (Figure 1). In addition, cross-conjugated poly-
enones are found in the framework of some synthetic
dyes5 and in photopolymerization initiator compositions6
and are key structural fragments of annulenones.7 Fur-
thermore, they are versatile intermediates in organic
synthesis, for instance, in the Nazarov cyclization,8 in the
synthesis of heterocycles,9 or in tandem reactions.10
F igu r e 1.
A number of methods are available for the synthesis
with R,â-unsaturated acid halides in the presence of
aluminum chloride usually leads to mixtures of prod-
ucts,12 while the reaction of R,â-unsaturated acid chlo-
rides with vinylic organometallic derivatives (Hg, Cu,
Sn)13 in the presence of Lewis acids is cleaner and gives
moderate to excellent yields of products. Other possibili-
ties are carbonylations,14 Horner-Wittig-Emmons reac-
tions,15 or isomerizations of triple bonds.16
of cross-conjugated polyenones. Aldol-type condensations
are generally efficient for the preparation of annulenone’s
fragments.11 Another route can be found in acylation
reactions: the direct Friedel-Crafts acylation of alkenes
X Abstract published in Advance ACS Abstracts, J uly 1, 1996.
(1) Kobayashi, M.; Yasuzawa, T.; Yoshihara, M.; Akutsu, H.;
Kyogoku, Y.; Kitawaga, I. Tetrahedron Lett. 1982, 23(50), 5331-5334.
Kikuchi, H.; Tsukitani, Y. Tetrahedron Lett. 1982, 23(49), 5171-5174.
(2) Lopez, A; Gerwick W. H. Tetrahedron Lett. 1988, 29(13), 1505-
1506.
In order to extend the synthetic potential of such
derivatives, it appears interesting to first provide selec-
(3) J ung, J . H.; Pummangura, S.; Chaichantipyuth, C.; Patarapan-
ich, C.; Fanwick, P. E.; Chang, C.-J .; Mc Laughlin, J . L. Tetrahedron
1990, 46, 5043-5054.
(4) Demole, E.; Enggist, P.; Sau¨berli, U.; Stoll, M. Helv. Chim. Acta
1977, 53(3), 541-551.
(11) See, for instance: Nakatsuji, S.; Akiyama, S.; Nakagawa, M.
Tetrahedron Lett. 1977, 42, 3723-3726. Higuchi, H.; Asano, K.;
Hiraiwa, N.; Kondo, S.; Ojima, J .; Yamamoto, G. J . Chem. Soc., Perkin
Trans. 1 1994, 1579-1587.
(12) Hacini, S.; Pardo, R.; Santelli, M. Tetrahedron Lett. 1979, 47,
4553-4556.
(13) (a) Larock, R. C.; Bernhardt, J . C. Tetrahedron Lett. 1976, 36,
3097-3100. (b) Marino, J . P.; Linderman, R. J . J . Org. Chem. 1981,
46, 3696-3702. J abri, N.; Alexakis, A.; Normant, J . F. Tetrahedron
1986, 42(5), 1369-1380. (c) Parrain, J . L.; Beaudet, I.; Ducheˆne, A.;
Watrelot, S.; Quintard, J . P. 1993, 34(34), 5445-5448.
(14) (a) Larock, R. C.; Hershberger, S. S. J . Org. Chem. 1980, 45,
3840-3846. (b) Goure, W. F.; Wright, M. E.; Davis, P. D.; Stille, J . K.
J . Am. Chem. Soc. 1984, 106, 6417-6422.
(5) Venkataraman, K., Ed. The Chemistry of Synthetic Dyes; Aca-
demic Press: New York, 1971; Vol. 4.
(6) Goto, Y.; Nakayama, M. Nippon Oils and Fats Co, Ltd. J apan
Kokai Tokkyo Koho J P62,174,203[87,174,203] (C1008F2/50), 1987; App
86/14,740, 1986.
(7) See, for instance: Higuchi, H.; Kondo, S.; Watanabe, Y.; Ojima,
J .; Yamamoto, G. J . Chem. Soc., Perkin Trans. 1 1994, 14, 1957-1968
and references cited therein.
(8) Habermas, K. L.; Denmark, S. E.; J ones, T. K. Org. React. (New
York) 1994, 45, 1-158.
(9) (a) Hermann, K.; Dreiding, A. S. Helv. Chim. Acta 1976, 59, 626-
642. (b) J akubcova´, M.; Ve´gh, D.; Kozisek, J .; Dvorsky, A. Synth.
Commun. 1994, 24, 1333-1338.
(15) Motoyoshiya, J .; Miyajima, M.; Hirakawa, K.; Kakurai, T. J .
Org. Chem. 1985, 50, 1326-1327.
(16) Guo, C.; Lu, X. Tetrahedron Lett. 1991, 32(51), 7549-7552. Guo,
C.; Lu, X. Synlett 1992, 405-406.
(10) (a) Winkler, J . D.; Kim, S.; Condroski, K. R.; Asensio, A.; Houk,
K. N. J . Org. Chem. 1994, 59, 6879-6881. (b) Winkler, J . D.; Kim, H.
S.; Kim, S. Tetrahedron Lett. 1995, 36, 687-690.
S0022-3263(96)00364-7 CCC: $12.00 © 1996 American Chemical Society

5064 J . Org. Chem., Vol. 61, No. 15, 1996
Marchand et al.
Sch em e 2
F igu r e 2.
Sch em e 1a
pared from acetophenone-d3 by oxidation with SeO2. 6d
was prepared similarly from methyl glyoxylate.
a
Reagents and conditions: (i) Swern, (66%); (ii) MnO2, CH2Cl2,
rt, 2 h (89%); (iii) PPh3, CHCl3, 75 °C, 72 h and then Et3N (50%);
(iv) (EtO2C)2CO, toluene, 75 °C, 3 h (98%); (v) PhCOCHO, H2O,
toluene, molecular sieves, 75 °C, 2 h (83%); (vi) PhCOCDO,
toluene, 75 °C, 1 h (90%); (vi) MeO2C-CHO, toluene, 75 °C, 3 h
(54%).
Reactivity in cycloaddition reactions was studied first
(Scheme 2). Diels-Alder reactions with an excess of 2,3-
dimethylbutadiene at 45 °C gave good yields of a mixture
of the two adducts, which could be easily separated by
silica gel chromatography. The diastereoselectivity of
these reactions (10a /11a ) 55/45 and 10b/11b ) 64/36)
was determined by high-field NMR studies on the crude
reaction mixtures, and the stereochemistry of the cy-
cloadducts was unambiguously established by X-ray
crystallography21 of 10a and 11b (Figure 3). In each case
the major diastereoisomer corresponds to a reaction of
the diene on the face anti to the bulky Fe(CO)3 group on
the conformer represented for 6.
In the same manner, 1,3-dipolar addition with azome-
thine ylide 12 generated by the method of Achiwa22 led
to a mixture of two diastereoisomers. While the adducts
13b and 14b were easily separated by chromatography,
pyrrolidines 13a and 14a from 6a obtained as a 70/30
mixture could not be separated. The stereochemistry of
these cycloadducts was tentatively assigned as indicated
by analogy with the preceding Diels-Alder reactions; it
is also in agreement with the other types of addition, vide
infra.
tive and temporary protection for one of the two polyenic
chains and second introduce chirality in the molecule.
Both aspects can be solved by the use of organometallic
complexes. In this paper, we want to describe the
synthesis and studies on the reactivity of new complexes
of type 6 (Figure 2); to the best of our knowledge, these
are the first examples of cross conjugated polyenones
bearing a planar chirality.17 The versatile key interme-
diate for the preparation of 6 is the organometallic
phosphorane 9.
Complexes 6 were prepared by a three-step sequence
starting from the readily available chlorhydrins 7 (Scheme
1).18 In agreement with previous results,19 oxidation is
compatible with the organometallic moiety, but it is
interesting to note that, for the synthesis of 8, the best
yields were obtained using Swern oxidation in the case
of the more polar Ψ-exo20 complex, while MnO2 proved
to be more efficient for the Ψ-endo derivative.
Complexes 6a ,b also reacted with nucleophiles, and
parathiocresol, for instance, added readily to 6a at room
temperature to give a (63:37) mixture of two adducts
(Scheme 3); they were separated by chromatography, and
the stereochemistry of the major isomer 15a was unam-
biguously established by X-ray crystallography analysis
(Figure 4). The free double bond in the selectively
protected polyenone 6a also reacted with the cyclopentyl
radical generated by the method of Chatgiglialoglu23 to
Reaction of chloro ketone 8 with PPh3 followed by basic
treatment yielded the stable, crystalline, phosphorane 9
(50% yield). Wittig reactions with diethyl mesoxalate,
or with phenylglyoxal monohydrate, gave the desired
model compounds 6a and 6b in high yields. The deu-
terated complex 6c was necessary to study the regiose-
lectivity of the additions; it was obtained by reaction of
9 with deuterated phenylglyoxal, the latter being pre-
(17) An interesting type of biscomplexed polyene has been reported
very recently: Nakanishi, S.; Kumeta, K.; Terada, K. Synthesis 1995,
33-35.
(21) The atomic coordinates for these structures have been deposited
with the Cambridge Crystallographic Data Centre. The coordinates
can be obtained, on request, from the Director, Cambridge Crystal-
lographic Data Centre, 12 Union Road, Cambridge, CB2 1EZ, UK.
(22) Terao, Y.; Kotaki, H.; Imai, N.; Achiwa, K. Chem. Pharm. Bull.
1985, 33(7), 2762-2766.
(23) (a) Chatgilialoglu, C.; Griller, D.; Lesage, M. J . Org. Chem.
1988, 53, 3641-3642. (b) Ballestri, M.; Chatgilialoglu, C. J . Org. Chem.
1991, 56, 678-683.
(18) Lellouche, J . P.; Bulot, E.; Beaucourt, J . P.; Martelli, J .; Gre´e,
R. J . Organomet. Chem. 1988, 342, C21-C25.
(19) (a) Gre´e, R. Synthesis 1989, 341-355. (b) Gre´e, R.; Lellouche,
J . P. Advances in Metal Organic Chemistry, Liebeskind, L. S., Ed.; J AI
Press Ltd.: Greenwich, Vol. 4, in press.
(20) For an explanation of the Ψexo/Ψendo nomenclature see: Clinton,
N. A.; Lillya, C. P. J . Am. Chem. Soc. 1970, 92, 3058-3064.

Synthesis of Cross-Conjugated Polyenones
J . Org. Chem., Vol. 61, No. 15, 1996 5065
F igu r e 3.
Sch em e 3a
F igu r e 4.
Sch em e 4a
a
Reagents and conditions: (i) p-thiocresol, THF, 0 °C f rt, 4
h, 15a (44%) and 16a (25%); (ii) cyclopentyl bromide, AIBN,
toluene, 90 °C and then (Me3Si)3SiH in toluene via syringe pump
over 3 h, 17a (52%) and 18a (20%).
give a mixture of diastereoisomeric adducts 17a , 18a
readily separated by chromatography (Scheme 3). The
stereochemistry of the major isomer 17a was also estab-
lished by X-ray crystallography (Figure 4). It is impor-
tant to note that both adducts are again in agreement
with an addition anti to the bulky Fe(CO)3 group, in the
conformation indicated for 6a (Figure 2).
a
Reagents and conditions: (i) p-thiocresol, THF, 0 °C f rt, 4
h, 15b (31%), 16b (28%), 19b (12.5%), and 20b (12.5%); (ii)
cyclopentyl bromide, AIBN, toluene, 90 °C and then (Me3Si)3SiH
in toluene via syringe pump over 5 h, 17b (19%), 18b (14%), 21b
(13%), and 22b (13%).
The same reactions carried out in parallel for 6b led
to four adducts reflecting the two possible sites of
addition (Scheme 4). Derivatives corresponding to an
addition close to the organometallic complex are the
major adducts (70% for nucleophilic addition and 56%
for the radical type reaction), and they were isolated in
stereoisomerically pure form. The adducts corresponding
to the addition vicinal to the benzoyl group were iso-
lated as a 1:1 mixture of epimers. The attribution
was particularly difficult, using NMR data, because
both types of structures were almost identical: in the
case of the addition close to the organometallic complex,
the skeleton was -COCHRCH2CO-, while it became
-COCH2CHRCO- in the case of the addition vicinal to
the benzoyl group.
In order to unambiguously solve this problem, deuter-
ated analogs were synthetized from 6c. The attribution
of the structures was achieved using 13C NMR experi-
ments and especially DEPT spectra: in the case of type
A structures, the DEPT spectrum showed one CH and
one CHD signal, while it showed one CH2 and one CD

5066 J . Org. Chem., Vol. 61, No. 15, 1996
Marchand et al.
Sch em e 5
Sch em e 8
Sch em e 6
Sch em e 7
reactions are possible, leading to polyfunctionalized
molecules of interest, for instance, in the total synthesis
of complex natural products and structural analogs.
Furthermore, to the best of our knowledge, we have
described here the first examples of radical type reactions
in the presence of carbonyliron complexes. It indicates
that it should be possible to combine the synthetic
potentialities of both the organometallic complexes and
the recently developped organic chemistry of radicals.25
Exp er im en ta l Section
Melting points are uncorrected. IR spectra were recorded
on a Nicolet 205. 1H NMR spectra were recorded at 300 and
400 MHz and 13C NMR at 100.6 and 22.5 MHz. Elemental
analyses were performed by the “Service de microanalyses”
(IdRS Suresnes and ICSN Gif sur Yvette). All separations
were carried out under flash chromatographic conditions on
Merck silica gel Geduran Si60 (230-240 mesh) using, as
eluent, mixtures of ether and low-boiling (e60 °C) petroleum
ether. CH2Cl2 was distilled on P2O5, toluene on CaCl2, and
THF on natrium/benzophenone complex.
Ch lor o Keton e 8. Meth od A. To a solution of the endo
chlorohydrin 7 (2.1g; 6.35 mmol) in CH2Cl2 (50 mL) was added
freshly prepared MnO2 (5.5 g; 10 equiv). The reaction mixture
was stirred at room temperature for 2 h. The dark solution
was filtered on celite and the solvent removed in vacuo, giving
a crude oil that was purified by chromatography on silica gel
(elution with ether/petroleum ether 1/1). Pure product 8 was
obtained as a yellow oil (1.85 g; 89%).
Meth od B. To a well-stirred solution of (COCl)2 (3.5 mL)
in anhydrous CH2Cl2 (17 mL) was added slowly at -70 °C a
solution of DMSO (4.6 mL) in anhydrous CH2Cl2 (12 mL). The
reaction mixture was stirred at -70 °C for 20 min, and then
a solution of the exo chlorohydrin 7 (2.9 g; 8.77 mmol) in
anhydrous CH2Cl2 (17 mL) was added dropwise at -70 °C.
The resulting mixture was stirred for 30 min at -70 °C before
Et3N (5.7 mL) was slowly added. The solution was stirred for
30 min at -70 °C and then allowed to warm to -30 °C,
quenched with saturated aqueous NH4Cl, and extracted with
two portions of ether. The combined organic extracts were
washed with water, dried (MgSO4), and concentrated in vacuo
to give a crude oil that was purified by chromatography on
silica gel (elution with ether/petroleum ether 3/7). Pure
product 8 was obtained as a yellow solid (1.9 g; 66%).
8. Mp: 48 °C (from ether). 1H NMR (400 MHz; C6D6): δ
1.15 (d, J ) 8.1 Hz, 1H, H2 or H5); 1.18 (d, J ) 8.1 Hz, 1H, H2
or H5); 3.39 (s, 3H, CO2Me); 3.41 (s, 2H, CH2Cl); 5.50 (dd, J )
7.9, 5.2 Hz, 1H, H3 or H4); 5.55 (dd, J ) 7.9, 5.2 Hz, 1H, H3 or
signal for type B structures (Scheme 5). These 13C NMR
experiments, done for each of the isolated deuterated
adducts, permitted the attribution of their structures and
thus also for corresponding products derived from 6b. The
stereochemistry of the major isomers was tentatively
assigned in analogy with preceding results.
It is well recognized that addition reactions on a ketone
vicinal to a diene-tricarbonyliron complex lead exclu-
sively to the Ψ-endo derivative via an addition (anti to
the bulky iron carbonyl unit) on the cisoid conformer
(Scheme 6).19
This is indeed the case with these new type 6 deriva-
tives since the reduction of 6d , used as a model, gives
exclusively the Ψ-endo derivative 23d (R3 ) CO2Me; Nu
) H; R4 ) CHdCHCO2Me). Thus, from the four con-
formers A to D theoretically possible for 6 (Scheme 7),
only conformations A and B should probably be consid-
ered. Then, the low diastereoselectivities may reflect the
relatively low energy difference between the cisoid con-
formation A and the transoid B. The approach of the
reagent would again occur exclusively from the face
opposite the metal in both conformations to give the
previously described mixtures of diastereoisomers. The
major adducts come from addition on type A conformers.
The decomplexation of all these adducts under usual
conditions (Ce4+, MeOH, -15 °C) gave the corresponding
racemic derivatives in good yields (Scheme 8). The diene
units of these new compounds can be further utilized in
synthesis as already demonstrated in a related system.19
In conclusion, it is possible using this strategy to build
a novel class of cross-conjugated polyenones bearing an
organometallic protective group. Since the starting
complex is easily resolved,24 these derivatives should be
accessible in optically pure form. Various types of
(24) Monpert, A.; Martelli, J .; Gre´e, R.; Carrie´, R. Tetrahedron Lett.
1981, 22, 1961-1964.
(25) Giese, B. Radicals in Organic Synthesis; Pergamon Press: New
York, 1986.

Synthesis of Cross-Conjugated Polyenones
J . Org. Chem., Vol. 61, No. 15, 1996 5067
H4). 13C NMR (100 MHz; CDCl3): δ 47.3 and 49.6 (C2 and
C5); 47.4 (CH2Cl); 52.1 (CO2Me); 85.3 and 87.9 (C3 and C4);
171.7 (C1); 198.4 (C6). IR (Nujol): 1675 (ketone); 1712 (ester);
2006 and 2075 (Fe(CO)3). Anal. Calcd for C11H9ClFeO6: C,
46.37; H, 3.24. Found: C, 46.18; H, 3.32.
Hz, 1H, H7 or H8); 7.45 (2H, arom); 7.55 (1H, arom); 7.91 (2H,
arom). 13C NMR (100 MHz, CDCl3): δ 47.2 and 54.4 (C2 and
C5); 52.0 (CO2Me); 85.0 and 87.5 (C3 and C4); 128.5, 128.7,
133.5, 133.6, 135.7, and 138.5 (C7 and C8 and arom); 171.8 (C1);
194.1 and 194.3 (C6 and C9). IR (Nujol): 1582, 1602, and 1610
(arom and alkene); 1663 (ketone); 1714 (ester); 2001 and 2068
(Fe(CO)3).
Keto P h osp h or a n e 9. In a dry three-necked round-bottom
flask fitted with a reflux condenser were placed chloro ketone
8 (1.79 g; 5.45 mmol), freshly distilled chloroform (140 mL),
and anhydrous potassium carbonate (1.4 g). Argon was
bubbled in the mixture for 20 min, then anhydrous triph-
enylphosphine (1.37 g; 0.96 equiv) was added and the reaction
mixture was refluxed for 3 days under argon. After removal
of chloroform in vacuo, the crude oil was rapidly filtered
through silica gel (elution with ether + 833 µL (1.1 equiv) of
Et3N). The solvents were removed in vacuo, and the crude
product was purified by chromatography on silica gel (elution
with ether/petroleum ether 1/1) to yield pure keto phosphorane
as an orange solid (1.55 g; 51%) and chloro ketone 8 (300 mg),
which can be recycled. 9. Mp: 166-168 °C (from ether). 1H
NMR (400 MHz; CDCl3): δ 1.15 (d, J ) 8.3 Hz, 1H, H2 or H5);
1.98 (d, J ) 8.5 Hz, 1H, H2 or H5); 3.66 (s, 3H, CO2Me); 3.91
(d, J HP ) 24.5 Hz, 1H, H7); 5.85 (dd, J ) 8.0, 5.4 Hz, 1H, H3 or
H4); 6.00 (dd, J ) 8.4, 5.2 Hz, 1H, H3 or H4); 7.45 (6H, arom);
7.55 (3H, arom); 7.60-7.65 (6H, arom). 13C NMR (100 MHz;
CDCl3): δ 45.4 (C2); 51.6 (CO2Me); 53.4 (d, J CP ) 110.9 Hz,
C7); 62.5 (d, J CP ) 20.3 Hz, C5); 83.7 (C3); 85.6 (d, J CP ) 3 Hz,
C4); 126.8 (d, J CP ) 90.5 Hz, Cipso); 128.8 (d, J CP ) 12.2 Hz,
Cortho); 132.1 (d, J CP ) 3.1 Hz, Cpara); 133.0 (d, J CP ) 10.2 Hz,
Cmeta); 173.0 (C1); 185.0 (d, J CP ) 3.0 Hz, C6). 31P NMR (162
MHz; CDCl3): δ 15.16. IR (Nujol): 1627 (ketone); 1708 (ester);
1970, 2001, and 2057 (Fe(CO)3). Anal. Calcd for C29H23FeO6P:
C, 62.84; H, 4.18. Found: C, 62.59; H, 4.39.
Deu ter a ted P h en ylglyoxa l. In
a two-necked round-
bottom flask fitted with a reflux condenser were introduced
dioxane (50 mL), water (1 mL), and SeO2 (1.82 g; 2.7 equiv).
The reaction mixture was heated at 65 °C until complete
dissolution of SeO2, and then acetophenone-d3 (700 µL; 5.99
mmol) was added and the mixture refluxed for 48 h. After
rapid filtration on silica gel and removal of the solvents, the
crude product was purified by chromatography on silica gel
(elution with ether/petroleum ether 3/7), yielding deuterated
phenylglyoxal as a white solid (800 mg; quant). The NMR
spectra were similar to those of commercial phenylglyoxal
monohydrate, except for the disappearance of the singlet at
9.67 ppm (CHO f CDO) for the
1H NMR spectrum and the
weakness of the signal at 87.1 ppm (CHO,H2O f CDO) for
the 13C NMR spectrum.
Olefin 6c. A solution of keto phosphorane 9 (150 mg; 0.27
mmol) and deuterated phenylglyoxal (42 mg; 1 equiv) in
toluene (8 mL) was stirred under N2
at 75 °C for 1 h. Toluene
was removed in vacuo, and chromatography of the crude oil
(elution with ether/petroleum ether 4/6) yielded 6c (65 mg;
90%) as a yellow solid. NMR spectra were similar to those of
6b, except for the
1H NMR spectrum, where the doublet at
7.16 ppm was simplified into a singlet (H7) and the doublet at
7.83 ppm (H8 f D) disappeared, and for the 13C NMR
spectrum, where a triplet appeared at 133.1 ppm instead of a
singlet (C8).
Olefin 6a . A solution of keto phosphorane 9 (750 mg; 1.37
mmol) and diethyl ketomalonate (206 µL; 1 equiv) in toluene
(40 mL) was stirred under N2 at 75 °C for 3 h. The reaction
mixture was filtered, and toluene was removed in vacuo.
Chromatography of the crude oil (elution with ether/petroleum
ether 4/6) yielded 6a (605 mg; 98%) as an orange solid. 6a .
Mp: 93 °C (from ether). Rf ) 0.36 (E/PE 1/1). 1H NMR (400
MHz, C6D6): δ 0.69 (d, J ) 8.1 Hz, 1H, H2 or H5); 0.86 (t, J )
7.1 Hz, 3H, CO2CH2CH3); 1.04 (d, J ) 8.6 Hz, 1H, H2 or H5);
1.12 (t, J ) 7.1 Hz, 3H, CO2CH2CH3); 3.29 (s, 3H, CO2Me);
3.91 (q, J ) 7.1 Hz, 2H, CO2CH2CH3); 4.30 (q, J ) 7.1 Hz, 2H,
CO2CH2CH3); 5.38 (dd, J ) 8.1, 5.6 Hz, 1H, H3 or H4); 5.44
(dd, J ) 8.1, 5.6 Hz, 1H, H3 or H4). 13C NMR (100 MHz,
C6D6): δ 14.5 and 14.6 (CO2CH2CH3); 48.3 and 55.9 (C2 and
C5); 51.2 (CO2Me); 62.5 and 62.9 (CO2CH2CH3); 85.5 and 88.5
(C3 and C4); 135.7 (C7); 137.8 (C8); 163.8, 165.3, and 172.1 (CO2-
Et and C1); 192.3 (C6). IR (Nujol): 1622 (alkene); 1670
(ketone); 1718 and 1742 (ester); 2013 and 2073 (Fe(CO)3). Anal.
Calcd for C18H18FeO10: C, 48.02, H, 4.03. Found: C, 48.10,
H, 4.08.
Olefin 6d . A solution of keto phosphorane 9 (740 mg; 1.33
mmol) and freshly distilled methyl glyoxylate (400 mg; 1.3
equiv) in toluene (20 mL) was stirred under N2 at 75 °C for 3
h. The reaction mixture was filtered, and toluene was removed
in vacuo. Chromatography of the crude oil (elution with ether/
petroleum ether 4/6) allowed the separation of 6d from its
Z-isomer. 6d (260 mg; 54%) is an orange solid. Mp: 151 °C
(from ether). Rf ) 0.38 (E/PE 1/1). 1H NMR (400 MHz,
C6D6): δ 0.86 (d, J ) 7.9 Hz, 1H, H2 or H5); 0.90 (d, J ) 8.1
Hz, 1H, H2 or H5); 3.30 (s, 3H, CO2Me); 3.31 (s, 3H, CO2Me);
5.46 (dd, J ) 7.8, 5.1 Hz, 1H, H3 or H4); 5.54 (dd, J ) 7.8, 5.6
Hz, 1H, H3 or H4); 6.78 (d, J ) 15.8 Hz, 1H, H7 or H8); 7.02 (d,
J ) 15.8 Hz, 1H, H7 or H8). 13C NMR (100 MHz, C6D6): δ
48.3 and 55.1 (C2 and C5); 52.2 and 52.3 (CO2Me); 85.8 and
88.5 (C3 and C4); 130.7 and 130.1 (C7 and C8); 166.4 and 172.1
(C1 and C9); 193.0 (C6). IR (Nujol): 1627 (alkene); 1671
(ketone); 1702 and 1721 (ester); 2006, 2018, and 2075 (Fe-
(CO)3). Anal. Calcd for C14H12FeO8: C, 46.18, H, 3.32.
Found: C, 46.37, H, 3.24.
Olefin 6b. A solution of keto phosphorane 9 (500 mg; 0.90
mmol) and phenylglyoxal monohydrate (165 mg; 1.2 equiv) in
toluene (20 mL) was stirred in the presence of molecular sieves
(4 Å) under N2 at 75 °C for 2 h. The reaction mixture was
filtered, and toluene was removed in vacuo. Chromatography
of the crude oil (elution with ether/petroleum ether 4/6) allowed
the separation of 6b from a small amount of its Z-isomer. 6b
(305 mg; 83%) is a yellow solid. Mp: 136-137 °C (from ether).
Rf ) 0.42 (E/PE 1/1). 1H NMR (400 MHz, CDCl3): δ 1.53 (d,
J ) 8.2 Hz, 1H, H2 or H5); 1.73 (d, J ) 8.1 Hz, 1H, H2 or H5);
3.73 (s, 3H, CO2Me); 6.11 (dd, J ) 8.2, 5.2 Hz, 1H, H3 or H4);
6.17 (dd, J ) 8.1, 5.8 Hz, 1H, H3 or H4); 7.16 (d, J ) 15.3 Hz,
1H, H7); 7.83 (d, J ) 15.3 Hz, 1H, H8); 7.52 (2H, arom); 7.63
(1H, arom); 8.02 (2H, arom). 13C NMR (100 MHz, CDCl3): δ
47.5 and 54.7 (C2 and C5); 52.0 (CO2Me); 85.2 and 88.0 (C3
and C4); 128.8, 128.9, 133.9, and 137.8 (CH arom and C7); 133.1
(C8); 136.8 (C arom); 171.7 (C1); 189.9 and 193.7 (C6 and C9).
IR (Nujol): 1608 (arom and alkene); 1641 and 1661 (ketone);
1713 (ester); 1991 and 2072 (Fe(CO)3). Anal. Calcd for
C19H14FeO7: C, 55.64, H, 3.44. Found: C, 55.75, H, 3.61.
Z-Isomer (8%). Rf ) 0.24 (E/PE 1/1). 1H NMR (400 MHz,
CDCl3): δ 1.39 (d, J ) 7.1 Hz, 1H, H2 or H5); 1.53 (d, J ) 7.1
Hz, 1H, H2 or H5); 3.70 (s, 3H, CO2Me); 5.96-6.02 (m, 2H, H3
and H4); 6.56 (d, J ) 11.7 Hz, 1H, H7 or H8); 6.82 (d, J ) 11.7
Z-isomer (21%). Mp: 76 °C (from ether). Rf ) 0.21 (E/PE
1/1).
1H NMR (400 MHz, C6D6): δ 1.08 (d, J ) 8.1 Hz, 2H, H2
and H5); 3.31 (s, 3H, CO2Me); 3.35 (s, 3H, CO2Me); 5.49 (dd, J
) 8.1, 5.1 Hz, 1H, H3 or H4); 5.62 (dd, J ) 8.1, 5.6 Hz, 1H, H3
or H4); 5.66 (d, J ) 12.0 Hz, 1H, H7 or H8); 5.82 (d, J ) 12.0
Hz, 1H, H7
or H8). 13C NMR (100 MHz, C6D6): δ 48.0 and
55.2 (C2 and C5); 52.1 and 52.2 (CO2Me); 85.8 and 88.0 (C3
and C4); 127.1 and 139.9 (C7 and C8); 166.4 and 172.2 (C1 and
C9); 196.0 (C6); 205.6, 206.1, and 206.6 (Fe(CO)3). IR (Nujol):
1618 (alkene); 1668 (ketone); 1704 and 1724 (ester); 2003 and
2072 (Fe(CO)3).
Cycloa d d ition w ith 2,3-Dim eth yl-1,3-bu ta d ien e: fr om
6a . A solution of olefin 6a (140 mg; 0.31 mmol) and dimeth-
ylbutadiene (1 mL) in CH2Cl2 (2 mL) was heated at 45 °C for
40 h. The reaction mixture was evaporated, and chromatog-
raphy of the residual oil (elution with ether/petroleum ether
2/8) allowed the separation of the two isomers 10a and 11a
(93%; 10a /11a ) 55/45).
Isom er 10a . Mp: 108 °C (from ether). Rf ) 0.57 (E/PE
1/1). 1H NMR (300 MHz, CDCl3): δ 1.22 (t, J ) 7.1 Hz, 3H,
CO2CH2CH3); 1.23 (t, J ) 7.1 Hz, 3H, CO2CH2CH3); 1.34 (d, J
) 7.3 Hz, 1H, H2 or H5); 1.56 (d, J ) 7.4 Hz, 1H, H2 or H5);
1.57 (s, 3H, Me); 1.63 (s, 3H, Me); 2.18 (m, 1H, H12); 2.49 (m,
1H, H12); 2.63 (d, J ) 16.9 Hz, 1H, H9); 2.89 (d, J ) 17.3 Hz,

5068 J . Org. Chem., Vol. 61, No. 15, 1996
Marchand et al.
1H, H9); 3.49 (dd, J ) 7.7, 4.4 Hz, 1H, H7) 3.70 (s, 3H, CO2Me);
4.07-4.23 (m, 4H, CO2CH2CH3); 5.93-6.01 (m, 2H, H3 and H4).
13C NMR (22.5 MHz, CDCl3): δ 13.9 (CO2CH2CH3); 18.7 and
18.9 (Me); 31.8 and 35.1 (CH2); 46.5 and 53.2 (C2 and C5); 48.6
(C7); 51.8 (CO2Me); 55.5 (C8); 61.4 and 62.6 (CO2CH2CH3); 85.9
and 86.5 (C3 and C4); 121.4 and 124.6 (MeCdCMe); 169.8,
170.6, and 172.0 (C1 and CO2Et); 203.8 (C6). IR (Nujol): 1668
(alkene), 1719 (broad, ketone and ester), 2001, 2022 and 2075
(Fe(CO)3). Anal. Calcd for C24H28FeO10: C, 54.15; H, 5.30.
Found: C, 54.08; H, 5.30.
Isom er 11a . Mp: 114 °C (from ether). Rf ) 0.41 (E/PE
1/1). 1H NMR (300 MHz, CDCl3): δ 1.21 (t, J ) 7.1 Hz, 3H,
CO2CH2CH3); 1.23 (t, J ) 7.1 Hz, 3H, CO2CH2CH3); 1.33 (d, J
) 8.4 Hz, 1H, H2 or H5); 1.56 (d, J ) 8.1 Hz, 1H, H2 or H5);
1.63 (s, 3H, Me); 1.66 (s, 3H, Me); 2.40 (broad dd, J ) 17.5,
14.0 Hz, 1H, H12); 2.52 (broad dd, J ) 17.8, 7.2 Hz, 1H, H12);
2.58 (d, J ) 16.9 Hz, 1H, H9); 2.75 (d, J ) 17.3 Hz, 1H, H9);
3.48 (dd, J ) 14.0, 7.0 Hz, 1H, H7); 3.71 (s, 3H, CO2Me); 4.11-
4.21 (m, 4H, CO2CH2CH3); 5.93-6.06 (m, 2H, H3 and H4). 13C
NMR (22.5 MHz, CDCl3): δ 14.0 (CO2CH2CH3); 18.6 and 18.9
(Me); 32.7 and 35.6 (CH2); 46.7 and 52.9 (C2 and C5); 49.6 (C7);
51.9 (CO2Me); 55.9 (C8); 61.3 and 61.7 (CO2CH2CH3); 86.2 and
87.3 (C3 and C4); 121.6 and 124.7 (MeCdCMe); 170.0, 170.9,
and 171.9 (C1 and CO2Et); 204.8 (C6). IR (Nujol): 1663
(alkene), 1719 (ketone), 1756 (ester), 1997 and 2065 (Fe(CO)3).
Anal. Calcd for C24H28FeO10: C, 54.15; H, 5.30. Found: C,
53.82; H, 5.35.
CO2CH2CH3 14a ); 1.22 (t, J ) 7.1 Hz, CO2CH2CH3 13a ); 1.24
(t, J ) 7.1 Hz, CO2CH2CH3 14a ); 1.25 (t, J ) 7.1 Hz, CO2-
CH2CH3 13a ); 1.33 (d, J ) 8.1 Hz, H5 13a ); 1.39 (d, J ) 8.1
Hz, H5 14a and H2 13a ); 1.72 (d, J ) 8.1 Hz, H2 14a ); 2.56
(dd, J ) 9.4, 6.4 Hz, H10 13a and 14a ); 2.70 (t, J ) 8.7 Hz, H10
13a ); 3.07 (d, J ) 9.7 Hz, H9 13a ); 3.23 (s, NCH2Ph 14a ); 3.25
(s, NCH2Ph 13a ); 3.28 (d, J ) 10.7 Hz, H9 14a ); 3.36 (d, J )
9.7 Hz, H9 13a ); 3.58-3.65 (m, H7 13a and 14a ); 3.66 (s, CO2Me
13a ); 3.70 (s, CO2Me 14a ); 3.96-4.11 (m, CO2CH2CH3 13a and
14a ); 4.19 and 4.27 (m, CO2CH2CH3 13a and 14a ); 5.90-6.03
(m, H3 and H4 13a and 14a ); 7.23-7.31 (5H, arom 13a and
14a ). 13C NMR (100 MHz, CDCl3): δ 13.8 (CO2CH2CH3 13a );
13.9 (CO2CH2CH3 14a ); 46.7 and 55.1 (C2 and C5, 13a ); 47.1
and 54.8 (C2 and C5, 14a ); 51.9 (CO2Me, 13a ); 52.0 (CO2Me,
14a ); 54.1 (C7, 13a and 14a ); 56.4 and 59.1 (CH2, 13a ); 56.6
and 59.1 (CH2, 14a ); 59.6 (NCH2Ph 13a ); 60.3 (NCH2Ph 14a );
61.6 and 62.1 (CO2CH2CH3, 13a ); 61.8 and 62.3 (CO2CH2CH3,
14a ); 62.0 (C8 13a ); 63.1 (C8 14a ); 85.0 and 87.3 (C3 and C4,
13a ); 85.9 and 86.7 (C3 and C4, 14a ); 127.1, 128.3, 128.4, 128.5,
and 138.4 (C arom, 13a and 14a ); 168.7, 170.4, and 171.9 (C1
and CO2Et, 14a ); 169.0, 170.2, and 172.0 (C1 and CO2Et, 13a );
203.2 (C6 13a ); 203.5 (C6 14a ). IR (Nujol): 1590 (arom and
alkene), 1679 (ketone), 1725 (broad, ester), 1998 and 2072 (Fe-
(CO)3). Anal. Calcd for C27H29FeNO10
Found: C, 55.63; H, 5.16.
: C, 55.59; H, 5.01.
F r om 6b. To the solution of olefin 6b (300 mg; 0.73 mmol)
and amino ether (610 µL) in CH2Cl2 (30 mL) was added under
N2 at 0 °C a 0.1 M solution of trifluoroacetic acid in CH2Cl2
(3.6 mL; 0.5 equiv). The reaction mixture was stirred for 4 h
and then hydrolyzed with saturated aqueous Na2CO3 and
extracted with ether. The organic layer was washed with
water until neutral pH, dried (MgSO4), and evaporated.
Chromatography of the residual oil (elution with ether/
petroleum ether 2/8) allowed the separation of the two isomers
13b and 14b (78%; 13b/14b ) 70/30).
Isom er 13b. Mp: 110 °C (from ether). Rf ) 0.35 (E/PE
1/1). 1H NMR (400 MHz, CDCl3): δ 1.31 (d, J ) 7.2 Hz, 1H,
H2 or H5); 1.47 (d, J ) 7.2 Hz, 1H, H2 or H5); 2.68 (dd, J ) 9.0,
6.7 Hz, 1H, H10); 2.88 (dd, J ) 9.2, 6.2 Hz, 1H, H11); 2.97 (t, J
) 8.9 Hz, 1H, H10); 3.03 (t, J ) 9.2 Hz, 1H, H11); 3.61 (s, 2H,
NCH2Ph); 3.68 (s, 3H, CO2Me); 3.71 (q, J ) 6.2 Hz, 1H, H7);
4.40 (m, 1H, H8); 5.98-6.03 (m, 2H, H3 and H4); 7.24-7.30
(5H, arom); 7.43 (2H, arom); 7.55 (1H, arom); 7.92 (2H, arom).
13C NMR (100 MHz, CDCl3): δ 47.2 and 52.0 (C2 and C5); 47.1
(C8); 52.0 (CO2Me); 53.5 (C7); 56.9 and 56.9 (CH2); 59.4 (NCH2-
Ph); 85.5 and 87.1 (C3 and C4); 127.2, 128.4, 128.6, 128.6, 128.7,
and 133.3 (CH arom); 136.1 and 138.3 (C arom); 171.9 (C1);
199.1 and 204.1 (C6 and C9). IR (Nujol): 1596 (arom and
alkene), 1656 and 1693 (ketone), 1713 (ester), 2004 and 2060
(Fe(CO)3). Anal. Calcd for C28H25FeNO7: C, 61.89; H, 4.64.
Found: C, 61.69; H, 4.82.
F r om 6b. A solution of olefin 6b (200 mg; 0.49 mmol) and
dimethylbutadiene (2 mL) in CH2Cl2 (4 mL) was heated at 45
°C for 4 h. The reaction mixture was evaporated, and
chromatography of the residual oil (elution with ether/
petroleum ether 2/8) allowed the separation of the two isomers
10b and 11b (quant; 10b/11b ) 64/36).
Isom er 10b. Mp: 132 °C (from ether). Rf ) 0.56 (E/PE
1/1). 1H NMR (300 MHz, CDCl3): δ 1.36 (d, J ) 7.5 Hz, 1H,
H2 or H5); 1.60 (d, J ) 8.0 Hz, 1H, H2 or H5); 1.62 (s, 3H, Me);
1.66 (s, 3H, Me); 2.06 (m, 2H, CH2); 2.29 (broad dd, J ) 15.9,
5.2 Hz, 2H, CH2); 3.22 (td, J ) 11.4, 5.2 Hz, 1H, H7); 3.70 (s,
3H, CO2Me); 3.86 (td, J ) 11.3, 5.5 Hz, 1H, H8); 5.90 (ddd, J
) 8.1, 5.5, 0.7 Hz, 1H, H4); 5.96 (dd, J ) 8.1, 5.2 Hz, 1H, H3);
7.43 (2H, arom); 7.53 (1H, arom); 7.98 (2H, arom). 13C NMR
(22.5 MHz, CDCl3): δ 18.6 (Me); 34.7 and 37.5 (CH2); 43.8 (C8);
46.2 and 54.0 (C2 and C5); 49.2 (C7); 51.7 (CO2Me); 84.9 and
86.6 (C3 and C4); 124.0 and 124.7 (MeCdCMe); 128.2, 128.4,
and 132.7 (CH arom); 136.4 (C arom); 172.1 (C1); 202.6 and
206.8 (C6 and C9). IR (Nujol): 1672 (arom and alkene), 1719
(ketone), 1743 (ester), 1989, 2006 and 2063 (Fe(CO)3). Anal.
Calcd for C25H24FeO7: C, 60.99; H, 4.91. Found: C, 60.79; H,
5.02.
Isom er 11b. Mp: 90 °C (from ether). Rf ) 0.50 (E/PE 1/1).
1H NMR (300 MHz, CDCl3): δ 1.42 (d, J ) 8.5 Hz, 1H, H2 or
H5); 1.62 (s, 3H, Me); 1.71 (s, 3H, Me); 1.73 (d, J ) 8.3 Hz, 1H,
H2 or H5); 2.00 (m, 1H, H10); 2.13-2.30 (broad, 2H, H10 and
H13); 2.43 (broad dd, J ) 16.6, 4.9 Hz, 1H, H13); 3.25 (td, J )
11.2, 5.4 Hz, 1H, H7); 3.71 (s, 3H, CO2Me); 3.86 (td, J ) 11.5,
5.4 Hz, 1H, H8); 5.91 (ddd, J ) 8.3, 5.2, 1.2 Hz, 1H, H4); 6.02
(dd, J ) 8.4, 5.2 Hz, 1H, H3); 7.45 (2H, arom); 7.55 (1H, arom);
7.94 (2H, arom). 13C NMR (22.5 MHz, CDCl3): δ 18.7 (Me);
35.8 and 36.2 (CH2); 45.8 (C8); 47.2 and 54.3 (C2 and C5);
49.3 (C7); 51.9 (CO2Me); 85.7 and 87.3 (C3 and C4); 124.5
(MeCdCMe); 128.5, 128.6 and 133.1 (CH arom); 136.2 (C
arom); 171.9 (C1); 203.3 and 208.7 (C6 and C9). IR (Nujol):
1666 (arom and alkene), 1720 (ketone), 1755 (ester), 2004 and
2070 (Fe(CO)3). Anal. Calcd for C25H24FeO7: C, 60.99; H, 4.91.
Found: C, 61.25; H, 4.91.
Isom er 14b. Yellow oil. Rf ) 0.40 (E/PE 1/1). 1H NMR
(400 MHz, CDCl3): δ 1.31 (d, J ) 8.1 Hz, 1H, H2 or H5); 1.47
(d, J ) 8.1 Hz, 1H, H2 or H5); 2.72 (dd, J ) 9.7, 6.3 Hz, 1H,
H10); 2.85 (dd, J ) 8.7, 6.4 Hz, 1H, H11); 3.06 (t, J ) 8.6 Hz,
1H, H10); 3.10 (t, J ) 9.2 Hz, 1H, H11); 3.64 (s, 2H, NCH2Ph);
3.69 (s, 3H, CO2Me); 3.83 (dt, J ) 7.6, 6.1 Hz, 1H, H7); 4.39
(dt, J ) 9.2, 6.1 Hz, 1H, H8); 5.97 (dd, J ) 8.1, 5.5 Hz, 1H, H3
or H4); 6.01 (dd, J ) 7.9, 5.5 Hz, 1H, H3 or H4); 7.22-7.34 (5H,
arom); 7.44 (2H, arom); 7.55 (1H, arom); 7.92 (2H, arom). 13C
NMR (100 MHz, CDCl3): δ 47.0 and 53.1 (C2 and C5); 47.5
(C8); 51.9 (C7); 52.0 (CO2Me); 57.2 and 57.5 (CH2); 59.4 (NCH2-
Ph); 86.0 and 87.3 (C3 and C4); 127.2, 128.3, 128.6, 128.7, 128.7,
and 133.3 (CH arom); 136 and 138.3 (C arom); 171.8 (C1); 199.1
and 205.0 (C6 and C9). IR (Nujol): 1581 and 1598 (arom and
alkene), 1675 (ketone), 1723 (ester), 2006 and 2071 (Fe(CO)3).
Anal. Calcd for C28H25FeNO7: C, 61.89; H, 4.64. Found: C,
61.86; H, 4.75.
Nu cleop h ilic Ad d ition w ith p-Th iocr esol: fr om 6a . To
a stirred solution of olefin 6a (250 mg; 0.55 mmol) in dry THF
(10 mL) was added, under N2 at 0 °C, p-thiocresol (140 mg; 2
equiv). The mixture was stirred for 10 min at 0 °C and then
4 h at room temperature, hydrolyzed with saturated aqueous
Na2CO3, and extracted with ether. The separated organic
layer was washed with water, dried (MgSO4), and evaporated.
Chromatography of the residual oil (elution with ether/
Cycloa d d ition w ith Azom eth in e Ylid e: fr om 6a . To the
solution of olefin 6a (240 mg; 0.43 mmol) and amino ether (240
µL) in CH2Cl2 (25 mL) was added under N2 at 0 °C a 0.1 M
solution of trifluoroacetic acid in CH2Cl2 (3.4 mL; 0.8 equiv).
The reaction mixture was stirred for 24 h and then hydrolyzed
with saturated aqueous Na2CO3 and extracted with ether. The
organic layer was washed with water until neutral pH, dried
(MgSO4), and evaporated. Chromatography of the residual oil
(elution with ether/petroleum ether 2/8) yielded a 70/30
unseparable mixture of 13a and 14a (240 mg; 96%). Rf ) 0.52
(E/PE 7/3). 1H NMR (400 MHz, CDCl3): δ 1.17 (t, J ) 7.1 Hz,

Synthesis of Cross-Conjugated Polyenones
J . Org. Chem., Vol. 61, No. 15, 1996 5069
petroleum ether 2/8) allowed the separation of the two isomers
15a and 16a (69%; 15a /16a ) 63/37).
(ester), 1989, 2011, and 2063 (Fe(CO)3). Anal. Calcd for
C26H22FeO7S: C, 58.44; H, 4.15; S, 6.00. Found: C, 58.59; H,
4.26; S, 5.95.
Isom er 15a . Mp: 109 °C (from ether). Rf ) 0.6 (E/PE 1/1).
1H NMR (300 MHz, CDCl3): δ 1.18 (t, J ) 7.1 Hz, 3H, CO2-
CH2CH3); 1.36 (t, J ) 7.1 Hz, 3H, CO2CH2CH3); 1.35 (d, J )
7.3 Hz, 1H, H2 or H5); 1.85 (d, J ) 8.1 Hz, 1H, H2 or H5); 2.34
(s, 3H, Me); 3.71 (s, 3H, CO2Me); 3.83 (d, J ) 11.6 Hz, 1H, H7
or H8); 4.13 (d, J ) 11.6 Hz, 1H, H8 or H7); 4.09 (q, J ) 7.1 Hz,
2H, CO2CH2CH3); 4.34 (q, J ) 7.0 Hz, 2H, CO2CH2CH3); 5.93
(ddd, J ) 7.9, 5.2, 0.8 Hz, 1H, H3 or H4); 6.02 (ddd, J ) 8.4,
5.2, 0.8 Hz, 1H, H3 or H4); 7.13 (2H, arom); 7.30 (2H, arom).
13C NMR (22.5 MHz, CDCl3): δ 13.9 and 14.1 (CO2CH2CH3);
21.2 (Me); 46.5 and 52.5 (C2 and C5); 51.8 (CO2Me); 53.9 and
54.2 (C7 and C8); 61.8 (CO2CH2CH3); 85.2 and 86.9 (C3 and
C4); 125.3 (C arom); 130.0 and 135.8 (CH arom); 140.1 (C
arom); 167.1 and 172.1 (C1 and CO2Et); 196.7 (C6). IR
(Nujol): 1668 (arom and alkene), 1706 (ketone), 1733 and 1754
(ester), 1998, 2023, and 2078 (Fe(CO)3). Anal. Calcd for
C25H26FeO10S: C, 52.28; H, 4.56; S, 5.58. Found: C, 52.17;
H, 4.58; S, 5.39.
Isom er 16a . Mp: 92 °C (from ether). Rf ) 0.44 (E/PE 1/1).
1H NMR (300 MHz, CDCl3): δ 1.20 (t, J ) 7.1 Hz, 3H, CO2-
CH2CH3); 1.26 (t, J ) 7.1 Hz, 3H, CO2CH2CH3); 1.36 (dd, J )
8.1, 0.9 Hz, 1H, H2 or H5); 1.69 (dd, J ) 7.9, 0.8 Hz, 1H, H2 or
H5); 2.33 (s, 3H, Me); 3.71 (s, 3H, CO2Me); 3.97 (d, J ) 10.5
Hz, 1H, H7 or H8); 4.23 (d, J ) 10.5 Hz, 1H, H7 or H8); 4.06-
4.25 (m, 4H, CO2CH2CH3); 5.88 (ddd, J ) 8.0, 5.1, 0.9 Hz, 1H,
H3 or H4); 5.99 (ddd, J ) 8.1, 5.1, 0.8 Hz, 1H, H3 or H4); 7.13
(2H, arom); 7.39 (2H, arom). 13C NMR (22.5 MHz, CDCl3): δ
13.9 and 14.0 (CO2CH2CH3); 21.2 (Me); 46.7 and 55.3 (C2 and
C5); 51.9 (CO2Me); 53.8 and 53.9 (C7 and C8); 61.9 and 62.0
(CO2CH2CH3); 86.6 and 87.5 (C3 and C4); 127.7 (C arom); 130.0
and 133.4 (CH arom); 139.0 (C arom); 167.0 and 167.6 (CO2-
Et); 171.9 (C1); 201.0 (C6). IR (Nujol): 1680 (arom and alkene),
1705 (ketone), 1726 and 1747 (ester), 1994, 2025, and 2071
(Fe(CO)3). Anal. Calcd for C25H26FeO10S: C, 52.28; H, 4.56;
S, 5.58. Found: C, 52.19; H, 4.62; S, 5.75.
F r om 6b. To the stirred solution of olefin 6b (250 mg; 0.61
mmol) in dry THF (20 mL) was added under N2 at 0 °C
p-thiocresol (150 mg; 2 equiv). The reaction mixture was
stirred for 4 h and then hydrolyzed with saturated aqueous
Na2CO3 and extracted with ether. The organic layer was
washed with water, dried (MgSO4), and evaporated. Chro-
matography of the residual oil (elution with ether/petroleum
ether 2/8) allowed the separation of three fractions: 15b, 16b,
and a 50/50 unseparable mixture of 19b and 20b (84%; 15b/
16b/19b/20b ) 37/33/15/15).
Isom er 15b. Mp: 195 °C (from ethyl acetate). Rf ) 0.72
(E/PE 1/1). 1H NMR (400 MHz, CDCl3): δ 1.32 (d, J ) 7.1
Hz, 1H, H2 or H5); 1.88 (d, J ) 7.1 Hz, 1H, H2 or H5); 2.35 (s,
3H, Me); 3.21 (dd, J ) 17.8, 3.5 Hz, 1H, H8); 3.69 (dd, J )
17.8, 10.7 Hz, 1H, H8); 3.72 (s, 3H, CO2Me); 4.19 (dd, J ) 10.7,
3.1 Hz, 1H, H7); 5.98-6.03 (m, 2H, H3 and H4); 7.15 (2H, arom);
7.32 (2H, arom); 7.42 (2H, arom); 7.53 (1H, arom); 7.87 (2H,
arom). 13C NMR (100 MHz, CDCl3): δ 21.2 (Me); 39.8 (C8);
46.4 and 54.1 (C2 and C5); 50.7 (C7); 51.9 (CO2Me); 85.1 and
86.9 (C3 and C4); 127.2, 136.5, and 139.6 (C arom); 128.0, 128.5,
130.1, 133.2, and 134.9 (CH arom); 172.2 (C1); 197.1 and 198.5
(C6 and C9). IR (Nujol): 1582 and 1594 (arom and alkene),
1670 (ketone), 1714 (ester), 2005, 2021 and 2062 (Fe(CO)3).
Anal. Calcd for C26H22FeO7S: C, 58.44; H, 4.15; S, 6.00.
Found: C, 58.23; H, 4.22; S, 5.80.
Isom er s 19b a n d 20b. Rf ) 0.55 (E/PE 1/1). 1H NMR (400
MHz, CDCl3): δ 1.33 (d, J ) 7.6 Hz, 1H, H5 19b); 1.33 (d, J )
8.1 Hz, 1H, H5 20b); 1.44 (d, J ) 8.1 Hz, 1H, H2 19b); 1.49 (d,
J ) 7.6 Hz, 1H, H2 20b); 2.33 (s, 3H, Me 20b); 2.34 (s, 3H, Me
19b); 2.86 (dd, J ) 17.3, 4.1 Hz, 1H, H7 19b); 2.93 (dd, J )
17.8, 4.5 Hz, 1H, H7 20b); 3.25 (dd, J ) 17.8, 9.2 Hz, 1H, H7
20b); 3.28 (dd, J ) 17.8, 11.7 Hz, 1H, H7 19b); 3.69 (s, 3H,
CO2Me 19b); 3.70 (s, 3H, CO2Me 20b); 4.90 (dd, J ) 9.2, 4.6
Hz, 1H, H8 19b); 4.90 (dd, J ) 10.2, 4.6 Hz, 1H, H8 20b); 5.88-
5.99 (m, 4H, H3 and H4 19b and 20b); 7.09 (2H, arom 20b);
7.10 (2H, arom 19b); 7.19 (2H, arom 20b); 7.21 (2H, arom 19b);
7.43 (4H, arom 19b and 20b); 7.52-7.56 (2H, arom 19b and
20b); 7.94 (2H, arom 20b); 7.97 (2H, arom 19b). 13C NMR
(100 MHz, CDCl3): δ 21.2 and 21.2 (Me 19b and 20b); 44.1
(C7 20b); 44.5 (C7 19b); 45.5 (C8 19b); 47.2 (C8 20b); 46.6 and
53.8 (C2 and C5 19b); 47.2 and 54.1 (C2 and C5 20b); 51.9 and
52.0 (CO2Me 19b and 20b); 84.2 and 86.9 (C3 and C4 19b);
85.0 and 87.1 (C3 and C4 20b); 126.9, 135.7, and 139.6 (C arom
19b); 126.9, 135.8, and 139.5 (C arom 20b); 128.5, 128.8, 129.9,
132.9, and 135.3 (CH arom 20b); 128.5, 128.8, 129.9, 133.1,
and 135.5 (CH arom 19b); 171.8 (C1 19b); 172.0 (C1 20b); 194.4
and 202.3 (C6 and C9 20b); 194.8 and 202.3 (C6 and C9 19b).
IR (Nujol): 1574 and 1598 (arom and alkene), 1674 (ketone),
1712 (ester), 2002 and 2073 (Fe(CO)3). Anal. Calcd for
C26H22FeO7S: C, 58.44; H, 4.15; S, 6.00. Found: C, 58.42; H,
4.48.
F r om 6c. The reaction yielded, as from 6b, four adducts.
Chromatography allowed the separation of three fractions:
15c, 16c, and a 50/50 unseparable mixture of 19c and 20c.
15c. 13C NMR-DEPT (100 MHz, CDCl3): no CH2 at 39.8 ppm
(C8 f CHD) and one CH at 50.7 ppm (C7). 13C NMR (100 MHz,
CDCl3): modification of the signal at 39.8 ppm into a triplet
(C8 f CHD). 1H NMR (400 MHz, CDCl3): disappearance of
the dd at 3.21 ppm (H8 f D); simplification of the dd at 3.69
ppm into a d (J ) 10.7 Hz, 1H, H8); simplification of the dd at
4.19 ppm into a d (J ) 10.7 Hz, H7). 16c. 13C NMR-DEPT
(100 MHz, CDCl3): no CH2 at 41.3 ppm (C8 f CHD) and one
CH at 51.2 ppm (C7). 13C NMR (100 MHz, CDCl3): modifica-
tion of the signal at 41.3 ppm into a triplet (C8 f CHD). 1H
NMR (400 MHz, CDCl3): disappearance of the dd at 3.28 ppm
(H8 f D); simplification of the dd at 3.77 ppm into a d (J )
10.0 Hz, 1H, H8); simplification of the dd at 4.30 ppm into a d
(J ) 10.0 Hz, H7). 19c and 20c. 13C NMR-DEPT (100 MHz,
CDCl3): no modification of the CH2 at 44.1 and 44.5 ppm (C7).
1H NMR (400 MHz, CDCl3): simplification of the dd at 2.86
and 2.93 ppm into d (J ) 17.3 Hz, H7); simplification of the dd
at 3.25 and 3.28 ppm into d (J ) 17.8 Hz, H7); disappearance
of the dd at 4.90 and 4.90 ppm (H8 f D).
Ra d ica l-Typ e Ad d ition . fr om 6a . To a solution of olefin
6a (195 mg; 0.43 mmol), cyclopentyl bromide (1 equiv; 46 µL),
and a crystal of AIBN in dry toluene (7 mL) at 90 °C was added
via syringe pump a solution of cyclopentyl bromide (185 µL; 4
equiv) and tris(trimethylsilyl)silane (145 µL; 1.1 equiv) in dry
toluene (15 mL) over a 3 h period. After 1 h 30 min of stirring,
a second portion of cyclopentyl bromide (185 µL; 4 equiv) and
tris(trimethylsilyl)silane (145 µL; 1.1 equiv) in toluene (15 mL)
was added dropwise over a 3 h period. The reaction mixture
was stirred again at 90 °C for 1 h 30 min, and then toluene
was removed in vacuo and the crude product purified by
chromatography on silica gel. Elution with ether/petroleum
ether 2/8 allowed the separation of the two isomers 17a and
18a (72%; 17a /18a ) 72/28).
Isom er 16b. Mp: 165 °C (from ethyl acetate/hexane). Rf
) 0.63 (E/PE 1/1). 1H NMR (400 MHz, CDCl3): δ 1.45 (d, J )
8.1 Hz, 1H, H2 or H5); 1.87 (d, J ) 8.1 Hz, 1H, H2 or H5); 2.34
(s, 3H, Me); 3.28 (dd, J ) 18.0, 3.0 Hz, 1H, H8); 3.72 (s, 3H,
CO2Me); 3.77 (dd, J ) 18.0, 10.0 Hz, 1H, H8); 4.30 (dd, J )
9.9, 3.5 Hz, 1H, H7); 5.96 (ddd, J ) 7.9, 5.6, 1.0 Hz, 1H, H3 or
H4); 6.03 (ddd, J ) 8.4, 5.6, 1.0 Hz, 1H, H3 or H4); 7.15 (2H,
arom); 7.38 (2H, arom); 7.42 (2H, arom); 7.55 (1H, arom); 7.87
(2H, arom). 13C NMR (100 MHz, CDCl3): δ 21.2 (Me); 41.3
(C8); 46.4 and 53.6 (C2 and C5); 51.2 (C7); 52.0 (CO2Me); 86.9
and 86.9 (C3 and C4); 128.1, 128.6, 130.1, 133.0, and 133.5 (CH
arom); 128.9, 136.0, and 138.6 (C arom); 172.0 (C1); 197.6 and
202.4 (C6 and C9); 205.2, 205.5, and 212.0 (Fe(CO)3). IR
(Nujol): 1581 and 1600 (arom and alkene), 1665 (ketone), 1708
Isom er 17a . Mp: 120 °C (from ether). Rf ) 0.55 (E/PE
1/1). 1H NMR (400 MHz, CDCl3): δ 1.21 (t, J ) 7.1 Hz, 3H,
CO2CH2CH3); 1.28 (t, J ) 7.1 Hz, 3H, CO2CH2CH3); 1.30 (d, J
) 8.2 Hz, 1H, H2 or H5); 1.53 (d, J ) 8.1 Hz, 1H, H2 or H5);
1.40-1.48, 1.53-1.61, 1.65-1.75, and 1.83-1.93 (series of m,
9H, Hcyclopentyl); 3.39 (dd, J ) 10.6, 6.2 Hz, 1H, H7); 3.70 (s,
3H, CO2Me); 3.86 (d, J ) 10.6 Hz, 1H, H8); 4.06-4.17 (m, 2H,
CO2CH2CH3); 4.21 (q, J ) 7.1 Hz, 2H, CO2CH2CH3); 5.88 (dd,
J ) 8.0, 5.3 Hz, 1H, H3 or H4); 5.96 (dd, J ) 8.0, 5.3 Hz, 1H,
H3 or H4). 13C NMR (100 MHz, CDCl3): δ 13.9 and 14.0 (CO2-
CH2CH3); 24.1, 24.5, 28.6, and 31.0 (CH2 cyclopentyl); 41.5 (CH

5070 J . Org. Chem., Vol. 61, No. 15, 1996
Marchand et al.
cyclopentyl); 46.0 and 56.9 (C2 and C5); 51.9 (CO2Me); 53.5 and
53.9 (C7 and C8); 61.5 and 61.6 (CO2CH2CH3); 85.9 and 86.4
(C3 and C4); 168.0 and 168.7 (CO2Et); 172.3 (C1); 204.8, 206.0,
and 211.4 (Fe(CO)3); 205.9 (C6). IR (Nujol): 1656 (ketone),
1703 and 1756 (ester), 2001, 2015, and 2079 (Fe(CO)3). Anal.
Calcd for C23H28FeO10: C, 53.09; H, 5.42. Found: C, 53.59;
H, 5.54.
J ) 17.6, 10.0 Hz, 1H, H7 21b); 3.25 (dd, J ) 17.5, 10.6 Hz,
1H, H7 22b); 3.69 (s, 3H, CO2Me 21b); 3.69 (s, 3H, CO2Me 22b);
3.88 (td, J ) 10.1, 3.6 Hz, 1H, H8 21b); 3.91 (td, J ) 11, 3.1
Hz, 1H, H8 22b); 5.86-5.99 (m, H3 and H4 21b and 22b); 7.44
(2H, arom 21b and 22b); 7.51 (1H, arom 22b); 7.54 (1H, arom
21b); 7.99 (2H, arom 21b and 22b). 13C NMR (100 MHz,
CDCl3): δ 24.5, 25.1, 30.2, 31.1 (CH2 cyclopentyl 22b); 24.5,
25.1, 30.1 and 31.0 (CH2 21b); 42.8 (CH 22b); 43.0 (CH 21b);
43.7 (C7 21b); 44.0 (C7 22b); 45.4 (C8 22b); 45.7 (C8 21b); 46.5
and 54.3 (C2 and C5 22b); 47.2 and 54.2 (C2 and C5 21b); 51.9
(CO2Me 22b); 51.9 (CO2Me 21b); 84.4 and 86.9 (C3 and C4 22b);
85.0 and 87.0 (C3 and C4 21b); 128.4, 128.4, and 132.6 (CH
arom 22b); 128.5, 128.5 and 132.8 (CH arom 21b); 137.9 (C
arom 21b); 138.1 (C arom 22b); 171.9 (C1 21b); 172.1 (C1 22b);
203.6, 203.7, 203.7, and 203.9 (C6 and C9 21b and 22b); 202.0,
203.2, and 203.3 (Fe(CO)3). IR (Nujol): 1583 and 1603 (arom
and alkene), 1673 (ketone), 1717 (ester), 2005 and 2070 (Fe-
(CO)3). Anal. Calcd for C24H24FeO7: C, 60.02; H, 5.04.
Found: C, 60.65; H, 5.34.
F r om 6c. The reaction yielded, as for 6b, four adducts.
Chromatography allowed the separation of three fractions:
17c, 18c, and a 50/50 unseparable mixture of 21c and 22c.
17c: 13C NMR-DEPT (100 MHz, CDCl3): no CH2 at 39.2 ppm
(C8 f CHD) and one CH at 51.2 ppm (C7). 13C NMR (100 MHz,
CDCl3): modification of the signal at 39.2 ppm into a triplet
(C8 f CHD). 1H NMR (400 MHz, CDCl3): disappearance of
the dd at 2.95 ppm (H8 f D); simplification of the ddd at 3.11
ppm into a dd (J ) 7.9 and 2.0 Hz, H7); simplification of the
dd at 3.64 ppm into a d (J ) 11.2 Hz, H8). 18c: 13C NMR-
DEPT (100 MHz, CDCl3): no CH2 at 39.7 ppm (C8 f CHD)
and one CH at 51.5 ppm (C7). 13C NMR (100 MHz, CDCl3):
Isom er 18a . Yellow oil. Rf ) 0.43 (E/PE 1/1). 1H NMR
(400 MHz, CDCl3): δ 1.22 (t, J ) 7.1 Hz, 3H, CO2CH2CH3);
1.27 (t, J ) 7.1 Hz, 3H, CO2CH2CH3); 1.35 (d, J ) 8.3 Hz, 1H,
H2 or H5); 1.54-1.56, 1.60-1.70, 1.72-1.75, and 2.03-2.10
(series of m, 9H, Hcyclopentyl); 1.68 (d, J ) 8.0 Hz, 1H, H2 or
H5); 3.34 (dd, J ) 8.5, 7.7 Hz, 1H, H7); 3.71 (s, 3H, CO2Me);
3.78 (d, J ) 8.9 Hz, 1H, H8); 4.06 to 4.15 (m, 2H, CO2CH2-
CH3); 4.19 (q, J ) 7.1 Hz, 2H, CO2CH2CH3); 5.87 (dd, J ) 8.0,
5.2 Hz, 1H, H3 or H4); 5.96 (dd, J ) 8.2, 5.2 Hz, 1H, H3 or H4).
13C NMR (100 MHz, CDCl3): δ 14.0 and 14.2 (CO2CH2CH3);
24.6, 24.7, 30.1 and 30.2 (CH2 cyclopentyl); 41.2 (CH cyclo-
pentyl); 46.7 and 57.5 (C2 and C5); 52.0 (CO2Me); 54.5 and 54.6
(C7 and C8); 61.7 and 61.8 (CO2CH2CH3); 86.6 and 87.8 (C3
and C4); 168.3 and 168.7 (CO2Et); 172.0 (C1); 205.5, 205.6, and
211.4 (Fe(CO)3); 207.0 (C6). IR (Nujol): 1663 (ketone), 1705
and 1733 (ester), 1998, 2012 and 2070 (Fe(CO)3). Anal. Calcd
for C23H28FeO10: C, 53.09; H, 5.42. Found: C, 53.15; H, 5.89.
fr om 6b. To a solution of olefin 6b (300 mg; 0.73 mmol),
cyclopentyl bromide (1.2 equiv; 120 µL), and a crystal of AIBN
in dry toluene (25 mL) at 75 °C was added via syringe pump
a solution of cyclopentyl bromide (275 µL; 3.5 equiv), tris-
(trimethylsilyl)silane (270 µL; 1.2 equiv), and a crystal of AIBN
in dry toluene (35 mL) over a 5 h period. After 1 h 30 min of
stirring, toluene was removed in vacuo. Chromatography of
the residual oil (elution with ether/petroleum ether 2/8)
allowed the separation of three fractions: 17b, 18b, and a 50/
50 unseparable mixture of 21b and 22b (59%; 17b/18b/21b/
22b ) 19/14/13/13).
Isom er 17b. Mp: 131 °C (from ether). Rf ) 0.58 (E/PE
1/1). 1H NMR (400 MHz, CDCl3): δ 1.16-1.31 (m, 4H, CH2
cyclopentyl); 1.34 (d, J ) 7.6 Hz, 1H, H2 or H5); 1.44-1.60 (m,
2H, CH2 cyclopentyl); 1.67 (d, J ) 7.6 Hz, 1H, H2 or H5); 1.70-
1.83 (m, 2H, CH2 cyclopentyl); 1.88-1.98 (m, 1H, CH cyclo-
pentyl); 2.95 (dd, J ) 17.8, 2.5 Hz, 1H, H8); 3.11 (ddd, J )
10.7, 8.1, 2.5 Hz, 1H, H7); 3.64 (dd, J ) 18.1, 10.6 Hz, 1H, H8);
3.71 (s, 3H, CO2Me); 5.94 (dd, J ) 7.4, 5.1 Hz, 1H, H3 or H4);
5.98 (dd, J ) 7.9, 5.1 Hz, 1H, H3 or H4); 7.43 (2H, arom); 7.53
(1H, arom); 7.95 (2H, arom). 13C NMR (100 MHz, CDCl3): δ
24.3, 25.2, 30.5, 31.4 (CH2 cyclopentyl); 39.2 (C8); 42.7 (CH
cyclopentyl); 46.0 and 55.9 (C2 and C5); 51.2 and 51.9 (C7 and
CO2Me); 85.6 and 86.4 (C3 and C4); 128.0, 128.4, and 132.9
(CH arom); 136.9 (C arom); 172.3 (C1); 198.4 and 207.5 (C6
and C9); 204.6, 206.0, and 212.0 (Fe(CO)3). IR (Nujol): 1563
and 1599 (low, arom and alkene), 1665 and 1689 (ketone), 1721
(ester), 1987, 2014, and 2068 (Fe(CO)3). Anal. Calcd for
C24H24FeO7: C, 60.02; H, 5.04. Found: C, 60.13; H, 5.25.
Isom er 18b. Rf ) 0.53 (E/PE 1/1). 1H NMR (400 MHz,
CDCl3): δ 1.16-1.28 (m, 1H, CH2 cyclopentyl); 1.29-1.42 (m,
1H, CH2 cyclopentyl); 1.39 (d, J ) 7.9 Hz, 1H, H2 or H5); 1.46-
1.66 and 1.67-1.78 (m, 5H, CH2 cyclopentyl); 1.74 (d, J ) 7.3
Hz, 1H, H2 or H5); 1.79-1.91 (m, 1H, CH2 cyclopentyl); 2.19-
2.31 (m, 1H, CH cyclopentyl); 3.08 (dd, J ) 18.0, 3.0 Hz, 1H,
H8); 3.20 (ddd, J ) 9.9, 7.4, 2.7 Hz, 1H, H7); 3.51 (dd, J ) 18.0,
10.1 Hz, 1H, H8); 3.71 (s, 3H, CO2Me); 5.90 (dd, J ) 8.1, 5.6
Hz, 1H, H3 or H4); 6.02 (dd, J ) 8.2, 5.2 Hz, 1H, H3 or H4);
7.45 (2H, arom); 7.56 (1H, arom); 7.92 (2H, arom). 13C NMR
(100 MHz, CDCl3): δ 25.0, 25.3, 29.5, 31.3 (CH2 cyclopentyl);
39.7 (C8); 41.9 (CH cyclopentyl); 46.8 and 56.2 (C2 and C5); 51.5
and 52.0 (C7 and CO2Me); 86.7 and 87.3 (C3 and C4); 128.1,
128.6, and 133.3 (CH arom); 136.5 (C arom); 172.0 (C1); 198.8
and 208.8 (C6 and C9). IR (Nujol): 1598 (low, arom and
alkene), 1675 (ketone), 1707 (ester), 2001 and 2069 (Fe(CO)3).
Isom er s 21b a n d 22b. Rf ) 0.45 (E/PE 1/1). 1H NMR (400
MHz, CDCl3): δ 1.01 to 1.30 (m, CH2 cyclopentyl); 1.35 (d, J
) 8.1 Hz, 1H, H5 22b); 1.38 (d, J ) 8.1 Hz, 1H, H5 21b); 1.43-
1.65 (m, 4H, CH2 cyclopentyl); 1.52 (d, J ) 8.0 Hz, 2H, H2 21b
and H2 22b); 1.67-1.80 (m, 1H, CH cyclopentyl 21b); 1.93-
2.08 (m, 1H, CH cyclopentyl 22b); 2.64 (dd, J ) 17.8, 3.6 Hz,
1H, H7 22b); 2.68 (dd, J ) 17.8, 3.6 Hz, 1H, H7 21b); 3.24 (dd,
modification of the signal at 39.7 ppm into a triplet (C8
f
CHD). 1H NMR (400 MHz, CDCl3): disappearance of the dd
at 3.08 ppm (H8 f D); simplification of the ddd at 3.20 ppm
into a dd (J ) 10.1 and 7.8 Hz, H7); simplification of the dd at
3.48 ppm into a d (J ) 9.8 Hz, H8). 19c and 20c: 13C NMR-
DEPT (100 MHz, CDCl3): no modification of the CH2 at 43.7
and 44.0 ppm (C7). 13C NMR (100 MHz, CDCl3): modification
of the signals at 45.4 and 45.7 ppm into triplets (C8 f CHD).
1H NMR (400 MHz, CDCl3): simplification of the dd at 2.64
and 2.68 ppm into d (J ) 17.8 Hz, H7); simplification of the dd
at 3.24 and 3.25 ppm into d (J ) 17.7 Hz, H7); disappearance
of the dd at 3.88 and 3.91 ppm (H8 f D).
Hyd r id e Red u ction of 6d . To a stirred solution of 6d (150
mg; 0.41 mmol) in MeOH/CH2Cl2 (10 mL/5 mL) at -30 °C was
added NaBH4 (15 mg; 1 equiv) in one portion. The reaction
mixture was allowed to warm to 0 °C in 30 min and then
hydrolyzed and extracted with ether. The separated organic
layer was washed with water, dried (MgSO4), and evaporated.
Purification of the crude product yielded 23d (130 mg; 86%)
as a yellow solid. 23d : Mp: 112 °C (from ether). Rf ) 0.18
(E/PE 1/1). 1H NMR (400 MHz, CDCl3): δ 0.99 (d, J ) 8.2
Hz, 1H, H2); 1.23 (t, J ) 7.6 Hz, 1H, H5); 2.34 (d, J ) 3.6 Hz,
1H, OH); 3.67 (s, 3H, CO2Me); 3.77 (s, 3H, CO2Me); 4.33 (m,
1H, H6); 5.45 (dd, J ) 8.4, 5.1 Hz, 1H, H3); 5.85 (dd, J ) 7.8,
5.3 Hz, 1H, H4); 6.04 (d, J ) 15.9 Hz, 1H, H8); 6.96 (dd, J )
15.6, 5.0 Hz, 1H, H7). 13C NMR (100 MHz, CDCl3): δ 46.0
and 65.1 (C2 and C5); 51.8 and 51.9 (CO2Me); 72.1 (C6); 83.5
and 83.8 (C3 and C4); 118.6 (C8) and 148.8 (C7); 166.7 and 172.5
(C1 and C9). IR (Nujol): 1660 (alkene); 1691 (ketone); 1708
(ester); 1972, 1997, and 2048 (Fe(CO)3). Anal. Calcd for
C14H14FeO8: C, 45.93, H, 3.85. Found: C, 45.96, H, 3.85.
Gen er a l P r oced u r e for th e Decom p lexa tion of Ad -
d u cts 24a , 25a ,b, a n d 26-31. To a stirred solution of the
corresponding complex in a mixture of MeOH/CH2Cl2 was
added, under N2 at -15 °C, ammonium cerium nitrate (10
equiv). The reaction mixture was stirred for 45 min and
allowed to rise up to room temperature, before addition of
water and extraction with ether. The separated organic layer
was washed with water, dried (MgSO4), and evaporated in
vacuo. Chromatography of the residual oil (elution with ether/
petroleum ether 4/6) yielded the desired dienes 24 (except 24b)
to 31.
Dien e 24a . 69% yield from 10a or 11a . 24a . Rf ) 0.33
(E/PE 1/1). 1H NMR (400 MHz, CDCl3): δ 1.21 (t, J ) 7.2 Hz,
3H, CO2CH2CH3); 1.25 (t, J ) 7.1 Hz, 3H, CO2CH2CH3); 1.58

Synthesis of Cross-Conjugated Polyenones
J . Org. Chem., Vol. 61, No. 15, 1996 5071
(s, 3H, Me); 1.65 (s, 3H, Me); 2.20 (broad d, J ) 18.5 Hz, 1H,
MHz, CDCl3): δ 47.0 and 50.0 (C7 and C8); 52.0 (CO2Me); 56.3,
57.6, and 59.3 (CH2); 127.2, 128.3, 128.6, 128.7, 128.7, and
129.0 (CH arom); 133.4, 134.4, 139.6, and 141.3 (C2 to C5);
135.9 and 138.1 (C arom); 166.2 (C1); 198.6 and 199.1 (C6 and
C9). IR (Nujol): 1596 (arom and alkene), 1682 (ketone), 1713
(ester). Anal. Calcd for C25H25NO4: C, 74.42; H, 6.24; N, 3.47.
Found: C, 74.06; H, 6.15; N, 3.36.
Dien e 28. 89% yield from 15b or 16b. 28. Mp: 110 °C
(from hexane/ethyl acetate). Rf ) 0.41 (E/PE 1/1). 1H NMR
(400 MHz, CDCl3): δ 2.34 (s, 3H, Me); 3.38 (dd, J ) 17.8, 4.6
Hz, 1H, H8); 3.70 (dd, J ) 17.8, 9.1 Hz, 1H, H8); 3.79 (s, 3H,
CO2Me); 4.37 (dd, J ) 9.4, 4.6 Hz, 1H, H7); 6.21 (d, J ) 15.3
Hz, 1H, H2 or H5); 6.80 (d, J ) 14.8 Hz, 1H, H2 or H5); 7.13
(2H, arom); 7.25 (dd, J ) 14.7, 11.2 Hz, 1H, H3 or H4); 7.30
(2H, arom); 7.37 (dd, J ) 15.2, 11.2 Hz, 1H, H3 or H4); 7.45
(2H, arom); 7.56 (1H, arom); 7.92 (2H, arom). 13C NMR (100
MHz, CDCl3): δ 21.2 (Me); 39.7 (C8); 50.4 and 51.9 (C7 and
CO2Me); 126.9, 133.5, and 139.7 (C arom); 128.1, 128.5, 128.6,
130.1, 133.5, 134.3, 135.1, 139.1, and 141.6 (C2 to C5 and CH
arom); 166.4 (C1); 193.0 and 197.2 (C6 and C9). IR (Nujol):
1594 (alkene and arom); 1677 and 1690 (ketone); 1708 (ester).
Anal. Calcd for C23H22O4S: C, 70.03; H, 5.62. Found: C,
69.55; H, 5.62.
Dien e 30. 85% yield from 19b and 20b. 30. Rf ) 0.51 (E/
PE 1/1). 1H NMR (400 MHz, CDCl3): δ 2.31 (s, 3H, Me); 3.09
(dd, J ) 17.8, 4.6 Hz, 1H, H7); 3.77 (s, 3H, CO2Me); 3.81 (m,
1H, H7); 4.96 (dd, J ) 9.1, 4.6 Hz, 1H, H8); 6.11 (d, J ) 14.7
Hz, 1H, H2 or H5); 6.65 (d, J ) 14.2 Hz, 1H, H2 or H5); 7.13
(2H, arom); 7.25 (dd, J ) 14.7, 11.2 Hz, 1H, H3 or H4); 7.30
(2H, arom); 7.37 (dd, J ) 15.2, 11.2 Hz, 1H, H3 or H4); 7.45
(2H, arom); 7.56 (1H, arom); 7.92 (2H, arom). 13C NMR (100
MHz, CDCl3): δ 21.2 (Me); 42.1 (C8); 51.0 and 51.8 (C7 and
CO2Me); 127.8, 135.5, and 140.0 (C arom); 128.1, 128.5, 128.6,
130.1, 133.5, 134.3, 135.1, 139.1, and 141.6 (C2-C5 and CH
arom); 166.6 (C1); 193.5 and 195.0 (C6 and C9). IR (film): 1592
(alkene and arom); 1682 and 1702 (ketone); 1714 (ester). High-
resolution mass spectrum for C23H22O4S: calcd 394.1239, found
394.1261.
Dien e 29. 64% yield from 17b or 18b. 29: Rf ) 0.51 (E/
PE 1/1). 1H NMR (400 MHz, CDCl3): δ 1.17-1.29, 1.49-1.59,
1.63-1.72, 1.79-1.90, and 1.93-2.03 (series of m, 9H, H
cyclopentyl); 3.18 (dd, J ) 18.1, 3.0 Hz, 1H, H8); 3.30 (td, J )
10.7, 3.0 Hz, 1H, H7); 3.68 (dd, J ) 18.1, 10.4 Hz, 1H, H8);
3.81 (s, 3H, CO2Me); 6.25 (d, J ) 15.1 Hz, 1H, H2 or H5); 6.69
(d, J ) 15.1 Hz, 1H, H2 or H5); 7.27 (dd, J ) 15.1, 11.7 Hz,
1H, H3 or H4); 7.39 (dd, J ) 15.0, 11.7 Hz, 1H, H3 or H4); 7.45
(2H, arom); 7.56 (1H, arom); 7.94 (2H, arom). 13C NMR (100
MHz, CDCl3): δ 24.4, 25.2, 30.8, and 31.1 (CH2 cyclopentyl);
40.9 (C8); 42.7 (CH cyclopentyl); 49.8 (C7); 51.9 (CO2Me); 128.1,
128.3, and 128.6 (CH arom); 133.3, 136.6, 137.9, and 142.0
(C2-C5); 136.3 (C arom); 166.4 (C1); 198.8 and 202.9 (C6 and
C9). IR (film): 1582 and 1598 (alkene and arom), 1682
(ketone), 1722 (ester). High-resolution mass spectrum for ion
C19H21O2: calcd 281.1541, found 281.1438.
H
12); 2.49 (dd, J ) 18.3, 7.7 Hz, 1H, H12); 2.65 (d, J ) 17.3 Hz,
1H, H9); 2.80 (d, J ) 17.3 Hz, 1H, H9); 3.68 (m, 1H, H7); 3.78
(s, 3H, CO2Me); 4.15 (q, J ) 7.1 Hz, 2H, CO2CH2CH3); 4.20 (q,
J ) 7.1 Hz, 2H, CO2CH2CH3); 6.23 (d, J ) 15.0 Hz, 1H, H2 or
H5); 6.62 (d, J ) 14.9 Hz, 1H, H2 or H5); 7.23 (dd, J ) 15.1,
11.5 Hz, 1H, H3 or H4); 7.34 (dd, J ) 14.9, 11.5 Hz, 1H, H3 or
H4). 13C NMR (100 MHz, CDCl3): δ 13.9 and 14.0 (CO2-
CH2CH3); 18.7 and 19.0 (Me); 34.2 and 35.0 (CH2); 48.2 (C7);
51.9 (CO2Me); 55.6 (C8); 61.5 and 61.8 (CO2CH2CH3); 121.4 and
124.5 (MeCdCMe); 128.6, 133.8, 138.8, and 141.5 (C2 to C5);
166.4 (C1); 170.1 and 170.7 (CO2Et); 198.6 (C6). IR (film): 1597
(alkene), 1692 (ketone), 1729 (ester). Anal. Calcd for
C
21H28O7: C, 64.24; H, 7.19. Found: C, 64.24; H, 7.34.
Dien e 25a . 65% yield from 13a or 14a . 25a . Rf ) 0.38
(E/PE 1/1). 1H NMR (400 MHz, CDCl3): δ 1.14 (t, J ) 7.1 Hz,
3H, CO2CH2CH3); 1.25 (t, J ) 7.1 Hz, 3H, CO2CH2CH3); 2.67
(dd, J ) 9.2, 7.6 Hz, 1H, H10); 3.17 (broad t, J ) 8.7 Hz, 1H,
H10); 3.20 (d, J ) 9.8 Hz, 1H, H9); 3.31 (d, J ) 9.8 Hz, 1H, H9);
3.65 (s, 2H, NCH2Ph); 3.78 (s, 3H, CO2Me); 4.00-4.12 (m, 2H,
CO2CH2CH3); 4.25 (q, J ) 7.1 Hz, 2H, CO2CH2CH3); 4.33 (t, J
) 7.7 Hz, H7); 6.25 (d, J ) 14.7 Hz, 1H, H2 or H5); 6.55 (d, J
) 14.8 Hz, 1H, H2 or H5); 7.22-7.34 (m, 7H, H3 and H4 and
arom).13C NMR (100 MHz, CDCl3): δ 13.8 and 14.0 (CO2-
CH2CH3); 52.0 (CO2Me); 53.2 (C7); 55.9, 59.0, and 60.1 (CH2);
61.7 and 62.3 (CO2CH2CH3); 62.8 (C8); 127.1, 128.3, 128.4,
129.0, 135.2, 139.2, and 141.4 (C2 to C5 and CH arom); 138.4
(C arom); 166.2, 168.5, and 170.4 (C1 and CO2Et); 197.7 (C6).
IR (film): 1597 (arom and alkene), 1670 (ketone), 1697 and
1729 (ester). Anal. Calcd for C24H29NO7: C, 65.00; H, 6.59.
Found: C, 65.04; H, 6.78.
Dien e 26. 97% yield from 15a or 16a . 26. Mp: 142 °C
(from ethyl acetate). Rf ) 0.35 (E/PE 1/1). 1H NMR (400 MHz,
CDCl3): δ 1.19 (t, J ) 7.1 Hz, 3H, CO2CH2CH3); 1.37 (t, J )
7.1 Hz, 3H, CO2CH2CH3); 2.33 (s, 3H, Me); 3.80 (s, 3H, CO2Me);
3.91 (d, J ) 11.7 Hz, 1H, H7 or H8); 4.12 (q, J ) 7.1 Hz, 2H,
CO2CH2CH3); 4.31-4.39 (m, 2H, CO2CH2CH3); 4.33 (d, J )
11.7 Hz, 1H, H7 or H8); 6.21 (d, J ) 15.2 Hz, 1H, H2 or H5);
6.76 (d, J ) 15.2 Hz, 1H, H2 or H5); 7.12 (2H, arom); 7.22 (dd,
J ) 15.1, 11.5 Hz, 1H, H3 or H4); 7.29 (2H, arom); 7.37 (dd, J
) 15.2, 11.5 Hz, 1H, H3 or H4). 13C NMR (100 MHz, CDCl3):
δ 13.9 and 14.2 (CO2CH2CH3); 21.3 (Me); 52.0 (CO2Me); 52.7
and 53.9 (C7 and C8); 62.1 and 62.1 (CO2CH2CH3); 125.2 and
140.2 (C arom); 128.8, 133.9, 139.5, and 141.4 (C2 to C5); 130.2
and 135.9 (CH arom); 166.1 (C1); 167.3 and 167.3 (CO2Et);
191.0 (C6). IR (Nujol): 1597 (alkene and arom); 1682 (ketone);
1708 and 1730 (ester). Anal. Calcd for C22H26O7S: C, 60.81;
H, 6.03. Found: C, 60.76; H, 6.18.
Dien e 27. 78% yield from 17a or 18a . 27. Mp: 108 °C
(from ether). Rf ) 0.37 (E/PE 1/1). 1H NMR (400 MHz,
CDCl3): δ 1.20 (t, J ) 7.1 Hz, 3H, CO2CH2CH3); 1.29 (t, J )
7.1 Hz, 3H, CO2CH2CH3); 1.14-1.24, 1.36-1.50, 1.52-1.61,
and 1.62-1.80 (m, 8H, CH2 cyclopentyl); 1.86-2.02 (m, 1H,
CH cyclopentyl); 3.58 (dd, J ) 10.2, 7.1 Hz, 1H, H7); 3.79 (s,
3H, CO2Me); 3.93 (d, J ) 10.2 Hz, 1H, H8); 4.05-4.16 (m, 2H,
CO2CH2CH3); 4.23 (q, J ) 7.1 Hz, 2H, CO2CH2CH3); 6.26 (d,
J ) 15.3 Hz, 1H, H2 or H5); 6.60 (d, J ) 15.3 Hz, 1H, H2 or
H5); 7.22 (dd, J ) 15.3, 11.4 Hz, 1H, H3 or H4); 7.35 (dd, J )
15.3, 11.4 Hz, 1H, H3 or H4). 13C NMR (100 MHz, CDCl3): δ
13.9 and 14.0 (CO2CH2CH3); 24.2, 24.5, 28.8, and 30.8 (CH2
cyclopentyl); 41.7 (CH cyclopentyl); 52.0 (CO2Me); 51.9 and 54.7
(C7 and C8); 61.5 and 61.8 (CO2CH2CH3); 128.7, 136.8, 138.1,
and 141.7 (C2-C5); 166.3 (C1); 168.4 and 168.8 (CO2Et); 200.7
(C6). IR (Nujol): 1591 (alkene); 1684 (ketone); 1728 (ester).
Anal. Calcd for C20H28O7: C, 63.14; H, 7.42. Found: C, 63.01;
H, 7.32.
Dien e 31. 90% yield from 21b and 22b. 30: Rf ) 0.39 (E/
PE 1/1). 1H NMR (400 MHz, CDCl3): δ 1.06-1.15, 1.21-1.30,
1.41-1.59, 1.63-1.82, and 1.94-2.07 (series of m, 9H, H
cyclopentyl); 2.84 (dd, J ) 17.8, 3.1 Hz, 1H, H7); 3.43 (dd, J )
17.8, 10.2 Hz, 1H, H7); 3.77 (s, 3H, CO2Me); 3.93 (td, J ) 10.7,
3.0 Hz, 1H, H8); 6.22 (d, J ) 15.3 Hz, 1H, H2 or H5); 6.43 (d,
J ) 15.3 Hz, 1H, H2 or H5); 7.17 (dd, J ) 15.3, 11.2 Hz, 1H,
H3 or H4); 7.28 (dd, J ) 15.3, 11.2 Hz, 1H, H3 or H4); 7.47 (2H,
arom); 7.56 (1H, arom); 8.04 (2H, arom). 13C NMR (100 MHz,
CDCl3): δ 24.4, 25.1, 30.4, and 31.1 (CH2 cyclopentyl); 42.7
(C8); 43.0 (CH cyclopentyl); 45.3 (C7); 51.9 (CO2Me); 128.5 and
128.7 (CH arom); 132.8, 135.1, 138.6, and 141.5 (C2 to C5);
138.0 (C arom); 166.2 (C1); 198.6 and 203.9 (C6 and C9). IR
(film): 1598 (alkene and arom), 1679 (ketone), 1728 (ester).
High-resolution mass spectrum for C21H24O4: calcd 340.1674,
found 340.1672.
Dien e 25b. 64% yield from 13b or 14b. 25b. Mp: 110 °C
(from ethyl acetate). Rf ) 0.21 (E/PE 1/1). 1H NMR (400 MHz,
CDCl3): δ 2.73 (dd, J ) 9.2, 6.6 Hz, 1H, CH2); 2.83 (dd, J )
9.7, 5.7 Hz, 1H, CH2); 2.98 (t, J ) 9.2 Hz, 1H, CH2); 3.13 (t, J
) 9.2 Hz, 1H, CH2); 3.62 (s, 2H, NCH2Ph); 3.77 (s, 3H, CO2Me);
4.07 (dt, J ) 8.6, 5.6 Hz, 1H, H7 or H8); 4.45 (dt, J ) 8.6, 6.1
Hz, 1H, H7 or H8); 6.18-6.28 (m, 1H, H2 or H3); 6.43-6.51 (m,
1H, H2 or H5); 7.22-7.31 (m, 7H, H3 and H4 and arom); 7.45
(2H, arom); 7.56 (1H, arom); 7.95 (2H, arom). 13C NMR (100
Dien e 24b. A solution of trimethylamine N-oxide dihydrate
(300 mg; 15 equiv) in CH2Cl2 (20 mL) was refluxed in the
presence of molecular sieves (4 Å). After 30 min, 10 mL of
this solution was added under N2 at room temperature to a
stirred solution of 10b or 11b (110 mg; 0.22 mmol) in CH2Cl2

5072 J . Org. Chem., Vol. 61, No. 15, 1996
Marchand et al.
(20 mL). The reaction mixture was refluxed in the presence
of molecular sieves (4 Å) for 1 h 30 min and then allowed to
cool to room temperature, quenched with water, and extracted
with dichloromethane. The separated organic layer was
washed with water, dried (MgSO4), and concentrated in vacuo.
Chromatography of the residual oil (elution with ether/
petroleum ether 3/7) yielded 24b (62 mg; 80%) as an oil. 24b.
Rf ) 0.33 (E/PE 3/7). 1H NMR (400 MHz, CDCl3): δ 1.63 (s,
3H, Me); 1.68 (s, 3H, Me); 1.98-2.15 (m, 2H, CH2); 2.32 (broad
d, J ) 16.5 Hz, 2H, CH2); 3.45 to 3.52 (m, 1H, H7); 3.78 (s, 3H,
CO2Me); 3.93 (td, J ) 11.2, 5.6 Hz, 1H, H8); 6.23 (d, J ) 14.8
Hz, 1H, H2 or H5); 6.58 (d, J ) 15.3 Hz, 1H, H2 or H5); 7.24
(dd, J ) 15.0, 10.8 Hz, 1H, H3 or H4); 7.35 (dd, J ) 15.2, 11.2
Hz, 1H, H3 or H4); 7.46 (2H, arom); 7.56 (1H, arom); 7.98 (2H,
arom). 13C NMR (100 MHz, CDCl3): δ 18.7 and 19.0 (Me);
34.6 and 35.8 (CH2); 44.3 (C8); 47.4 (C7); 51.9 (CO2Me); 124.3
and 124.7 (MeCdCMe); 128.5, 128.6, and 128.6 (CH arom);
133.1, 134.9, 138.8, and 141.8 (C2 to C5); 136.2 (C arom); 166.3
(C1); 202.4 and 203.2 (C6 and C9). IR (film): 1596 (arom
and alkene), 1682 (ketone), 1713 (ester). Anal. Calcd for
C22H24O4: C, 74.98; H, 6.86. Found: C, 75.05; H, 7.25.
Ack n ow led gm en t. We thank Dr. Y. Rolland (Insti-
tut de Recherches Servier, Suresnes) for very fruitful
discussions and Drs. M. Amm and J . P. Volland (IdRS)
for the microanalyses. Mrs. Roc-Schneider and Labo-
ratoires Servier are acknowledged for financial support.
J O9603643