Synthesis of 2,4-furanophanes by palladium-catalyzed macrocyclization reactions of 1,n-diallenyl diketones

Article abstract of DOI:10.1002/ejoc.200300792

The 1,n-diallenyl diketones 8a-j were prepared and subjected to reactions with the [PdCl₂(MeCN)₂] catalyst. Upon decreasing the length of the bridge between the allenyl ketone units, first we obtained the (E) isomer 10 as the macrocy

Full text of DOI:10.1002/ejoc.200300792

FULL PAPER
Synthesis of 2,4-Furanophanes by Palladium-Catalyzed Macrocyclization
Reactions of 1,n-Diallenyl Diketones
A. Stephen K. Hashmi,*[a] Lothar Schwarz,[b] and Michael Bolte[b][‡]
Keywords: Cyclophanes / Heterocycles / Homogeneous catalysis / Macrocycles / Palladium
The 1,n-diallenyl diketones 8a−j were prepared and sub-
jected to reactions with the [PdCl2(MeCN)2] catalyst. Upon configuration of the double bond. The ring closure of a furan
decreasing the length of the bridge between the allenyl ke- derivative, having vinyl groups in its substituents at the 2-
tone units, first we obtained the (E) isomer 10 as the macro- and 4-positions, to a related product by Ru-catalyzed olefin
rocycles 21a, 21b, 26a, and 26b with only the expected (E)
cyclic product and then the (Z) isomer 11 accompanied by
the exocyclic double bond isomer 12. In all cases, the open-
metathesis delivered yields similar to the Pd-catalyzed mac-
rocyclization, but provided a mixture of both double bond
chained 1,n-difuryl alkanes were isolated as side-products. isomers.
The analogous preparation and conversion of the diallenyl
diketones 19 and 24, which have even longer bridges and
( Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
ether-functionalities, delivered the 20- to 52-membered mac-
Germany, 2004)
Introduction
We have described the palladium-catalyzed cycloiso-
merization/dimerization of allenyl ketones 1, which, apart
from CϪO bond formation, also involves CϪC bond
formation.[28Ϫ32] Under optimized conditions, 3 was the
major product, accompanied by small amounts of 2. It was
only during early experiments under non-optimized con-
ditions that we observed some 4 as a side-product; we never
observed compound 5, the (Z) isomer of 3.
We were interested in investigating whether this CϪC
bond formation can, in principle, be used for the synthesis
of macrocyclic furanophanes from open-chained diallenyl
diketones as precursors.
The field of furanophanes is dominated by macrocycles
that contain several heterocyclic units;[1Ϫ7] in most cases,
several furans are present in a macrocycle obtained from
the condensation of furans with aldehydes or ketones.[8]
Because of the difficulties encountered in their synthesis,
single furan moieties in furanophanes are quite rare. Recent
examples of such systems having 2,5-bridging are found in
model studies toward the total syntheses of chatancin[9Ϫ11]
and eleutherobin.[12] There are other synthetic targets feat-
uring 2,4-bridging that have aroused interest in furan-
ophanes having only one furan unit; for example, a class
of furanocembrenoids found in ant venoms is of biological
importance.[13] The silver-catalyzed isomerization of allenyl
ketones 1 to furans 2[14Ϫ20] has been utilized successfully by
Marshall et al. for the synthesis of macrocyclic furans.[21]
In these reactions, the allenyl ketone was already part of a
macrocycle; the isomerization had the character of a ring-
contraction reaction, adding strain to the macrocycle
through the 2,5-bridging of the furan system. Similar struc-
tural motifs can be found in natural products, such as lo-
photoxin,[22] or have been prepared by other methods.[23Ϫ27]
[a]
Institut für Organische Chemie, Universität Stuttgart
Pfaffenwaldring 55, 70569 Stuttgart, Germany
Fax:(internat.) ϩ49-(0)711-685-4321
E-mail: hashmi@hashmi.de
[b]
Institut für Organische Chemie und Chemische Biologie,
Johann Wolfgang Goethe-Universität Frankfurt am Main
Marie-Curie-Straße 11, 60439 Frankfurt, Germany
Crystallographic investigation.
[‡]
Scheme 1. Different furans obtained from allenyl ketones
Eur. J. Org. Chem. 2004, 1923Ϫ1935
DOI: 10.1002/ejoc.200300792
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
1923

A. S. K. Hashmi, L. Schwarz, M. Bolte
FULL PAPER
Results and Discussion
ophanes 12, each having an exocyclic double bond; this type
of product has been observed only in early investigations of
the intermolecular coupling of allenyl ketones,[28] but had
never formed when the [PdCl2(MeCN)2] catalyst was ap-
plied.[30]
Bidirectional synthesis delivered the 1,n-diallenyl dike-
tones 8. Starting from dialkyl 1,n-alkanedicarboxylates 6, a
DIBALH reduction at Ϫ78 °C and a subsequent reaction of
the 1,n-alkanedialdehydes with allenylmagnesium bromide
The results depend strongly on the length of the tether
delivered the bis(homopropargylic alcohol)s 7 as mixtures between the carbonyl groups. With a short bridge of only
of diastereoisomers, which, because of the 4Ϫ14 atoms be- four or five CH2 units, no macrocycles were formed
tween the stereogenic centers, do not exhibit significantly (Scheme 2, Entries 1 and 2). The yield of 9 corresponds to
different spectroscopic data. The latter compounds were ox- the yield of the analogous monosubstituted furans obtained
idized to 8 using the DessϪMartin periodinane[33Ϫ37] re- in the intermolecular reactions of simple allenyl ketones
agent (this step includes a subsequent isomerization of the with the [PdCl2(MeCN)2] catalyst.[30] A bridge of sixϪeight
propargyl to the allenyl ketone during the workup[38]).
methylene units (Entries 3Ϫ5) lead to only a very small
Then solutions of 8 (0.125 ) in acetonitrile were slowly amount of 10; 11 was the major product and the proportion
added to a solution of the [PdCl2(MeCN)2] catalyst in of 12 increased sequentially over these three Entries. The
about the same volume of acetonitrile. The results are listed different products could be differentiated conveniently by
1
in Scheme 1. Four different non-oligomeric/ non-polymeric their H NMR spectra. The allylic methyl group of 10 ap-
products were isolated: (a) The 1,n-difurylalkanes 9 formed pears at δ ϭ 2.3Ϫ2.4 ppm while the same signal for 11 is
by Marshall reactions[21Ϫ27] at both ends of the chain. (b) found at δ ϭ 2.0Ϫ2.1 ppm; 12 is characterized by a singlet
The furanophanes 10, each having an (E) configuration of at δ ϭ 3.3Ϫ3.4 ppm. When n ϭ 9 (Entry 6), we obtained
the olefin in the bridge. These compounds correspond to more of 10 and less of 11, while the amount of 12 still in-
the known products from Pd-catalyzed intermolecular creased. With ten and eleven CH2 units (Entries 7 and 8),
coupling of allenyl ketones.[28Ϫ32] (c) The furanophanes 11, this trend remained for 9: together with 10, it was the major
each possessing a (Z) configuration of the olefin in the product, while the amounts of 11 and 12 decreased sharply.
bridge; such (Z) olefins have never been observed pre- When n ϭ 12 and 14 (Entries 9 and 10), 10 was the only
viously in such intermolecular couplings. (d) The furan- macrocycle observed. In Entries 3Ϫ10, the amount of 9 was
Scheme 2. Synthesis and palladium-catalyzed cyclization of 1,n-diallenyl diketones 8aϪj
1924
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
Eur. J. Org. Chem. 2004, 1923Ϫ1935

Synthesis of 2,4-Furanophanes by Palladium-Catalyzed Macrocyclization Reactions
FULL PAPER
higher than it was in the first Entries (7Ϫ16%). Apart from
the first four Entries, the sum of the yields of macrocycles bidirectional synthesis. The precursors 15 and 16 were syn-
was between 27 and 38%. thesized from the benzyl bromide 13 and the diols 14
Next, we explored even larger rings. Again, we used a
How can these results be explained? For long bridges, the (Scheme 3).
meta bridging of the furan ring and the (E) configuration
of the double bond in this bridges are tolerated without
serious difficulties being encountered. Fortunately, we were
able to obtain crystals from the 16-membered ring of 10g
(n ϭ 10) that were suitable for X-ray crystallographic inves-
tigation (Figure 1).[39] The furan ring and the neighboring
carbon atoms are coplanar; no unusual bond lengths or
angles are observed.
Figure 1. X-ray crystal structure of the furanophane 10g (ORTEP
plot)
Scheme 3. Synthesis of the 1,n-diols 15 and 16
With n ϭ 9, the strain seemed to increase: the double
bond geometry in the bridge switches to the (Z) configura-
tion and some of the exocyclic olefin is formed. We ob-
tained an X-ray crystal structure of the twelve-membered
macrocycle 12c (n ϭ 6, Figure 2).[39] Here, we see that C12
and C4 are bent out of the plane of the furan ring (the ring
itself is planar; the rmsd of the five atoms from the ring
plane is 0.0045 A) by 0.195(4) A (C4) and 0.234 A (C12) in
the direction of the bridge, which reflects the strain
originating from the 2,4-bridging of the furan ring.
Swern oxidation of 15 delivered 17 (Scheme 4), and the
dialdehydes 22 were obtained from 16 (Scheme 5). Addition
of allenylmagnesium bromide provided 18 or 23, each as a
mixture of diastereoisomers that, like 7, show practically
identical spectroscopic data because of the 14Ϫ48 spacer
atoms between the stereogenic centers. Finally,
DessϪMartin oxidation led to the diallenyl diketones 19
and 24.
˚
˚
˚
From 19 we obtained the twenty- and thirty-four-mem-
bered 21a and 21b, respectively, and from 24 we obtained
the thirty-one- and fifty-two-membered 26a and 26b,
respectively. Again the Marshall-type products 20 or 25
were isolated in low yields.
How do these yields compare to those obtained from
other macrocyclization methods? One of today’s most
popular methods for macrocyclization is olefin-metath-
esis.[40] Thus, we prepared the divinyl compounds 27 and
subjected it to Grubbs’ [Cl2(PCy3)2RuϭCHϪCϭCPh2]
catalyst. While the reaction with 27a delivered only poly-
meric material, from 27b we obtained only 31% of 28b (the
length of the bridge corresponded to a bridge of 16 methyl-
ene groups) as an (E)/(Z) mixture. This reaction is not an
ideal model for a comparison because of the additional
double bond in 28, but a better one was not readily avail-
able (Scheme 6). Still, the reaction proved the difficulties
encountered in bridging the furan in the 2,4-position and
having an (E) double bond in that bridge.
Figure 2. X-ray crystal structure of the furanophane 12c (ORTEP
plot)
Finally, with n Յ 5, the macrocyclization was no longer
possible.
Compounds 10, 11 and 12 do not interconvert under the
reaction conditions[30] and, thus, the different double bond
geometries are the result of kinetic control — for example,
different regio- and facial selectivities of the ring closing
step — rather than thermodynamic control.
We obtained no evidence of any dynamic behavior from
the NMR spectra of any of the macrocycles reported
herein.[41,42]
Eur. J. Org. Chem. 2004, 1923Ϫ1935
www.eurjoc.org
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
1925

A. S. K. Hashmi, L. Schwarz, M. Bolte
FULL PAPER
Scheme 4. Synthesis and palladium-catalyzed cyclization of the 1,n-diallenyl diketones 19a,b
Scheme 5. Synthesis and palladium-catalyzed cyclization of the 1,n-diallenyl diketones 24a,b
both, in principle, are known from intermolecular versions
of this reaction, we observed a new type of product in the
intramolecular case: the (Z) olefin 11. In the range from
sixteen- to fifty-two-membered macrocycles, the (E) olefins
were the major products.
Experimental Section
1. General Procedure for the Preparation of Homopropargylic Al-
cohols 7: DIBAH solution (1.2 equiv.) was added with stirring to
the ester (1 equiv.) in absolute diethyl ether at Ϫ78 °C over 30 min.
Stirring at Ϫ78 °C was continued for 5 h before a solution of pro-
pargylmagnesium bromide (1.1 equiv.) in diethyl ether was added
at Ϫ78 °C over 15 min; after another 5 min, the solution was
warmed to room temperature. A suspension of NaF (7Ϫ8 equiv.)
in a saturated NH4Cl solution was then added slowly at Ϫ20 °C.
Scheme 6. Ru-catalyzed macrocyclization of the furans 27a,b.
Conclusion
The results of the palladium-catalyzed reaction of the di-
allenyl diketones depend strongly on the length of the
bridge. Besides the products of types 10 and 12, of which Extraction of the aqueous phase three times with diethyl ether, dry-
1926  2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim www.eurjoc.org
Eur. J. Org. Chem. 2004, 1923Ϫ1935

Synthesis of 2,4-Furanophanes by Palladium-Catalyzed Macrocyclization Reactions
FULL PAPER
ing of the combined organic phases over MgSO4, filtration and
evaporation of the solvent in vacuo, and purification of the residue
by column chromatography on silica gel delivered the homopropar-
gylic alcohols 7.
250 MHz): δ ϭ 1.20Ϫ1.59 (m, 16 H), 2.06 (t, J ϭ 2.7 Hz, 2 H),
2.13 (br. s, 2 H), 2.31 (ddd, J ϭ 2.7, 6.6, 16.7 Hz, 2 H), 2.44 (ddd,
J ϭ 2.6, 4.8, 16.7 Hz, 2 H), 3.70Ϫ3.80 (m, 2 H) ppm. 13C NMR
(CDCl3, 62.9 MHz): δ ϭ 25.38 (t, 2 C), 27.18 (t, 2 C), 29.27 (t, 2
C), 29.30 (t, 2 C), 36.03 (t, 2 C), 69.70 (d, 2 C), 70.59 (d, 2 C),
80.84 (s, 2 C) ppm. IR (neat): ν˜ ϭ 3404 (ϪOH), 3283 (ϵCϪH),
2913, 2848, 2114 (CϵC) cmϪ1. MS (70 eV): m/z (%) ϭ 211 (16) [M
Ϫ C3H3]ϩ, 171 (37), 133 (18), 119 (17), 109 (39), 95 (100), 81 (94),
67 (66), 55 (60). C16H26O2 (250.38): calcd. C 76.75, H 10.47; found
C 76.88, H 10.52.
7a: Diethyl adipate (2.02 g, 10.0 mmol), DIBAH (1.5 , 17.3 mL,
26.0 mmol), propargylmagnesium bromide in diethyl ether (1.6 ,
13.1 mL, 21.0 mmol), diethyl ether (25 mL). Yield: 558 mg (29%).
Rf (H/EA, 1:2) ϭ 0.4. 1H NMR (CDCl3, 250 MHz): δ ϭ 1.31Ϫ1.61
(br. s, 8 H), 2.08 (t, J ϭ 2.7 Hz, 2 H), 2.32 (ddd, J ϭ 2.7, 6.5,
16.7 Hz, 2 H), 2.43 (ddd, J ϭ 2.6, 5.1, 16.7 Hz, 2 H), 2.51 (br. s, 2
H), 2.72Ϫ3.81 (m, 2 H) ppm. 13C NMR (CDCl3, 62.9 MHz): δ ϭ
25.32 (t, 2 C), 27.22 (t, 2 C), 35.83 (t, 2 C), 69.58 (d, 2 C), 70.70
(d, 2 C), 80.92 (s, 2 C) ppm. IR (neat): ν˜ ϭ 3401 (ϪOH), 3280 (ϭ
CϪH), 2938, 2910, 2879, 2855, 2115 (CϵC) cmϪ1. MS (70 eV):
m/z (%) ϭ 195 (0.3) [MHϩ], 155 (52), 137 (86), 119 (48), 93 (100),
79 (59), 67 (72), 55 (51). C12H18O2 (194.27): calcd. C 74.19, H 9.34;
found C 73.98, H 9.17.
7f: Dimethyl 1,9-nonanedicarboxylate (4.64 g, 19.0 mmol), DIBAH
(1 , 41.9 mL, 41.9 mmol), propargylmagnesium bromide in diethyl
ether (1.6 , 26.1 mL, 41.8 mmol), diethyl ether (200 mL). Yield:
2.31 g (46%). M.p. 55 °C. Rf (H/EA, 1:2) ϭ 0.6. 1H NMR (CDCl3,
250 MHz): δ ϭ 1.25Ϫ1.52 (m, 18 H), 1.95 (s, 2 H), 2.02 (t, J ϭ
2.6 Hz, 2 H), 2.28 (ddd, J ϭ 2.7, 6.6, 16.7 Hz, 2 H), 2.40 (ddd, J ϭ
2.6, 4.8, 16.7 Hz, 2 H), 3.67Ϫ3.77 (m, 2 H) ppm. 13C NMR
(CDCl3, 62.9 MHz): δ ϭ 21.12 (t, 2 C), 22.88 (t, 2 C), 25.06 (t, 5
C), 31.73 (t, 2 C), 65.41 (d, 2 C), 66.28 (d, 2 C), 76.69 (s, 2 C) ppm.
IR (neat): ν˜ ϭ 3406 (ϪOH), 3281 (ϵCϪH), 2916, 2850, 2114
(CϵC) cmϪ1. MS (70 eV): m/z (%) ϭ 265 (0.5) [MHϩ], 225 (1), 121
(19), 109 (25), 107 (29), 95 (81), 81 (100), 67 (67), 55 (65). C
17H28O2 (264.41): calcd. C 77.22, H 10.67; found C 77.24, H 10.62.
7b: Diethyl pimelate (2.16 g, 10.0 mmol), DIBAH (1.2 , 18.3 mL,
22.0 mmol), propargylmagnesium bromide in diethyl ether (1.6 ,
13.1 mL, 21.0 mmol), diethyl ether (25 mL). Yield: 1.37 g (66%). Rf
1
(H/EA, 1:2) ϭ 0.4. H NMR (CDCl3, 250 MHz): δ ϭ 1.37Ϫ1.56
(br., 10 H), 2.07 (t, J ϭ 2.6 Hz, 2 H), 2.09 (br. s, 2 H), 2.32 (ddd,
J ϭ 2.7, 6.6, 16.7 Hz, 2 H), 2.44 (ddd, J ϭ 2.6, 4.9, 16.7 Hz, 2 H),
3.71Ϫ3.80 (br., 2 H) ppm. 13C NMR (CDCl3, 62.9 MHz): δ ϭ
25.31 (t, 2 C), 27.18 (t, 2 C), 29.19 (t), 35.87 (t, 2 C), 69.62 (d, 2
C), 70.65 (d, 2 C), 80.87 (s, 2 C) ppm. IR (neat): ν˜ ϭ 3374 (ϪOH),
3296 (ϵCϪH), 2934, 2858, 2118 (CϵC) cmϪ1. MS (70 eV): m/z
(%) ϭ 209 (0.5) [MHϩ], 169 (0.5) [M Ϫ C3H3]ϩ, 133 (36), 109 (21),
107 (97), 91 (95), 79 (84), 67 (88), 55 (100). C13H20O2 (208.30):
calcd. C 74.96, H 9.68; found C 75.10, H 9.84.
7g: Diethyl 1,10-decanedicarboxylate (5.73 g, 20.0 mmol), DIBAH
(1.5 , 30.0 mL, 45.0 mmol), propargylmagnesium bromide in di-
ethyl ether (1.6 , 26.3 mL, 42.0 mmol), diethyl ether (40 mL).
Yield: 1.89 g (34%). M.p. 76Ϫ77 °C. Rf (H/EA, 1:1) ϭ 0.5. 1H
NMR (CDCl3, 250 MHz): δ ϭ 1.26 (br. s, 16 H), 1.34Ϫ1.53 (m, 4
H), 2.04 (t, J ϭ 2.6 Hz, 2 H), 2.09 (d, J ϭ 4.7 Hz, 2 H), 2.30 (ddd,
J ϭ 2.7, 6.6, 16.7 Hz, 2 H), 2.41 (ddd, J ϭ 2.6, 4.8, 16.7 Hz, 2 H),
3.68Ϫ3.79 (m, 2 H) ppm. 13C NMR (CDCl3, 62.9 MHz): δ ϭ 25.42
(t, 2 C), 27.19 (t, 2 C), 29.35 (t, 6C), 36.05 (t, 2 C), 69.72 (d, 2 C),
70.61 (d, 2 C), 80.86 (s, 2 C) ppm. IR (neat): ν˜ ϭ 3395 (ϪOH),
3282 (ϵCϪH), 2915, 2848, 2115 (CϵC) cmϪ1. MS (70 eV): m/z
(%) ϭ 279 (0.3) [MHϩ], 243 (3), 239 (1), 121 (38), 109 (35), 95
(100), 81 (98), 67 (52), 55 (63). C18H30O2 (278.44): calcd. C 77.65,
H 10.86; found C 77.38, H 10.84.
7c: Dimethyl suberate (2.02 g, 10.0 mmol), DIBAH (1.5 ,
14.7 mL, 22.0 mmol), propargylmagnesium bromide in diethyl
ether (1.6 , 13.1 mL, 21.0 mmol), diethyl ether (25 mL). Yield:
715 mg (32%). M.p. 67 °C. Rf (H/EA, 1:2) ϭ 0.5. 1H NMR (CDCl3,
250 MHz): δ ϭ 1.29Ϫ1.53 (m, 12 H), 2.05Ϫ2.08 (m, 2 H), 2.33 (br.
s, 2 H), 2.33Ϫ2.37 (m, 2 H), 2.43 (ddd, J ϭ 2.7, 4.9, 16.7 Hz, 2 H),
3.70Ϫ3.82 (m, 2 H) ppm. 13C NMR (CDCl3, 62.9 MHz): δ ϭ 25.31
(t, 2 C), 27.17 (t, 2 C), 29.22 (t, 2 C), 35.95 (t, 2 C), 69.65 (d, 2 C),
70.62 (d, 2 C), 80.87 (s, 2 C) ppm. IR (neat): ν˜ ϭ 3404 (ϪOH),
3282 (ϵCϪH), 2928, 2854, 2114 (CϵC) cmϪ1. MS (70 eV): m/z
(%) ϭ 223 (0.5) [MHϩ], 183 (0.5), 119 (25), 105 (60), 91 (45), 81
(100), 67 (63), 55 (82). C14H22O2 (222.33): calcd. C 75.63, H 9.97;
found C 75.49, H 9.95.
7h: Dimethyl 1,11-undecanedicarboxylate (4.90 g, 18.0 mmol), DI-
BAH (1 , 39.6 mL, 39.6 mmol), propargylmagnesium bromide in
diethyl ether (1.6 , 24.8 mL, 39.6 mmol), diethyl ether (200 mL).
Yield: 2.26 g (43%). Rf (H/EA, 1:2) ϭ 0.6. 1H NMR (CDCl3,
250 MHz): δ ϭ 1.26Ϫ1.65 (br. s, 22 H), 1.94 (m, 2 H), 2.05 (t, J ϭ
2.6 Hz, 2 H), 2.30 (ddd, J ϭ 2.6, 6.7, 16.6 Hz, 2 H), 2.43 (ddd, J ϭ
2.6, 4.7, 16.6 Hz, 2 H), 3.66Ϫ3.75 (m, 2 H) ppm. 13C NMR
(CDCl3, 62.9 MHz): δ ϭ 25.40 (t, 2 C), 27.14 (t, 2 C), 29.35 (t, 7
C), 36.02 (t, 2 C), 69.68 (d, 2 C), 70.54 (d, 2 C), 80.92 (s, 2 C) ppm.
IR (neat): ν˜ ϭ 3396 (ϪOH), 3284 (ϵCϪH), 2916, 2850, 2114
(CϵC) cmϪ1. MS (70 eV): m/z (%) ϭ 293 (0.2) [MHϩ], 253 (1), 135
(16), 121 (16), 109 (29), 95 (88), 81 (100), 67 (64), 55 (61). C19H32O2
(292.46): calcd. C 78.03, H 11.03; found C 77.72, H 10.73.
7d: Dimethyl azelate (2.16 g, 10.0 mmol), DIBAH (1.5 , 14.7 mL,
22.0 mmol), propargylmagnesium bromide in diethyl ether (1.6 ,
13.1 mL, 21.0 mmol), diethyl ether (25 mL). Yield: 1.32 g (56%).
M.p. 32Ϫ38 °C. Rf (H/EA, 1:2) ϭ 0.5. 1H NMR (CDCl3,
250 MHz): δ ϭ 1.26Ϫ1.55 (m, 14 H), 2.07 (t, J ϭ 2.6 Hz, 2 H),
2.21 (br. s, 2 H), 2.31 (ddd, J ϭ 2.7, 6.5, 16.5 Hz, 2 H), 2.43 (ddd,
J ϭ 2.7, 4.8, 16.7 Hz, 2 H), 3.70Ϫ3.80 (m, 2 H) ppm. 13C NMR
(CDCl3, 62.9 MHz): δ ϭ 25.37 (t, 2 C), 27.18 (t, 2 C), 29.24 (t, 3
C), 36.00 (t, 2 C), 69.68 (d, 2 C), 70.71 (d, 2 C), 80.86 (s, 2 C) ppm.
IR (neat): ν˜ ϭ 3378 (ϪOH), 3300 (ϵCϪH), 2931, 2855, 2118
(CϵC) cmϪ1. MS (70 eV): m/z (%) ϭ 237 (0.2) [MHϩ], 197 (0.6)
[M Ϫ C3H3]ϩ, 119 (2), 105 (23), 95 (74), 81 (100), 67 (57), 55 (53).
C15H24O2 (236.35): calcd. C 76.23, H 10.24; found C 75.97, H
10.15.
7i: Diethyl 1,12-dodecanedicarboxylate (5.66 g, 18.0 mmol), DI-
BAH (1.5 , 27.0 mL, 40.5 mmol), propargylmagnesium bromide
in diethyl ether (1.6 , 26.8 mL, 43.0 mmol), diethyl ether
(120 mL). Yield: 506 mg (9%). M.p. 99Ϫ101 °C. Rf (H/EA, 1:1) ϭ
0.5. 1H NMR (CDCl3, 250 MHz): δ ϭ 1.26 (br. s, 20 H), 1.36Ϫ1.55
(br. m, 4 H), 1.93 (d, J ϭ 5.1 Hz, 2 H), 2.05 (t, J ϭ 2.7 Hz, 2 H),
2.30 (ddd, J ϭ 2.6, 6.7, 16.7 Hz, 2 H), 2.43 (ddd, J ϭ 2.7, 4.7,
16.7 Hz, 2 H), 3.69Ϫ3.81 (br. m, 2 H) ppm. 13C NMR (CDCl3,
7e: Diethyl sebacate (2.30 g, 10.0 mmol), DIBAH (1.5 , 17.3 mL,
26.0 mmol), propargylmagnesium bromide solution (1.6 , 62.9 MHz): δ ϭ 25.44 (t, 2 C), 27.20 (t, 2 C), 29.39 (t, 6 C), 29.44
13.1 mL, 21.0 mmol), diethyl ether (25 mL). Yield: 2.07 g (83%). (t, 2 C), 36.09 (t, 2 C), 69.75 (d, 2 C), 70.61 (d, 2 C), 80.81 (s, 2 C)
M.p. 64Ϫ65 °C. Rf (H/EA, 2.5:1) ϭ 0.2. 1H NMR (CDCl3, ppm. IR (neat): ν˜ ϭ 3396 (ϪOH), 3284 (ϵCϪH), 2916, 2849, 2114
Eur. J. Org. Chem. 2004, 1923Ϫ1935
www.eurjoc.org
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
1927

A. S. K. Hashmi, L. Schwarz, M. Bolte
FULL PAPER
(CϵC) cmϪ1. MS (70 eV): m/z (%) ϭ 307 (0.8) [MHϩ], 267 (1), 249 (CϭO) cmϪ1. MS (70 eV): m/z (%) ϭ 218 (3) [Mϩ], 179 (94), 151
(10), 135 (17), 121 (17), 109 (41), 95 (91), 81 (100), 67 (69), 55 (13), 133 (34), 109 (25), 95 (29), 81 (25), 67 (100), 55 (44). C14H18O2
(64). C20H34O2 (306.49): calcd. C 78.38, H 11.18; found C 78.34, (218.30): calcd. C 77.03, H 8.31; found C 76.98, H 8.29.
H 11.38.
8d: 7d (380 mg, 1.61 mmol), DMP (1.65 g, 3.89 mmol), DCM
(6 mL). Yield: 308 mg (82%). Rf (H/EA, 1:1) ϭ 0.6. 1H NMR
(CDCl3, 250 MHz): δ ϭ 1.30 (br. s, 6 H), 1.58 (m, 4 H), 2.59 (t,
J ϭ 7.4 Hz, 4 H), 5.24 (d, J ϭ 6.5 Hz, 4 H), 5.76 (t, J ϭ 6.5 Hz, 2
H) ppm. 13C NMR (CDCl3, 62.9 MHz): δ ϭ 24.25 (t, 2 C), 28.76
(t, 2 C), 28.91 (t), 38.93 (t, 2 C), 79.15 (t, 2 C), 96.46 (d, 2 C),
200.64 (s, 2 C), 216.40 (s, 2 C) ppm. IR (neat): ν˜ ϭ 3065, 2987,
7j: Diethyl 1,14-tetradecanedicarboxylate (3.43 g, 10.0 mmol), DI-
BAH (1.5 , 14.7 mL, 22.0 mmol), propargylmagnesium bromide
in diethyl ether (1.6 , 13.1 mL, 21.0 mmol), diethyl ether
(140 mL). Yield: 2.59 g (77%). M.p. 95Ϫ96 °C. Rf (H/EA, 1:1) ϭ
1
0.5. H NMR (CDCl3, 250 MHz): δ ϭ 1.26Ϫ1.59 (m, 28 H), 1.90
(d, J ϭ 5.0 Hz, 2 H), 2.06 (t, J ϭ 2.6 Hz, 2 H), 2.31 (ddd, J ϭ 2.6,
6.7, 16.7 Hz, 2 H), 2.44 (ddd, J ϭ 2.6, 4.7, 16.7 Hz, 2 H), 3.76 (m,
2 H) ppm. 13C NMR (CDCl3, 62.9 MHz): δ ϭ 25.57 (t, 2 C), 27.35
(t, 2 C), 29.51 (t, 2 C), 29.53 (t, 4 C), 29.60 (t, 4 C), 36.24 (t, 2 C),
69.89 (d, 2 C), 70.73 (d, 2 C), 80.94 (s, 2 C) ppm. IR (neat): ν˜ ϭ
3396 (ϪOH), 3285 (ϵCϪH), 2916, 2848, 2114 (CϵC) cmϪ1. MS
(70 eV): m/z (%) ϭ 333 (1) [M Ϫ H]ϩ, 295 (34), 277 (58), 121 (15)
109 (49), 95 (98), 81 (100), 69 (36), 67 (32) 55 (30). C22H38O2
(334.54): calcd. C 78.99, H 11.45; found C 78.98, H 11.45.
2930, 2856, 1958 (CϭCϭC), 1934 (CϭCϭC), 1681 (CϭO) cmϪ1
.
MS (70 eV): m/z (%) ϭ 233 (8) [MHϩ], 193 (29), 165 (3), 147 (8),
109 (5), 95 (23), 81 (28), 67 (100), 55 (88). C15H20O2 (232.32): calcd.
C 77.55, H 8.68; found C 77.72, H 8.42.
8e: 7e (500 mg, 2.00 mmol), DMP (1.49 g, 3.51 mmol), DCM
(6 mL). Yield: 407 mg (83%). Rf (H/EA, 1:1) ϭ 0.6. 1H NMR
(CDCl3, 250 MHz): δ ϭ 1.28 (br. s, 8 H), 1.55Ϫ1.61 (br. m, 4 H),
2.59 (t, J ϭ 7.4 Hz, 4 H), 5.24 (d, J ϭ 6.5 Hz, 4 H), 5.76 (t, J ϭ
6.5 Hz, 2 H) ppm. 13C NMR (CDCl3, 62.9 MHz): δ ϭ 24.38 (t, 2
C), 28.97 (t, 2 C), 29.05 (t, 2 C), 39.04 (t, 2 C), 79.24 (t, 2 C), 96.55
(d, 2 C), 200.86 (s, 2 C), 216.49 (s, 2 C) ppm. IR (neat): ν˜ ϭ 3065,
2988, 2936, 2851, 1961m (CϭCϭC), 1934 (CϭCϭC), 1678 (CϭO)
cmϪ1. MS (70 eV): m/z (%) ϭ 247 (8) [MHϩ], 207 (88), 179 (1),
161 (5), 147 (4), 135 (6), 109 (26), 95 (38), 81 (29), 67 (100), 55
(86). C16H22O2 (246.35): calcd. C 78.01, H 9.00; found C 77.76,
H 9.05.
2. General Procedure for the Dess؊Martin Oxidation of 7 to 8: The
oxidation[33Ϫ37] itself oxidizes the homopropargylic alcohols to pro-
pargyl ketones; the latter compounds then isomerize spontaneously
to the allenyl ketones during the chromatographic workup.[38]
DessϪMartin periodinane (DMP; 1.2 equiv.) was added in small
portions to a stirred solution of 7 (1 equiv.) in DCM (ca. 1Ϫ3 mL)
at room temperature. A water bath was used for thermoregulation.
Stirring was continued until the reaction was complete, as moni-
tored by TLC (in most cases, about 20 min). The resulting mixture
was placed directly on a silica gel column for workup. After the
DCM phase entered the column, some hexane was placed on the
column; when the hexane had entered the column, the requisite
solvent mixture for separation was then applied.
8f: 7f (500 mg, 1.89 mmol), DMP (2.00 g, 4.72 mmol), DCM
(8 mL). Yield: 404 mg (82%). Rf (H/EA, 1:1) ϭ 0.6. 1H NMR
(CDCl3, 250 MHz): δ ϭ 1.25 (br. s, 10 H), 1.53Ϫ1.59 (m, 4 H),
2.57 (t, J ϭ 7.4 Hz, 4 H), 5.21 (d, J ϭ 6.5 Hz, 4 H), 5.74 (t, J ϭ
6.5 Hz, 2 H) ppm. 13C NMR (CDCl3, 62.9 MHz): δ ϭ 24.28 (t, 2
C), 28.89 (t, 2 C), 29.00 (t), 29.05 (t, 2 C), 38.93 (t, 2 C), 79.10 (t,
2 C), 96.39 (d, 2 C), 200.55 (s, 2 C), 216.34 (s, 2 C) ppm. IR (neat):
ν˜ ϭ 3065, 2988, 2928, 2854, 1959 (CϭCϭC), 1934 (CϭCϭC), 1682
(CϭO) cmϪ1. MS (70 eV): m/z (%) ϭ 261 (6) [MHϩ], 221 (27), 109
(11), 95 (15), 81 (13), 67 (100), 55 (61). C17H24O2 (260.38): calcd.
C 78.42, H 9.29; found C 78.31, H 9.32.
8a: 7a (412 mg, 2.12 mmol), DMP (1.70 g, 4.00 mmol), DCM
(4 mL). Yield: 327 mg (81%). Rf (H/EA, 1:1) ϭ 0.7. 1H NMR
(CDCl3, 250 MHz): δ ϭ 1.53Ϫ1.68 (m, 4 H), 2.57Ϫ2.69 (m, 4 H),
5.24 (d, J ϭ 6.5 Hz, 4 H), 5.77 (t, J ϭ 6.5 Hz, 2 H) ppm. 13C NMR
(CDCl3, 62.9 MHz): δ ϭ 23.82 (t, 2 C), 38.76 (t, 2 C), 79.41 (t, 2
C), 96.56 (d, 2 C), 200.32 (s, 2 C), 216.55 (s, 2 C) ppm. IR (neat):
ν˜ ϭ 3065, 2987, 2939, 2868, 1958, 1933 (CϭCϭC), 1681 (CϭO)
cmϪ1. MS (70 eV): m/z (%) ϭ 190 (2) [Mϩ], 151 (54) [M Ϫ C3H3]ϩ,
133 (27), 123 (64), 105 (81), 67 (100). C12H14O2 (190.24): calcd.
190.09938, found 190.09945 (MS).
8g: 7g (400 mg, 1.44 mmol), DMP (453 mg, 3.61 mmol), DCM
(4 mL). Yield: 244 mg (62%). M.p. 25Ϫ36 °C. Rf (H/EA, 2:1) ϭ
0.5. 1H NMR (CDCl3, 250 MHz): δ ϭ 1.25 (br. s, 12 H), 1.54Ϫ1.59
(br. m, 4 H), 2.57 (t, J ϭ 7.4 Hz, 4 H), 5.21 (d, J ϭ 6.5 Hz, 4 H),
5.75 (t, J ϭ 6.5 Hz, 2 H) ppm. 13C NMR (CDCl3, 62.9 MHz): δ ϭ
24.34 (t, 2 C), 28.96 (t, 2 C), 29.17 (t, 4 C), 39.00 (t, 2 C), 79.14 (t,
2 C), 96.47 (d, 2 C), 200.74 (s, 2 C), 216.41 (s, 2 C) ppm. IR (neat):
ν˜ ϭ 3065, 2988, 2927, 2854, 1959 (CϭCϭC), 1934 (CϭCϭC), 1682
(CϭO) cmϪ1. MS (70 eV): m/z (%) ϭ 274 (3) [Mϩ], 235 (100), 207
(3), 110 (59), 95 (30), 81 (27), 67 (50), 55 (32). C18H26O2 (274.40):
calcd. C 78.79, H 9.55; found C 78.64, H 9.51.
8b: 7b (400 mg, 1.92 mmol), DMP (2.08 g, 4.96 mmol), DCM
(6 mL). Yield: 372 mg (95%). Rf (H/EA, 1:1) ϭ 0.6. 1H NMR
(CDCl3, 250 MHz): δ ϭ 1.26Ϫ1.38 (br., 2 H), 1.55Ϫ1.67 (br., 4 H),
2.61 (t, J ϭ 7.4 Hz, 4 H), 5.25 (d, J ϭ 6.5 Hz, 4 H), 5.76 (t, J ϭ
6.5 Hz, 2 H) ppm. 13C NMR (CDCl3, 62.9 MHz): δ ϭ 23.95 (t, 2
C), 28.42 (t), 38.66 (t, 2 C), 79.26 (t, 2 C), 96.46 (d, 2 C), 200.47
(s, 2 C), 216.42 (s, 2 C) ppm. IR (neat): ν˜ ϭ 3065, 2987, 2936, 2862,
1958 (CϭCϭC), 1934 (CϭCϭC), 1681 (CϭO) cmϪ1. MS (70 eV):
m/z (%) ϭ 205 (1) [MHϩ], 165 (18), 137 (9), 119 (37), 95 (14), 91
(21), 81 (10), 67 (100), 55 (44). C13H16O2 (204.26): calcd. C 76.44,
H 7.90; found C 76.15, H 8.09.
8h: 7h (500 mg, 1.71 mmol), DMP (1.82 g, 4.29 mmol), DCM
(6 mL). Yield: 400 mg (81%). M.p. 66 °C. Rf (H/EA, 1:1) ϭ 0.6. 1H
NMR (CDCl3, 250 MHz): δ ϭ 1.24 (s, 14 H), 1.54Ϫ1.59 (br. m, 4
H), 2.57 (t, J ϭ 7.4 Hz, 4 H), 5.21 (d, J ϭ 6.5 Hz, 4 H), 5.74 (t,
J ϭ 6.5 Hz, 2 H) ppm. 13C NMR (CDCl3, 62.9 MHz): δ ϭ 24.31
(t, 2 C), 28.93 (t, 2 C), 29.13 (t, 2 C), 29.18 (t, 2 C), 29.27 (t), 38.94
8c: 7c (300 mg, 1.35 mmol), DMP (1.38 g, 3.25 mmol), DCM
(4 mL). Yield: 148 mg (50%). M.p. 39Ϫ40 °C. Rf (H/EA, 1:1) ϭ
0.6. 1H NMR (CDCl3, 250 MHz): δ ϭ 1.28Ϫ1.34 (m, 4 H), (t, 2 C), 79.08 (t, 2 C), 96.39 (d, 2 C), 200.54 (s, 2 C), 216.33 (s, 2
1.54Ϫ1.62 (m, 4 H), 2.60 (t, J ϭ 7.4 Hz, 4 H), 5.25 (d, J ϭ 6.5 Hz,
C) ppm. IR (neat): ν˜ ϭ 3065, 2988, 2926, 2853, 1959 (CϭCϭC),
4 H), 5.76 (t, J ϭ 6.5 Hz, 2 H) ppm. 13C NMR (CDCl3, 62.9 MHz): 1934 (CϭCϭC), 1682 (CϭO) cmϪ1. MS (70 eV): m/z (%) ϭ 289
δ ϭ 24.09 (t, 2 C), 28.66 (t, 2 C), 38.80 (t, 2 C), 79.20 (t, 2 C), (1) [Mϩ], 249 (3), 221 (10), 139 (9), 121 (10), 95 (5), 67 (100), 55
96.40 (d, 2 C), 200.52 (s, 2 C), 216.37 (s, 2 C) ppm. IR (neat): ν˜ ϭ (41). C19H28O2 (288.43): calcd. C 79.12, H 9.79; found C 78.90,
3065, 2988, 2933, 2858, 1958 (CϭCϭC), 1934 (CϭCϭC), 1680 H 9.77.
1928
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
Eur. J. Org. Chem. 2004, 1923Ϫ1935

Synthesis of 2,4-Furanophanes by Palladium-Catalyzed Macrocyclization Reactions
FULL PAPER
8i: 7i (260 mg, 848 µmol), DMP (891 mg, 2.10 mmol), DCM
(15 mL). Yield: 162 mg (63%). M.p. 42Ϫ43 °C. Rf (H/EA, 1:1) ϭ
(t), 28.94 (t, 2 C), 104.42 (d, 2 C), 109.89 (d, 2 C), 140.49 (d, 2 C),
156.39 (s, 2 C) ppm. IR (neat): ν˜ ϭ 3115, 2930, 2856, 1597, 1508,
0.6. 1H NMR (CDCl3, 250 MHz): δ ϭ 1.23 (br. s, 16 H), 1.53 Ϫ1.58 1464, 1147, 1008, 796, 726 cmϪ1. MS (70 eV): m/z (%) ϭ 232 (10)
(m, 4 H), 2.56 (t, J ϭ 7.5 Hz, 4 H), 5.20 (d, J ϭ 6.5 Hz, 4 H), 5.73 [Mϩ], 95 (68), 81 (100), 53 (25). C15H20O2 (232.32): calcd.
(t, J ϭ 6.5 Hz, 2 H) ppm. 13C NMR (CDCl3, 62.9 MHz): δ ϭ 24.41 232.14633, found 232.14639 (MS).
(t, 2 C), 29.02 (t, 2 C), 29.21 (t, 2 C), 29.27 (t, 2 C), 29.39 (t, 2 C),
9e: 8e (50.0 mg, 203 µmol), AgNO3 (15.0 mg, 88.3 µmol), acetone
39.07 (t, 2 C), 79.12 (t, 2 C), 96.51 (d, 2 C), 200.83 (s, 2 C), 216.45
(3 mL). Yield: 39.8 mg (80%). Rf (H/EA, 5:1) ϭ 0.6. 1H NMR
(s, 2 C) ppm. IR (neat): ν˜ ϭ 3064, 2985, 2932, 2850, 1960 (CϭCϭ
(CDCl3, 250 MHz): δ ϭ 1.32 (br. s, 8 H), 1.61 (br. m, 4 H), 2.60
C), 1926 (CϭCϭC), 1672 (CϭO) cmϪ1. MS (70 eV): m/z (%) ϭ
(t, J ϭ 7.5 Hz, 4 H), 5.96 (dd, J ϭ 0.8, 3.1 Hz, 2 H), 6.27 (dd, J ϭ
303 (13) [MHϩ], 263 (47), 235 (4), 123 (28), 121 (28), 110 (76), 95
1.9, 3.1 Hz, 2 H), 7.28 (dd, J ϭ 0.8, 1.9 Hz, 2 H) ppm. 13C NMR
(75), 81 (74), 67 (94), 55 (100). C20H30O2 (302.46): calcd. C 79.42,
H 10.00; found C 79.36, H 9.99.
(CDCl3, 62.9 MHz): δ ϭ 27.84 (t, 2 C), 27.89 (t, 2 C), 29.01 (t, 2
C), 29.12 (t, 2 C), 104.40 (d, 2 C), 109.89 (d, 2 C), 140.49 (d, 2 C),
156.44 (s, 2 C) ppm. IR (neat): ν˜ ϭ 3115, 2929, 2856, 1597, 1507,
1465, 1147, 1006, 796, 727 cmϪ1. MS (70 eV): m/z (%) ϭ 246 (23)
[Mϩ], 95 (42), 81 (100), 53 (12). C16H22O2 (246.35): calcd. C 78.01,
8j: 7j (1.37 g, 4.10 mmol), DMP (4.16 mg, 9.81 mmol), DCM
(40 mL). Yield: 543 mg (40%). M.p. 46Ϫ48 °C. Rf (H/EA, 1:1) ϭ
0.7. 1H NMR (CDCl3, 250 MHz): δ ϭ 1.25 (br. s, 20 H), 1.52Ϫ1.65
(br. m, 4 H), 2.59 (t, J ϭ 7.5 Hz, 4 H), 5.23 (d, J ϭ 6.5 Hz, 4 H),
5.77 (t, J ϭ 6.5 Hz, 2 H) ppm. 13C NMR (CDCl3, 62.9 MHz): δ ϭ
24.44 (t, 2 C), 29.05 (t, 2 C), 29.24 (t, 2 C), 29.32 (t, 2 C), 29.44 (t,
2 C), 29.47 (t, 2 C), 39.11 (t, 2 C), 79.12 (t, 2 C), 96.54 (d, 2 C),
200.89 (s, 2 C), 216.48 (s, 2 C) ppm. IR (neat): ν˜ ϭ 3063, 2986,
H
9.00; found
C 78.15, H 8.98. calcd. 246.16198, found
246.16171 (MS).
9f: 8f (53.0 mg, 204 µmol), AgNO3 (10.0 mg, 58.8 µmol), acetone
(1 mL). Yield: 34.6 mg (65%). Rf (H/EA, 5:1) ϭ 0.6. 1H NMR
(CDCl3, 250 MHz): d ϭ 1.30 (br. s, 10 H), 1.57Ϫ1.66 (m, 4 H),
2.61 (t, J ϭ 7.6 Hz, 4 H), 5.96Ϫ5.97 (m, 2 H), 6.26Ϫ6.28 (m, 2 H),
7.29Ϫ7.30 (m, 2 H) ppm. 13C NMR (CDCl3, 62.9 MHz): δ ϭ 27.85
(t, 2 C), 27.91 (t, 2 C), 29.03 (t, 2 C), 29.19 (t), 29.29 (t, 2 C),
104.38 (d, 2 C), 109.88 (d, 2 C), 140.48 (d, 2 C), 156.47 (s, 2 C)
ppm. IR (neat): ν˜ ϭ 3115, 2928, 2855, 1596, 1508, 1464, 1147, 1007,
795, 725 cmϪ1. MS (70 eV): m/z (%) ϭ 260 (49) [Mϩ], 151 (6), 123
(19), 95 (80), 81 (100). C17H24O2 (260.38): calcd. 260.17763, found
260.17715 (MS).
2918, 2850, 1959 (CϭCϭC), 1928 (CϭCϭC), 1673 (CϭO) cmϪ1
.
MS (70 eV): m/z (%) ϭ 330 (6) [Mϩ], 291 (100), 263 (10), 121 (19),
110 (51), 95 (28), 81 (26), 67 (28), 55 (27). C22H34O2 (330.51): calcd.
C 79.95, H 10.37; found C 79.69, H 10.08.
3. General Procedure for the Formation of the Bisfurans 9
The starting material (ca. 50 mg) in dry acetone (ca. 3 mL) was
subjected to AgNO3 (10Ϫ30 mol %).[14,19] The reaction mixture
was then either stirred at room temperature overnight or heated
under reflux for 1 h. The solvent was evaporated in vacuo and the
crude product purified by column chromatography on silica gel.
9g: 8g (104 mg, 379 µmol), AgNO3 (20.0 mg, 118 µmol), acetone
(5 mL). Yield: 53.0 mg (51%). M.p. 37Ϫ38 °C. Rf (H/EA, 5:1) ϭ
0.6. 1H NMR (CDCl3, 250 MHz): δ ϭ 1.30 (br. s, 12 H), 1.58Ϫ1.67
(br. m, 4 H), 2.62 (t, J ϭ 7.5 Hz, 4 H), 5.98 (dd, J ϭ 0.9, 3.1 Hz,
2 H), 6.28 (dd, J ϭ 1.9, 3.1 Hz, 2 H), 7.30 (dd, J ϭ 0.8, 1.8 Hz, 2
H) ppm. 13C NMR (CDCl3, 62.9 MHz): δ ϭ 27.86 (t, 2 C), 27.91
(t, 2 C), 29.05 (t, 2 C), 29.22 (t, 2 C), 29.38 (t, 2 C), 104.38 (d, 2
C), 109.89 (d, 2 C), 140.48 (d, 2 C), 156.49 (s, 2 C) ppm. IR (neat):
9a: This compound is known; it was identified by its NMR spec-
tra.[43,44]
9b: 8b (40.0 mg, 196 µmol), AgNO3 (10.0 mg, 58.8 µmol), acetone
(3 mL). Yield: 23.6 mg (59%). Rf (H/EA, 5:1) ϭ 0.60. 1H NMR
(CDCl3, 250 MHz): δ ϭ 1.36Ϫ1.45 (br., 2 H), 1.61Ϫ1.72 (m, 4 H),
2.62 (t, J ϭ 7.5 Hz, 4 H), 5.96 (dd, J ϭ 0.8, 3.1 Hz, 2 H), 6.26 (dd,
J ϭ 1.9, 3.1 Hz, 2 H), 7.28 (dd, J ϭ 0.8, 1.8 Hz, 2 H) ppm. 13C
NMR (CDCl3, 62.9 MHz): δ ϭ 27.63 (t, 2 C), 27.72 (t, 2 C), 28.52
(t), 104.49 (d, 2 C), 109.90 (d, 2 C), 140.55 (d, 2 C), 156.21 (s, 2 C)
ppm. IR (neat): ν˜ ϭ 3114, 2926, 2854, 1597, 1507, 1459, 1147, 1007,
794, 726 cmϪ1. MS (70 eV): m/z (%) ϭ 203 (4) [M Ϫ H]ϩ, 151 (11),
137 (7), 123 (12), 95 (74), 81 (100). C13H16O2 (204.26).
ν˜ ϭ 3114, 2927, 2854, 1596, 1508, 1465, 1146, 1006, 795, 726 cmϪ1
.
MS (70 eV): m/z (%) ϭ 274 (14) [Mϩ], 95 (59), 81 (100), 53 (16).
C18H26O2 (274.40): calcd. C 78.79, H 9.55; found C 78.59, H 9.63.
9h: 8h (100 mg, 347 mmol), AgNO3 (20.0 mg, 118 µmol), acetone
(3 mL). Yield: 21.0 mg (21%). M.p. 37Ϫ38 °C. Rf (H/EA, 5:1) ϭ
0.7. 1H NMR (CDCl3, 250 MHz): δ ϭ 1.28Ϫ1.31 (m, 14 H),
1.61Ϫ1.67 (m, 4 H), 2.62 (t, J ϭ 7.5 Hz, 4 H), 5.98 (dd, J ϭ 0.8,
3.1 Hz, 2 H), 6.28 (dd, J ϭ 1.9, 3.1 Hz, 2 H), 7.30 (dd, J ϭ 0.8,
1.8 Hz, 2 H) ppm. 13C NMR (CDCl3, 62.9 MHz): δ ϭ 27.84 (t, 2
C), 27.90 (t, 2 C), 29.05 (t, 2 C), 29.21 (t, 2 C), 29.38 (t, 2 C), 29.44
(t), 104.35 (d, 2 C), 109.87 (d, 2 C), 140.46 (d, 2 C), 156.49 (s, 2 C)
ppm. IR (neat): ν˜ ϭ 3114, 2926, 2854, 1596, 1507, 1464, 1146, 1007,
794, 725 cmϪ1. MS (70 eV): m/z (%) ϭ 288 (57) [Mϩ], 151 (5), 123
(13), 95 (62), 81 (100). C19H28O2 (288.43): calcd. 288.20893, found
288.20848 (MS).
9c: 8c (60.0 mg, 275 µmol), AgNO3 (11.0 mg, 64.7 µmol), acetone
(3 mL). Yield: 35.0 mg (58%). Rf (H/EA, 5:1) ϭ 0.6. 1H NMR
(CDCl3, 250 MHz): δ ϭ 1.37Ϫ1.45 (m, 4 H), 1.61Ϫ1.70 (m, 4 H),
2.64 (t, J ϭ 7.5 Hz, 4 H), 5.99 (dd, J ϭ 0.8, 3.2 Hz, 2 H), 6.30 (dd,
J ϭ 1.9, 3.1 Hz, 2 H), 7.32 (dd, J ϭ 0.8, 1.8 Hz, 2 H) ppm. 13C
NMR (CDCl3, 62.9 MHz): δ ϭ 27.79 (t, 4 C), 28.74 (t, 2 C), 104.46
(d, 2 C), 109.89 (d, 2 C), 140.52 (d, 2 C), 156.32 (s, 2 C) ppm. IR
(neat): ν˜ ϭ 3115, 2933, 2859, 1598, 1507, 1463, 1147, 1008, 796,
727 cmϪ1. MS (70 eV): m/z (%) ϭ 218 (14) [Mϩ], 95 (57), 81 (100),
53 (26). C14H18O2 (218.30): calcd. C 77.03, H 8.31; found C 77.19,
H 8.46.
9i: 8i (34 mg, 112 µmol), AgNO3 (12.0 mg, 70.6 µmol), acetone
(3 mL). Yield: 25.0 mg (74%). M.p. 37Ϫ38 °C. Rf (H/EA, 5:1) ϭ
0.7. 1H NMR (CDCl3, 250 MHz): δ ϭ 1.26Ϫ1.29 (br., 16 H),
1.57Ϫ1.68 (br., 4 H), 2.61 (t, J ϭ 7.5 Hz, 4 H), 5.96 (dd, J ϭ 0.8,
9d: 8d (50.0 mg, 215 µmol), AgNO3 (11.0 mg, 64.7 µmol), acetone 3.1 Hz, 2 H), 6.27 (dd, J ϭ 1.9, 3.1 Hz, 2 H), 7.29 (dd, J ϭ 0.8,
(3 mL). Yield: 42.6 mg (85%). Rf (H/EA, 5:1) ϭ 0.6. 1H NMR 1.8 Hz, 2 H) ppm. 13C NMR (CDCl3, 62.9 MHz): δ ϭ 27.85 (t, 2
(CDCl3, 250 MHz): δ ϭ 1.33 (br. s, 6 H), 1.57Ϫ1.68 (br. m, 4 H), C), 27.91 (t, 2 C), 29.06 (t, 2 C), 29.24 (t, 2 C), 29.41 (t, 2 C), 29.47
2.60 (t, J ϭ 7.5 Hz, 4 H), 5.96 (dd, J ϭ 0.8, 3.1 Hz, 2 H), 6.26 (dd,
(t, 2 C), 104.36 (d, 2 C), 109.87 (d, 2 C), 140.46 (d, 2 C), 156.49 (s,
J ϭ 1.9, 3.1 Hz, 2 H), 7.28 (dd, J ϭ 0.8, 1.9 Hz, 2 H) ppm. 13C 2 C) ppm. IR (neat): ν˜ ϭ 3129, 2916, 2847, 1599, 1507, 1468, 1135,
NMR (CDCl3, 62.9 MHz): δ ϭ 27.82 (t, 2 C), 27.88 (t, 2 C), 28.90 1004, 808, 724 cmϪ1. MS (70 eV): m/z (%) ϭ 303 (0.3) [Mϩ], 81
Eur. J. Org. Chem. 2004, 1923Ϫ1935
www.eurjoc.org
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
1929

A. S. K. Hashmi, L. Schwarz, M. Bolte
FULL PAPER
(100), 53 (20). C20H30O2 (302.46): calcd. C 79.42, H 10.00; found
C 79.22, H 9.86.
(288.43): calcd. C 79.12, H 9.79; found C 79.30, H 9.71. HRMS
calcd. 288.20893, found 288.20791 (MS).
9j: 8j (40.0 mg, 121 µmol), AgNO3 (11.0 mg, 64.7 µmol), acetone
(3 mL). Yield: 29.0 mg (73%). M.p. 45Ϫ46 °C. Rf (H/EA, 5:1) ϭ
0.7. H NMR (CDCl3, 250 MHz): δ ϭ 1.28 (m, 20 H), 1.54Ϫ1.65
10i: Rf (H/EA, 5:1) ϭ 0.44. 1H NMR (CDCl3, 250 MHz): δ ϭ
1.25Ϫ1.39 (m, 16 H), 1.65Ϫ1.73 (m, 4 H), 2.42 (t, J ϭ 7.1 Hz, 2
H), 2.42 (d, J ϭ 1.1 Hz, 3 H), 2.64Ϫ2.69 (m, 2 H), 6.24 (d, J ϭ
1.0 Hz, 1 H), 6.48 (d, J ϭ 0.9 Hz, 1 H), 7.56 (d, J ϭ 0.7 Hz, 1
1
(m, 4 H), 2.61 (t, J ϭ 7.5 Hz, 4 H), 5.96 (dd, J ϭ 0.8, 3.1 Hz, 2
H), 6.27 (dd, J ϭ 1.9, 3.1 Hz, 2 H), 7.29 (dd, J ϭ 0.8, 1.8 Hz, 2 H)
ppm. 13C NMR (CDCl3, 62.9 MHz): δ ϭ 27.84 (t, 2 C), 27.90 (t,
2 C), 29.05 (t, 2 C), 29.23 (t, 2 C), 29.41 (t, 2 C), 29.50 (t, 4 C),
104.35 (d, 2 C), 109.86 (d, 2 C), 140.46 (d, 2 C), 156.50 (s, 2 C)
ppm. IR (neat): ν˜ ϭ 3129, 2917, 2848, 1599, 1505, 1470, 1139, 1010,
813, 723 cmϪ1. MS (70 eV): m/z (%) ϭ 330 (2) [Mϩ], 95 (19), 81
(100), 53 (11). C22H34O2 (330.51): calcd. C 79.95, H 10.37; found
C 79.68, H 10.37.
1
H) ppm. H NMR (CDCl3, 400 MHz): δ ϭ 1.23Ϫ1.29 (m, 12 H),
1.36Ϫ1.39 (m, 4 H), 1.66Ϫ1.73 (m, 4 H), 2.41 (d, J ϭ 1.0 Hz, 3
H), 2.39Ϫ2.43 (m, 2 H), 2.64Ϫ2.67 (m, 2 H), 6.24 (d, J ϭ 0.8 Hz,
1 H), 6.47 (d, J ϭ 0.4 Hz, 1 H), 7.55 (s, 1 H) ppm. 13C NMR
(CDCl3, 62.9 MHz): δ ϭ 16.23 (q), 25.32 (t), 25.51 (t), 26.40 (t),
26.45 (t), 27.07 (t), 27.59 (t), 27.78 (t), 28.08 (t), 28.25 (t), 28.39 (t),
28.68 (t), 43.61 (t), 102.54 (d), 120.71 (d), 128.99 (s), 141.71 (d),
144.94 (s), 157.71 (s), 202.79 (s) ppm. IR (neat): ν˜ ϭ 3134, 2927,
2855, 1765, 1676, 1589, 1443, 1367, 1331, 1201, 1134, 1077, 1038,
934 cmϪ1. MS (70 eV): m/z (%) ϭ 302 (100) [Mϩ], 290 (32), 121
(68). C20H30O2 (302.46): calcd. C 79.42, H 10.00; found C 79.53,
H 10.15. calcd. 302.22458, found 302.22487 (MS).
4. General Procedure for the Palladium-Catalyzed Reactions
A solution of 8 in acetonitrile (2 mL) was added by syringe pump
to a stirred solution of [Pd(MeCN)2Cl2][45] in acetonitrile (3 mL) at
40 °C over 60Ϫ62 h, and then stirring was continued for another
8Ϫ10 h at 40 °C. The quantities of the reactants are listed in
Table 1.
10j: Rf (H/EA, 5:1) ϭ 0.50. 1H NMR (CDCl3, 250 MHz): δ ϭ
1.26Ϫ1.40 (br., 20 H), 1.63Ϫ1.74 (br., 4 H), 2.40Ϫ2.45 (m, 2 H),
2.42 (d, J ϭ 1.0 Hz, 3 H), 2.63Ϫ2.68 (m, 2 H), 6.22 (s, 1 H), 6.45
(d, J ϭ 0.7 Hz, 1 H), 7.57 (s, 1 H) ppm. 1H NMR (C6D6,
250 MHz): δ ϭ 1.21Ϫ1.30 (m, 20 H), 1.41Ϫ1.55 (m, 2 H),
1.58Ϫ1.63 (m, 2 H), 2.33 (t, J ϭ 7.1 Hz, 2 H), 2.40 (s, 3 H),
2.44Ϫ2.49 (m, 2 H), 6.06 (s, 1 H), 6.42 (s, 1 H), 6.13 (s, 1 H) ppm.
1H NMR (C6D6, 400 MHz): δ ϭ 1.18Ϫ1.30 (m, 20 H), 1.50Ϫ1.53
(m, 2 H), 1.57Ϫ1.66 (m, 2 H), 2.34 (t, J ϭ 7.1 Hz, 2 H), 2.42 (d,
J ϭ 1.2 Hz, 3 H), 2.46Ϫ2.49 (m, 2 H), 6.07 (d, J ϭ 0.9 Hz, 1 H),
6.43 (d, J ϭ 1.1 Hz, 1 H), 7.15 (s, 1 H) ppm. 13C NMR (CDCl3,
62.9 MHz): δ ϭ 16.34 (q), 25.37 (t), 25.95 (t), 26.61 (t), 26.90 (t),
27.48 (t, 2 C), 27.80 (t), 27.83 (t), 27.98 (t), 28.08 (t, 2 C), 28.12 (t),
28.72 (t), 44.41 (t), 102.46 (d), 120.24 (d), 128.86 (s), 141.54 (d),
145.09 (s), 157.60 (s), 202.53 (s) ppm. IR (neat): ν˜ ϭ 3141, 2926,
Table 1. Amount of substrate 8 and catalyst
n
Starting
material
Quantity
Quantity of catalyst
4
5
6
7
8
9
10
11
12
13
8a
8b
8c
8d
8e
8f
60 mg (315 µmol)
68 mg (333 µmol)
65 mg (298 µmol)
60 mg (258 µmol)
60 mg (244 µmol)
63 mg (242 µmol)
55 mg (200 µmol)
73 mg (253 µmol)
74 mg (245 µmol)
60 mg (182 µmol)
3.5 mg (13 µmol, 4 mol%)
4.4 mg (17 µmol, 5 mol%)
4.0 mg (15 µmol, 5 mol%)
3.6 mg (14 µmol, 5 mol%)
3.6 mg (14 µmol, 6 mol%)
3.4 mg (13 µmol, 5 mol%)
2.8 mg (11 µmol, 6 mol%)
3.4 mg (13 µmol, 5 mol%)
2.4 mg (9.0 µmol, 4 mol%)
2.7 mg (10 µmol, 5 mol%)
8g
8h
8i
2855, 1676, 1589, 1456, 1367, 1331, 1200, 1137, 1049, 929 cmϪ1
.
MS (70 eV): m/z (%) ϭ 330 (100) [Mϩ], 287 (24), 135 (23).
8j
C22H34O2 (330.51): calcd. 330.25588, found 330.25518 (MS).
11c: Rf (H/EA, 5:1) ϭ 0.34. 1H NMR (CDCl3, 250 MHz): δ ϭ
0.80Ϫ0.89 (m, 2 H), 1.13Ϫ1.25 (m, 2 H), 1.51 Ϫ1.70 (m, 4 H), 2.11
(d, J ϭ 1.4 Hz, 3 H), 2.15 (t, J ϭ 6.5 Hz, 2 H), 2.66 (t, J ϭ 6.7 Hz,
2 H), 5.84 (d, J ϭ 1.2 Hz, 1 H), 5.95 (s, 1 H), 7.36 (s, 1 H) ppm.
1H NMR (CDCl3, 400 MHz): δ ϭ 0.81Ϫ0.87 (m, 2 H), 1.15Ϫ1.22
(m, 2 H), 1.53Ϫ1.59 (m, 2 H), 1.62Ϫ1.68 (m, 2 H), 2.12 (d, J ϭ
1.4 Hz, 3 H), 2.15 (t, J ϭ 6.5 Hz, 2 H), 2.66 (t, J ϭ 6.7 Hz, 2 H),
5.85 (d, J ϭ 1.4 Hz, 1 H), 5.96 (s, 1 H), 7.37 (d, J ϭ 0.9 Hz, 1 H)
ppm. 13C NMR (CDCl3, 62.9 MHz): δ ϭ 20.35 (t), 23.15 (t), 23.46
(q), 23.88 (t), 24.53 (t), 25.49 (t), 38.54 (t), 111.06 (d), 125.62 (s),
129.05 (d), 137.11 (d), 138.45 (s), 156.02 (s), 207.07 (s) ppm. IR
(neat): ν˜ ϭ 3127, 2934, 2862, 1683, 1598, 1536, 1440, 1408, 1361,
1325, 1286, 1248, 1180, 1121, 1081, 1008, 951, 911 cmϪ1. MS
(70 eV): m/z (%) ϭ 218 (13) [Mϩ], 206 (27), 149 (100). C14H18O2
(218.30): calcd. C 77.03, H 8.31; found C 76.80, H 8.27. HRMS
calcd. 218.13068, found 218.12861 (MS).
The solvent was then removed in vacuo and the crude product was
purified by direct column chromatography on silica gel.
10g: Rf (H/EA, 5:1) ϭ 0.38. M.p. 77Ϫ78 °C. 1H NMR (CDCl3,
250 MHz): δ ϭ 1.20Ϫ1.42 (m, 12 H), 1.62Ϫ1.76 (m, 4 H), 2.41 (d,
J ϭ 1.1 Hz, 3 H), 2.43Ϫ2.48 (m, 2 H), 2.65 (t, J ϭ 5.8 Hz, 2 H),
6.26 (d, J ϭ 1.0 Hz, 1 H), 6.55 (s, 1 H), 7.55 (s, 1 H) ppm. 1H
NMR (CDCl3, 400 MHz): δ ϭ 1.26Ϫ1.43 (m, 12 H), 1.65Ϫ1.75
(m, 4 H), 2.41 (d, J ϭ 1.1 Hz, 3 H), 2.44Ϫ2.47 (m, 2 H), 2.64Ϫ2.67
(m, 2 H), 6.26 (d, J ϭ 0.9 Hz, 1 H), 6.55 (s, 1 H), 7.55 (s, 1 H)
ppm. 13C NMR (CDCl3, 62.9 MHz): δ ϭ 15.96 (q), 24.22 (t), 24.59
(t), 25.42 (t), 26.22 (t), 27.14 (t), 27.55 (t), 28.11 (t), 28.46 (t), 28.94
(t), 42.87 (t), 103.01 (d), 120.79 (d), 129.17 (s), 141.51 (d), 144.32
(s), 157.82 (s), 202.47 (s) ppm. IR (neat): ν˜ ϭ 3124, 2927, 2852,
1665, 1584, 1438, 1367, 1333, 1305, 1204, 1072, 1036 cmϪ1. MS
(70 eV): m/z (%) ϭ 274 (100) [Mϩ], 122 (61), 91 (30). C18H26O2
(274.40): calcd. C 78.79, H 9.55; found C 78.87, H 9.50. HRMS
calcd. 274.19328, found 274.19318 (MS).
11d: Rf (H/EA, 5:1) ϭ 0.40. 1H NMR (CDCl3, 250 MHz): δ ϭ
10h: Rf (H/EA, 5:1) ϭ 0.40. 1H NMR (CDCl3, 250 MHz): δ ϭ 0.74Ϫ0.83 (m, 2 H), 1.14Ϫ1.24 (m, 2 H), 1.30Ϫ1.40 (m, 2 H),
1.14Ϫ1.41 (m, 14 H), 1.51Ϫ1.67 (m, 4 H), 2.01 (d, J ϭ 1.3 Hz, 3
H), 2.34Ϫ2.39 (m, 2 H), 2.56Ϫ2.61 (m, 2 H), 5.91 (d, J ϭ 1.3 Hz, 2 H), 2.59 (t, J ϭ 6.0 Hz, 2 H), 5.82 (d, J ϭ 1.2 Hz, 1 H), 5.88 (s,
1 H), 6.01 (d, J ϭ 0.9 Hz, 1 H), 7.04 (d, J ϭ 0.9 Hz, 1 H) ppm. IR
1 H), 7.34 (s, 1 H) ppm. 13C NMR (CDCl3, 62.9 MHz): δ ϭ 20.46
1.49Ϫ1.64 (m, 4 H), 2.05 (d, J ϭ 1.3 Hz, 3 H), 2.29 (t, J ϭ 7.0 Hz,
(neat): ν˜ ϭ 3144, 2927, 2855, 1765, 1718, 1678, 1589, 1453, 1404, (t), 24.04 (q), 24.88 (t), 25.39 (t), 25.57 (t), 28.00 (t), 28.51 (t), 39.53
1368, 1338, 1208, 1137, 1080, 996, 938 cmϪ1. MS (70 eV): m/z (t), 108.03 (d), 126.07 (s), 128.53 (d), 137.61 (d), 138.87 (s), 156.46
(%) ϭ 288 (100) [Mϩ], 276 (20), 135 (39), 84 (60). C19H28O2
(s), 207.02 (s) ppm. C15H20O2 (232.32).
www.eurjoc.org Eur. J. Org. Chem. 2004, 1923Ϫ1935
1930
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Synthesis of 2,4-Furanophanes by Palladium-Catalyzed Macrocyclization Reactions
FULL PAPER
12e: Rf (H/EA, 5:1) ϭ 0.48. 1H NMR (CDCl3, 250 MHz): δ ϭ
0.80Ϫ0.91 (m, 2 H), 1.00Ϫ1.15 (m, 4 H), 1.17Ϫ1.26 (m, 2 H),
1.40Ϫ1.51 (m, 2 H), 1.57Ϫ1.67 (m, 2 H), 2.33 (t, J ϭ 7.1 Hz, 2 H),
2.61 (t, J ϭ 6.1 Hz, 2 H), 3.38 (s, 2 H), 5.05 (d, J ϭ 1.1 Hz, 1 H),
5.36 (d, J ϭ 1.2 Hz, 1 H), 6.08 (s, 1 H), 7.33 (s, 1 H) ppm. 1H
NMR (C6D6, 250 MHz): δ ϭ 0.27Ϫ0.80 (m, 2 H), 0.84Ϫ0.95 (m,
2 H), 0.99Ϫ1.20 (m, 4 H), 1.34Ϫ1.54 (m, 4 H), 2.02 (t, J ϭ 7.0 Hz,
2 H), 2.34 (t, J ϭ 6.1 Hz, 2 H), 3.05 (s, 2 H), 4.80 (s, 1 H), 5.17 (d,
J ϭ 1.3 Hz, 1 H), 5.76 (s, 1 H), 7.11 (s, 1 H) ppm. 1H NMR
(CDCl3, 400 MHz): δ ϭ 0.82Ϫ0.92 (m, 2 H), 1.01Ϫ1.14 (m, 4 H),
1.17Ϫ1.28 (m, 2 H), 1.42Ϫ1.49 (m, 2 H), 1.59Ϫ1.65 (m, 2 H),
2.39Ϫ2.43 (m, 2 H), 2.59Ϫ2.62 (m, 2 H), 3.38 (s, 2 H), 5.05 (d, J ϭ
1.2 Hz, 1 H), 5.36 (d, J ϭ 1.2 Hz, 1 H), 6.07 (s, 1 H), 7.32 (d, J ϭ
0.5 Hz, 1 H) ppm. 13C NMR (CDCl3, 62.9 MHz): δ ϭ 22.70 (t),
25.70 (t), 26.16 (t), 26.23 (t), 26.40 (t), 26.72 (t), 27.45 (t), 39.16 (t),
50.81 (t), 105.69 (d), 114.49 (t), 126.83 (s), 134.36 (s), 137.83 (d),
157.05 (s), 206.84 (s) ppm. IR (neat): ν˜ ϭ 3088, 2929, 2857, 1710
(CϭO), 1637, 1598, 1540, 1457, 1364, 1287, 1214, 1129, 1068, 927
cmϪ1. MS (70 eV): m/z (%) ϭ 246 (47) [Mϩ], 234 (37), 205 (18),
163 (17), 161 (20), 149 (100), 136 (38), 121 (44), 108 (28), 91 (26).
C16H22O2 (246.35): calcd. C 78.01, H 9.00; found C 77.79, H 8.87.
HRMS calcd. 246.16198, found 246.16146 (MS).
11e: Rf (H/EA, 5:1) ϭ 0.40. 1H NMR (CDCl3, 250 MHz): δ ϭ
0.90Ϫ0.99 (m, 2 H), 1.06Ϫ1.20 (m, 2 H), 1.21Ϫ1.32 (m, 4 H),
1.46Ϫ1.59 (m, 2 H), 1.65Ϫ1.75 (m, 2 H), 2.07 (d, J ϭ 1.4 Hz, 3
H), 2.27 (t, J ϭ 8.2 Hz, 2 H), 2.66 (t, J ϭ 1.4 Hz, 2 H), 5.90 (d,
J ϭ 1.4 Hz, 1 H), 6.00 (d, J ϭ 0.8 Hz, 1 H), 7.26 (d, J ϭ 0.8 Hz,
1 H) ppm. 1H NMR (CDCl3, 400 MHz): δ ϭ 0.86Ϫ0.97 (m, 2
H), 1.08Ϫ1.14 (m, 2 H), 1.19Ϫ1.32 (m, 4 H), 1.49Ϫ1.58 (m, 2 H),
1.67Ϫ1.73 (m, 2 H), 2.07 (d, J ϭ 2.2 Hz, 3 H), 2.25Ϫ2.29 (m, 2
H), 2.64Ϫ2.67 (m, 2 H), 5.91 (d, J ϭ 1.1 Hz, 1 H), 6.01 (s, 1 H),
7.27 (s, 1 H) ppm. 13C NMR (CDCl3, 62.9 MHz): δ ϭ 21.18 (t),
24.79 (q), 25.23 (t), 25.40 (t), 25.82 (t), 25.98 (t), 27.15 (t), 27.25
(t), 40.86 (t), 107.07 (d), 126.01 (s), 129.15 (d), 138.49 (d), 139.23
(s), 156.88 (s), 206.56 (s) ppm. IR (neat): ν˜ ϭ 3135, 2928, 2857,
1674 (CϭO), 1598, 1538, 1442, 1371, 1335, 1271, 1129, 1075, 1030,
927 cmϪ1. MS (70 eV): m/z (%) ϭ 246 (21) [Mϩ], 234 (42), 149
(100). C16H22O2 (246.35): calcd. C 78.01, H 9.00; found C 78.26,
H 8.96. HRMS calcd. 246.16198, found 246.16122 (MS).
11f: Rf (H/EA, 5:1) ϭ 0.46. 1H NMR (CDCl3, 250 MHz): δ ϭ
0.98Ϫ1.17 (m, 10 H), 1.42Ϫ1.57 (m, 4 H), 2.00 (d, J ϭ 1.0 Hz, 3
H), 2.32 (t, J ϭ 7.1 Hz, 2 H), 2.55 (t, J ϭ 6.0 Hz, 2 H), 5.85 (d,
J ϭ 1.2 Hz, 1 H), 6.00 (s, 1 H), 7.24 (s, 1 H) ppm. 1H NMR
(CDCl3, 400 MHz): δ ϭ 0.99Ϫ1.04 (m, 2 H), 1.11Ϫ1.17 (m, 8 H),
1.44Ϫ1.51 (m, 2 H), 1.54Ϫ1.58 (m, 2 H), 2.00 (d, J ϭ 1.4 Hz, 3
H), 2.31 (t, J ϭ 7.1 Hz, 2 H), 2.54Ϫ2.57 (m, 2 H), 5.85 (d, J ϭ
1.4 Hz, 1 H), 6.00 (d, J ϭ 0.9 Hz, 1 H), 7.24 (d, J ϭ 1.0 Hz, 1 H)
ppm. 13C NMR (CDCl3, 62.9 MHz): δ ϭ 22.24 (t), 24.50 (q), 25.00
(t), 25.47 (t), 25.87 (t), 25.90 (t), 26.11 (t), 26.72 (t), 26.91 (t), 41.55
(t), 106.23 (d), 125.28 (s), 128.36 (d), 137.39 (s), 139.08 (d), 156.61
(s), 205.90 (s) ppm. IR (neat): ν˜ ϭ 3140, 2930, 2857, 1767, 1686,
1598, 1539, 1443, 1405, 1369, 1260, 1136, 1083, 930 cmϪ1. MS
(70 eV): m/z (%) ϭ 260 (100) [Mϩ], 248 (60), 121 (99), 109 (70).
C17H24O2 (260.38). HRMS calcd. 260.177038, found 260.17715
(MS).
12f: Rf (H/EA, 5:1) ϭ 0.50. 1H NMR (CDCl3, 250 MHz): δ ϭ
0.85Ϫ1.05 (m, 8 H), 1.17Ϫ1.28 (m, 2 H), 1.42Ϫ1.52 (m, 2 H),
1.56Ϫ1.66 (m, 2 H), 2.39Ϫ2.44 (m, 2 H), 2.56Ϫ2.61 (m, 2 H), 3.35
(s, 2 H), 5.08 (s, 1 H), 5.39 (s, 1 H), 6.12 (s, 1 H), 7.30 (s, 1 H)
ppm. 1H NMR (CDCl3, 400 MHz): δ ϭ 0.79Ϫ0.86 (m, 2 H),
0.87Ϫ0.94 (m, 2 H), 0.95Ϫ1.00 (m, 4 H), 1.10Ϫ1.22 (m, 2 H),
1.33Ϫ1.44 (m, 2 H), 1.51Ϫ1.57 (m, 2 H), 2.35 (t, J ϭ 6.2 Hz, 2 H),
2.50Ϫ2.53 (m, 2 H), 3.28 (d, J ϭ 1.0 Hz, 2 H), 5.02 (d, J ϭ 1.2 Hz,
1 H), 5.33 (d, J ϭ 1.1 Hz, 1 H), 6.05 (d, J ϭ 0.8 Hz, 1 H), 7.24 (d,
J ϭ 0.8 Hz, 1 H) ppm. 13C NMR (CDCl3, 62.9 MHz): δ ϭ 22.81
(t), 25.05 (t), 25.95 (t), 26.66 (t), 26.94 (t), 26.98 (t), 27.41 (t), 27.64
(t), 37.55 (t), 51.92 (t), 104.84 (d), 114.32 (t), 126.19 (s), 134.15 (s),
138.61 (d), 157.08 (s), 210.00 (s) ppm. IR (neat): ν˜ ϭ 2930, 2857,
11h: Rf (H/EA, 5:1) ϭ 0.40. 1H NMR (CDCl3, 250 MHz): δ ϭ
1.14Ϫ1.41 (m, 14 H), 1.51Ϫ1.67 (m, 4 H), 2.32 (d, J ϭ 1.2 Hz, 3
H), 2.34Ϫ2.39 (m, 2 H), 2.56Ϫ2.61 (m, 2 H), 6.19 (d, J ϭ 0.9 Hz,
1 H), 6.42 (d, J ϭ 0.7 Hz, 1 H), 7.47 (d, J ϭ 0.7 Hz, 1 H) ppm.
13C NMR (CDCl3, 62.9 MHz): δ ϭ 16.36 (q), 25.28 (t), 25.70 (t),
26.04 (t), 26.62 (t), 27.39 (t), 27.75 (t), 28.25 (t), 28.36 (t), 28.64 (t),
28.80 (t), 43.95 (t), 103.05 (d), 120.68 (d), 129.18 (s), 141.31 (d),
144.48 (s), 157.60 (s), 202.49 (s) ppm. IR: ν˜ ϭ 3127, 2927, 2856,
1767, 1710, 1636, 1599, 1540, 1440, 1363, 1226, 1134, 928 cmϪ1
.
5. Preparation of the Diols 15a and 16a
1,5-Pentanediol (26.0 g, 250 mmol), 60% NaH-suspension (4.00 g,
100 mmol), 1,2-bis(bromomethyl)benzene (10.6 mg, 40.2 mmol),
THFabs (300ϩ50 mL). Purification by column chromatography on
silica gel (H/EE/methanol, 12:12:1). Yield: 16a (1.06 g, 5%) and 15a
(6.85 g, 55%).
1765, 1674, 1588, 1443, 1367, 1204, 1136, 1076, 1036, 920 cmϪ1
.
C19H28O2 (288.43): calcd. C 79.12, H 9.79; found C 79.02, H 9.66.
15a: Yield: 55%. Rf (H/EA/MeOH, 6:6:0.75) ϭ 0.16. 1H NMR
(CDCl3, 250 MHz): δ ϭ 1.39Ϫ1.69 (m, 12 H), 1.22 (d, J ϭ 5.4 Hz,
2 H), 3.48 (t, J ϭ 6.4 Hz, 4 H), 3.60 (t, J ϭ 6 Hz, 4 H), 4.56 (s, 4 H),
7.25Ϫ7.30 (m, 2 H), 7.34Ϫ7.39 (m, 2 H) ppm. 13C NMR (CDCl3,
62.9 MHz): δ ϭ 22.11 (t, 2 C), 29.09 (t, 2 C), 32.02 (t, 2 C), 61.93
(t, 2 C), 70.14 (t, 2 C), 70.16 (t, 2 C), 127.36 (d, 2 C), 128.34 (d, 2
C), 136.22 (s, 2 C) ppm. IR (neat): ν˜ ϭ 3384 (OH), 3069 (ArϪH),
3030 (ArϪH), 2935, 2863, 1455, 1362, 1217, 1186, 1091, 914, 752
cmϪ1. MS (70 eV): m/z (%) ϭ 206 (32) [M Ϫ HO(CH2)5OH]ϩ, 120
(100), 104 (18), 87 (14). C18H30O4 (310.43): calcd. C 69.64, H 9.74;
found C 69.47, H 9.65. 16a: Yield: 5%. Rf (H/EA/MeOH,
6:6:0.75) ϭ 0.20. 1H NMR (CDCl3, 250 MHz): δ ϭ 1.39Ϫ1.69 (m,
18 H), 1.88 (s, 2 H), 3.48 (t, J ϭ 6 Hz, 8 H), 3.60 (t, J ϭ 6 Hz, 4
H), 4.56 (s, 8 H), 7.25Ϫ7.30 (m, 4 H), 7.35Ϫ7.40 (m, 4 H) ppm.
13C NMR (CDCl3, 62.9 MHz): δ ϭ 22.25 (t, 2 C), 22.73 (t), 29.25
(t, 2 C), 29.36 (t, 2 C), 32.22 (t, 2 C), 62.32 (t, 2 C), 70.24 (t, 8 C),
127.42 (d, 2 C), 127.45 (d, 2 C), 128.36 (d, 2 C), 128.40 (d, 2 C),
136.33 (s, 2 C), 136.43 (s, 2 C) ppm. IR (neat): ν˜ ϭ 3410 (OH),
3067 (ArϪH), 3028 (ArϪH), 2935, 2862, 1455, 1362, 1218, 1187,
1092, 915, 754 cmϪ1. MS (70 eV): m/z (%) ϭ 412 (1.7) [M Ϫ
1
12c: Rf (H/EA, 5:1) ϭ 0.26. M.p. 122Ϫ124 °C. H NMR (CDCl3,
400 MHz): δ ϭ 0.29Ϫ0.36 (m, 2 H), 1.11Ϫ1.18 (m, 2 H), 1.42Ϫ1.58
(m, 4 H), 2.41Ϫ2.44 (m, 2 H), 2.58 (t, J ϭ 6.3 Hz, 2 H), 3.37 (s, 2
H), 5.03 (d, J ϭ 1.5 Hz, 1 H), 5.20 (m, 1 H), 6.10 (s, 1 H), 7.25 (d,
J ϭ 0.8 Hz, 1 H) ppm. 13C NMR (CDCl3, 62.9 MHz): δ ϭ 22.39
(t), 25.25 (t), 26.33 (t), 26.49 (t), 28.14 (t), 42.54 (t), 50.15 (t), 108.06
(d), 114.05 (t), 126.34 (s), 135.09 (s), 138.44 (d), 155.66 (s), 210.93
(s) ppm. IR (neat): ν˜ ϭ 3102, 2927, 2856, 1700 (CϭO), 1545, 1456,
1434, 1412, 1362, 1211, 1158, 1111, 1048, 934, 910 cmϪ1. C14H18O2
(218.30): calcd. C 77.03, H 8.31; found C 77.03, H 8.39.
12d: Rf (H/EA, 5:1) ϭ 0.48. 1H NMR (CDCl3, 250 MHz): δ ϭ
0.47Ϫ0.56 (m, 2 H), 0.97Ϫ1.08 (m, 2 H), 1.15Ϫ1.25 (m, 2 H),
1.38Ϫ1.48 (m, 2 H), 1.52Ϫ1.61 (m, 2 H), 2.27Ϫ2.32 (m, 2 H),
2.55Ϫ2.60 (m, 2 H), 3.34 (s, 2 H), 5.03 (d, J ϭ 1.1 Hz, 1 H), 5.28
(s, 1 H), 5.97 (s, 1 H), 7.38 (s, 1 H) ppm. 13C NMR (CDCl3,
62.9 MHz): δ ϭ 21.57 (t), 25.46 (t), 25.64 (t), 26.56 (t), 27.95 (t),
28.25 (t), 39.25 (t), 51.51 (t), 106.54 (d), 114.16 (t), 127.80 (s),
134.67 (s), 137.90 (d), 157.21 (s), 210.31 (s) ppm. C15H20O2
(232.32).
Eur. J. Org. Chem. 2004, 1923Ϫ1935
www.eurjoc.org
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
1931

A. S. K. Hashmi, L. Schwarz, M. Bolte
FULL PAPER
HO(CH2)5OH]ϩ, 206 (87), 120 (100), 105 (75), 87 (69). C31H48O4 3295 (ϵCϪH), 3069 (ArϪH), 3029 (ArϪH), 2935, 2863, 2117
(516.72): calcd. C 72.06, H 9.36; found C 71.89, H 9.38.
(CϵC), 1454, 1360, 1218, 1188, 1092, 756 cmϪ1. MS (70 eV): m/z
(%) ϭ 386 (0.05) [Mϩ], 244 (21), 142 (48), 120 (100), 105 (61), 91
(26), 85 (89). C24H34O4 (386.53): calcd. C 74.58, H 8.87; found C
74.36, H 8.95.
6. Preparation of the Diols 15b and 16b
1,12-Dodecandiol (58.4 g, 289 mmol), 60% NaH-suspension
(4.62 g, 116 mmol), 1,2-bis(bromomethyl)benzene (12.2 g, 46.2
mmol), THFabs (350 ϩ 50 mL). Purification by several recrystalli-
zations: the products stay in solution and the dodecandiol precipi-
tates. Subsequently, column chromatography on silica gel (H/EE,
2:1). Yield: 16b (2.25 g, 6%) and 15b (8.72 g, 37%).
19a: 18a (1.00 g, 2.61 mmol), DMP (2.63 g, 6.20 mmol), DCM
(3 mL), purification by column chromatography (H/EE, 2.5:1).
Yield: 729 mg (73%). Rf (H/EA, 1:1) ϭ 0.50. 1H NMR (CDCl3,
250 MHz): δ ϭ 1.58Ϫ1.73 (m, 8 H), 2.60Ϫ2.65 (m, 4 H), 3.45Ϫ3.50
(m, 4 H), 4.54 (s, 4 H), 5.20 (d, J ϭ 6.5 Hz, 4 H), 5.76 (t, J ϭ
6.5 Hz, 2 H), 7.25Ϫ7.30 (m, 2 H), 7.34Ϫ7.39 (m, 2 H) ppm. 13C
NMR (CDCl3, 62.9 MHz): δ ϭ 21.11 (t, 2 C), 29.03 (t, 2 C), 38.63
(t, 2 C), 69.99 (t, 2 C), 70.27 (t, 2 C), 79.24 (t, 2 C), 96.47 (d, 2 C),
127.44 (d, 2 C), 128.34 (d, 2 C), 136.38 (s, 2 C), 200.33 (s, 2 C),
216.41 (s, 2 C) ppm. IR (neat): ν˜ ϭ 3064 (ArϪH), 2937, 2863, 1934
(CϭCϭC), 1679 (CϭO), 1453, 1410, 1361, 1161, 1095, 857, 756
cmϪ1. MS (70 eV): m/z (%) ϭ 382 (1.6) [Mϩ], 242 (20), 123 (100),
104 (43), 81 (16). C24H30O4 (382.50): calcd. C 75.36, H 7.91; found
C 75.15, H 7.98.
15b: Yield: 37%. M.p. 51 °C. Rf (H/EA, 1:1) ϭ 0.30. 1H NMR
(CDCl3, 250 MHz): δ ϭ 1.27Ϫ1.30 (m, 32 H), 1.49 (br. s, 2 H),
1.50Ϫ1.64 (m, 8 H), 3.47 (t, J ϭ 6.6 Hz, 4 H), 3.63 (t, J ϭ 6.5 Hz,
4 H), 4.56 (s, 4 H), 7.25Ϫ7.30 (m, 2 H), 7.35Ϫ7.42 (m, 2 H) ppm.
13C NMR (CDCl3, 62.9 MHz): δ ϭ 25.58 (t, 2 C), 26.08 (t, 2 C),
29.26 (t, 2 C), 29.31 (t, 2 C), 29.42 (t, 8 C), 29.62 (t, 2 C), 32.60 (t,
2 C), 62.78 (t, 2 C), 70.28 (t, 2 C), 70.50 (t, 2 C), 127.41 (d, 2 C),
128.37 (d, 2 C), 136.53 (s, 2 C) ppm. IR (neat): ν˜ ϭ 3301 (OH),
3066 (ArϪH), 3028 (ArϪH), 2921, 2853, 1465, 1360, 1217, 1188,
1103, 1061, 746 cmϪ1. MS (70 eV): m/z (%) ϭ 504 (0.2), 304 (82),
120 (100), 105 (44). MS [FAB(ϩ), Xenon]: m/z (%) ϭ 507 (3)
[MHϩ], 305 (12), 121 (36), 105 (100), 92 (4). C32H58O4 (506.81):
calcd. C 75.84, H 11.54; found C 75.53, H 11.22. 16b: Yield: 6%.
8. Sequence 15b to 19b
17b: 15b (5.00 g, 9.87 mmol), oxayl chloride (7.80 g, 61.5 mmol),
DMSO (8.05 g, 103 mmol), Et3N (15.6 g, 154 mmol), purification
by column chromatography (H/EE, 7:1). Yield: 3.97 g (80%). Rf
1
M.p. 47 °C. Rf (H/EA, 1:1) ϭ 0.38. H NMR (CDCl3, 250 MHz):
δ ϭ 1.27 (br., 48 H), 1.44 (s, 2 H), 1.51Ϫ1.64 (m, 12 H), 3.47 (t,
J ϭ 6.6 Hz, 8 H), 3.63 (t, J ϭ 6.6 Hz, 4 H), 4.56 (s, 8 H), 7.25Ϫ7.30
(m, 4 H), 7.35Ϫ7.41 (m, 4 H) ppm. 13C NMR (CDCl3, 62.9 MHz):
δ ϭ 25.58 (t, 2 C), 26.09 (t, 4 C), 29.26 (t, 2 C), 29.31 (t, 2 C),
29.34 (t, 2 C), 29.42 (t, 8 C), 29.45 (t, 4 C), 29.63 (t, 4 C), 32.63 (t,
2 C), 62.81 (t, 2 C), 70.27 (t, 4 C), 70.51 (t, 4 C), 127.40 (d, 4 C),
128.36 (d, 4 C), 136.54 (s, 4 C) ppm. IR (neat): ν˜ ϭ 3410 (OH),
3066 (ArϪH), 3028 (ArϪH), 2926, 2854, 1459, 1361, 1216, 1186,
1095, 752 cmϪ1. MS (70 eV): m/z (%) ϭ 808 (0.1), 608 (16), 406
(23), 304 (100), 120 (36), 105 (15). MS [FAB(Ϫ), Xenon]: m/z (%) ϭ
810 (0.7) [M Ϫ H]ϩ, 153 (100). C52H90O6 (811.29): calcd. C 76.99,
H 11.18; found C 76.91, H 11.11.
1
(H/EA, 5:1) ϭ 0.30. H NMR (CDCl3, 250 MHz): δ ϭ 1.27 (br. s,
28 H), 1.55Ϫ1.68 (m, 8 H), 2.42 (dt, J ϭ 1.9, 7.3 Hz, 4 H), 3.47 (t,
J ϭ 6.6 Hz, 4 H), 4.56 (s, 4 H), 7.25Ϫ7.30 (m, 2 H), 7.35Ϫ7.40 (m,
2 H), 9.76 (t, J ϭ 1.9 Hz, 2 H) ppm. 13C NMR (CDCl3, 62.9 MHz):
δ ϭ 21.90 (t, 2 C), 26.08 (t, 2 C), 28.97 (t, 2 C), 29.16 (t, 2 C),
29.22 (t, 2 C), 29.29 (t, 2 C), 29.33 (t, 2 C), 29.38 (t, 2 C), 29.63 (t,
2 C), 43.71 (t, 2 C), 70.26 (t, 2 C), 70.47 (t, 2 C), 127.37 (d, 2 C),
128.31 (d, 2 C), 136.55 (s, 2 C), 202.61 (d, 2 C) ppm. IR (neat):
ν˜ ϭ 3066 (ArϪH), 3027 (ArϪH), 2927, 2854, 2716 (H-CO), 1725
(CϭO), 1459, 1361, 1216, 1187, 1096, 754 cmϪ1. MS (70 eV): m/z
(%) ϭ 502 (0.7) [Mϩ], 484 (0.7) [M Ϫ H2O]ϩ, 459 (3) [M Ϫ
CH2CHO]ϩ, 274 (46), 120 (100), 105 (23). C32H54O4 (502.78):
calcd. C 76.45, H 10.83; found C 76.21, H 10.59.
7. Sequence 15a to 19a
18b: 17b (2.60 g, 5.17 mmol), propargylmagnesium bromide (1.6 ,
11.3 mL, 18.1 mmol), purification by HPLC (H/dioxane, 10:2).
Yield: 2.51 mg (83%). Rf (H/EA, 2:1) ϭ 0.24. 1H NMR (CDCl3,
250 MHz): δ ϭ 1.27 (br. s, 32 H), 1.50Ϫ1.64 (m, 8 H), 1.87 (br. s,
2 H), 2.05 (t, J ϭ 2.6 Hz, 2 H), 2.31 (ddd, J ϭ 2.7, 6.7, 16.7 Hz, 2
H), 2.43 (ddd, J ϭ 2.6, 4.8, 16.7 Hz, 2 H), 3.47 (t, J ϭ 6.6 Hz, 4
H), 3.71Ϫ3.80 (m, 2 H), 4.56 (s, 4 H), 7.25Ϫ7.30 (m, 2 H),
7.35Ϫ7.40 (m, 2 H) ppm. 13C NMR (CDCl3, 62.9 MHz): δ ϭ 25.41
(t, 2 C), 26.08 (t, 2 C), 27.17 (t, 2 C), 29.30 (t, 2 C), 29.38 (t, 10
C), 29.61 (t, 2 C), 36.04 (t, 2 C), 69.67 (d, 2 C), 70.25 (t, 2 C), 70.47
(t, 2 C), 70.52 (d, 2 C), 80.89 (s, 2 C), 127.39 (d, 2 C), 128.36 (d, 2
C), 136.52 (s, 2 C) ppm. IR (neat): ν˜ ϭ 3422 (OH), 3307 (ϵCϪH),
3067 (ArϪH), 3028 (ArϪH), 2926, 2854, 2118 (CϵC), 1459, 1361,
1219, 1188, 1091, 753 cmϪ1. MS (70 eV): m/z (%) ϭ 582 (0.2) [Mϩ],
543 (8), [M Ϫ C3H3]ϩ, 342 (9), 324 (5), 303 (8), 171 (4), 142 (100),
120 (57), 105 (61). C38H62O4 (582.91): calcd. C 78.30 H, 10.72;
found C 78.05, H 10.48. M.p. 44Ϫ45 °C.
17a: 15a (5.00 g, 16.1 mmol), oxalyl chloride (9.81 g, 77.3 mmol),
DMSO (10.1 g, 129 mmol), Et3N (19.6 g, 194 mmol), purification
by column chromatography (H/EE, 2:1). Yield: 4.42 mg (90%). Rf
1
(H/EA, 1:1) ϭ 0.36. H NMR (CDCl3, 250 MHz): δ ϭ 1.58Ϫ1.80
(m, 8 H), 2.46 (dt, J ϭ 1.6, 7.1 Hz, 4 H), 3.49 (t, J ϭ 6.0 Hz, 4 H),
4.55 (s, 4 H), 7.26Ϫ7.31 (m, 2 H), 7.34Ϫ7.39 (m, 2 H), 9.76 (t, J ϭ
1.6 Hz, 2 H) ppm. 13C NMR (CDCl3, 62.9 MHz): δ ϭ 18.73 (t, 2
C), 28.92 (t, 2 C), 43.31 (t, 2 C), 69.69 (t, 2 C), 70.24 (t, 2 C),
127.46 (d, 2 C), 128.35 (d, 2 C), 136.24 (s, 2 C), 202.20 (d, 2 C)
ppm. IR (neat): ν˜ ϭ 3066 (ArϪH), 3029 (ArϪH), 2937, 2863, 2723
(H-CO), 1723 (CϭO), 1454, 1362, 1218, 1188, 1095, 756 cmϪ1. MS
(70 eV): m/z (%) ϭ 306 (0.7) [Mϩ], 204 (31), 120 (27), 105 (25), 85
(100). C18H26O4 (306.40): calcd. C 70.56, H 8.55; found C 70.39,
H 8.56.
18a: 17a (4.20 mg, 13.7 mmol), propargylmagnesium bromide (1.6
, 24.0 mL, 38.4 mmol), purification by column chromatography
(H/EE, 2:1). Yield: 1.99 mg (38%). Rf (H/EA, 1:1) ϭ 0.18. 1H
NMR (CDCl3, 250 MHz): δ ϭ 1.38Ϫ1.67 (m, 12 H), 2.04Ϫ2.06 19b: 18b (1.21 g, 2.08 mmol), DMP (2.21 g, 5.21 mmol), DCM
(m, 2 H), 2.14 (s, 2 H), 2.30 (ddd, J ϭ 2.7, 6.6, 16.7 Hz, 2 H), 2.41 (3 mL), purification by column chromatography (H/EE, 7:1). Yield:
(ddd, J ϭ 2.6, 5.0, 16.7 Hz, 2 H), 3.49 (t, J ϭ 6.2 Hz, 4 H), 1.00 g (83%). Rf (H/EA, 5:1) ϭ 0.28. M.p. 37Ϫ38 °C. 1H NMR
3.70Ϫ3.79 (m, 2 H), 4.56 (s, 4 H), 7.25Ϫ7.31 (m, 2 H), 7.34Ϫ7.39 (CDCl3, 250 MHz): δ ϭ 1.26 (br. s, 28 H), 1.58Ϫ2.02 (m, 8 H),
(m, 2 H) ppm. 13C NMR (CDCl3, 62.9 MHz): δ ϭ 22.03 (t, 2 C), 2.59 (t, J ϭ 7 Hz, 4 H), 3.47 (t, J ϭ 6.6 Hz, 4 H), 4.56 (s, 4 H),
27.04 (t, 2 C), 29.26 (t, 2 C), 35.58 (t, 2 C), 69.37 (d, 2 C), 70.04
(d, 2 C), 70.17 (t, 2 C), 70.43 (t, 2 C), 80.78 (s, 2 C), 127.38 (d, 2
C), 128.36 (d, 2 C), 136.27 (s, 2 C) ppm. IR (neat): ν˜ ϭ 3410 (OH),
5.22 (d, J ϭ 6.5 Hz, 4 H), 5.77 (t, J ϭ 6.5 Hz, 2 H), 7.25Ϫ7.29 (m,
2 H), 7.30Ϫ7.41 (m, 2 H) ppm. 13C NMR (CDCl3, 62.9 MHz): δ ϭ
24.40 (t, 2 C), 26.08 (t, 2 C), 29.02 (t, 2 C), 29.20 (t, 2 C), 29.27 (t,
1932
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
Eur. J. Org. Chem. 2004, 1923Ϫ1935

Synthesis of 2,4-Furanophanes by Palladium-Catalyzed Macrocyclization Reactions
FULL PAPER
2 C), 29.30 (t, 2 C), 29.36 (t, 2 C), 29.40 (t, 2 C), 29.63 (t, 2 C),
39.63 (t, 2 C), 70.26 (t, 2 C), 70.48 (t, 2 C), 79.09 (t, 2 C), 96.50 (d,
2 C), 127.38 (d, 2 C), 128.32 (d, 2 C), 136.54 (s, 2 C), 200.76 (s, 2
C), 216.42 (s, 2 C) ppm. IR (neat): ν˜ ϭ 3065 (ArϪH), 2926, 2854,
1934 (CϭCϭC), 1682 (CϭO), 1459, 1411, 1361, 1161, 1096, 851,
752 cmϪ1. MS (70 eV): m/z (%) ϭ 578 (3) [Mϩ], 379 (2), 340 (100),
237 (12), 197 (7), 183 (11), 120 (10), 105 (8). C38H58O4 (578.88):
calcd. C 78.85, H 10.10; found C 78.53, H 10.13.
10. Sequence 16b to 24b
22b: 16b (1.97 g, 2.43 mmol), oxalyl chloride (1.90 g, 15.0 mmol),
DMSO (1.99 g, 25.5 mmol), Et3N (3.90 g, 38.5 mmol), purification
by column chromatography (H/EE, 7:1). Yield: 1.83 mg (93%).
1
M.p. 36 °C. Rf (H/EA, 5:1) ϭ 0.36. H NMR (CDCl3, 250 MHz):
δ ϭ 1.17Ϫ1.28 (m, 44 H), 1.45Ϫ1.56 (m, 12 H), 2.28 (dt, J ϭ 1.8,
7.3 Hz, 4 H), 3.36 (t, J ϭ 6.5 Hz, 8 H), 4.45 (s, 8 H), 7.12Ϫ7.18
(m, 4 H), 7.24Ϫ7.31 (m, 4 H), 9.62 (t, J ϭ 1.8 Hz, 2 H) ppm. 13C
NMR (CDCl3, 62.9 MHz): δ ϭ 21.90 (t, 2 C), 26.10 (t, 4 C), 28.98
(t, 2 C), 29.18 (t, 2 C), 29.23 (t, 2 C), 29.30 (t, 2 C), 29.34 (t, 4 C),
29.39 (t, 4 C), 29.45 (t, 4 C), 29.66 (t, 2 C), 43.70 (t, 2 C), 70.28 (t,
4 C), 70.46 (t, 4 C), 127.35 (d, 4 C), 128.30 (d, 4 C), 136.57 (s, 4
C), 202.43 (d, 2 C) ppm. IR (neat): ν˜ ϭ 3066 (ArϪH), 3028
(ArϪH), 2926, 2854, 2715 (HϪCO), 1726 (CϭO), 1459, 1361,
1216, 1187, 1096, 753 cmϪ1. MS (70 eV): m/z (%) ϭ 806 (0.1) [M
Ϫ H]ϩ, 788 (1), 606 (33), 406 (42), 302 (78), 274 (44), 206 (20), 120
(100), 105 (86). MS [FAB(ϩ), Xenon]: m/z (%) ϭ 807 (0.7) [Mϩ],
607 (0.5), 406 (1), 303 (8), 207 (8), 105 (100), 91 (22). C52H86O6
(807.25): calcd. C 77.37, H 10.74; found C 77.35 H, 10.55.
9. Sequence 16a to 24a
22a: 16a (1.03 g, 1.99 mmol), oxalyl chloride (1.50 g, 11.8 mmol),
DMSO (1.54 g, 19.7 mmol), Et3N (2.99 g, 29.5 mmol), purification
by column chromatography (H/EE, 2:1). Yield: 943 mg (92%). Rf
1
(H/EA, 1:1) ϭ 0.40. H NMR (CDCl3, 250 MHz): δ ϭ 1.42Ϫ1.51
(m, 2 H), 1.57Ϫ1.76 (m, 12 H), 2.44 (dt, J ϭ 1.6, 7.1 Hz, 4 H),
3.45Ϫ3.50 (m, 8 H), 4.55 (s, 8 H), 7.23Ϫ7.30 (m, 4 H), 7.34Ϫ7.39
(m, 4 H), 9.74 (d, J ϭ 1.6 Hz, 2 H) ppm. 13C NMR (CDCl3,
62.9 MHz): δ ϭ 18.82 (t, 2 C), 22.81 (t), 29.01 (t, 2 C), 29.46 (t, 2
C), 43.40 (t, 2 C), 69.75 (t, 2 C), 70.31 (t, 6 C), 127.48 (d, 2 C),
127.51 (d, 2 C), 128.35 (d, 2 C), 128.42 (d, 2 C), 136.33 (s, 2 C),
136.46 (s, 2 C), 202.27 (d, 2 C) ppm. IR (neat): ν˜ ϭ 3066 (ArϪH),
3029 (ArϪH), 2936, 2861, 2722 (HϪCO), 1723 (CϭO), 1454, 1361,
1218, 1188, 1095, 755 cmϪ1. MS (70 eV): m/z (%) ϭ 410 (0.8), 204
(20), 119 (20), 105 (47), 85 (100). MS [FAB(ϩ), Xenon]: m/z (%) ϭ
513 (1.2) [MHϩ], 327 (1.2), 205 (10), 119 (20), 105 (84), 85 (100).
C31H44O6 (512.69), (C26H34O4): calcd. 410.24571, found
410.24562 (MS).
23b: 22b (1.81 g, 2.24 mmol), propargylmagnesium bromide (1.6 ,
4.88 mL, 7.80 mmol), purification by HPLC (H/E/EE, 10:10:1).
Yield: 1.45 g (73%). Rf (H/EA, 2:1) ϭ 0.36. 1H NMR (CDCl3,
250 MHz): δ ϭ 1.27 (br. s, 44 H), 1.50Ϫ1.64 (m, 16 H), 1.89 (br. s,
2 H), 2.05 (t, J ϭ 2.6 Hz, 2 H), 2.30 (ddd, J ϭ 2.7, 6.7, 16.7 Hz, 2
H), 2.43 (ddd, J ϭ 2.6, 4.7, 16.7 Hz, 2 H), 3.47 (t, J ϭ 6.6 Hz, 8
H), 3.70Ϫ3.79 (m, 2 H), 4.56 (s, 8 H), 7.25Ϫ7.30 (m, 4 H),
7.35Ϫ7.41 (m, 4 H) ppm. 13C NMR (CDCl3, 62.9 MHz): δ ϭ 25.43
(t, 2 C), 26.10 (t, 4 C), 27.18 (t, 2 C), 29.40 (t, 10 C), 29.46 (t, 8
C), 29.64 (t, 4 C), 36.06 (t, 2 C), 69.68 (d, 2 C), 70.27 (t, 4 C), 70.50
(t, 4 C), 70.54 (t, 2 C), 80.85 (s, 2 C), 127.41 (d, 4 C), 128.36 (d, 4
C), 136.53 (s, 4 C) ppm. IR (neat): ν˜ ϭ 3442 (OH), 3308 (ϵCϪH),
3066 (ArϪH), 3028 (ArϪH), 2926, 2854, 2118 (CϵC), 1495, 1361,
1317, 1187, 1093, 752 cmϪ1. MS (70 eV): m/z (%) ϭ 887 (0.7) [Mϩ],
606 (23), 442 (17), 340 (100), 302 (69), 274 (43), 206 (29), 135 (38),
120 (69), 105 (97); [FABϩ]: m/z (%) ϭ 888 (0.1) [MHϩ], 646 (0.2),
406 (0.3), 343 (2), 305 (2), 254 (15), 119 (50), 105 (100). C58H94O6
(887.38): calcd. C 78.50, H 10.68; found C 78.24, H 10.71.
23a: 22 (918 mg, 1.79 mmol), (1.6 , 4.5 mL, 7.2 mmol) propar-
gylmagnesium bromide, purification by column chromatography
(H/EE, 2:1). Yield: 649 mg (61%). Rf (H/EA, 1:1) ϭ 0.26. 1H NMR
(CDCl3, 250 MHz): δ ϭ 1.40Ϫ1.69 (m, 18 H), 1.99 (br. s, 2 H),
2.05 (t, J ϭ 2.6 Hz, 2 H), 2.30 (ddd, J ϭ 2.7, 6.6, 16.7 Hz, 2 H),
2.41 (ddd, J ϭ 2.6, 4.9, 16.7 Hz, 2 H), 3.45Ϫ3.51 (m, 8 H),
3.70Ϫ7.79 (m, 2 H), 4.56 (s, 8 H), 7.25Ϫ7.31 (m, 4 H), 7.35Ϫ7.40
(m, 4 H) ppm. 13C NMR (CDCl3, 62.9 MHz): δ ϭ 22.20 (t, 2 C),
22.79 (t), 27.20 (t, 2 C), 29.43 (t, 4 C), 35.75 (t, 2 C), 69.52 (d, 2
C), 70.18 (t, 2 C), 70.30 (t, 6 C), 70.61 (t, 2 C), 80.85 (s, 2 C),
127.49 (d, 2 C), 127.52 (d, 2 C), 128.43 (d, 2 C), 128.46 (d, 2 C),
136.38 (s, 2 C), 136.48 (s, 2 C) ppm; 1 ϵCH hidden/overlapping, 1
CH2 hidden/overlapping. IR (neat): ν˜ ϭ 3426 (OH), 3297 (ϵCϪH),
3066 (ArϪH), 3029 (ArϪH), 2935, 2862, 2117 (CϵC), 1454, 1360,
1218, 1187, 1093, 755 cmϪ1. MS (70 eV): m/z (%) ϭ 450 (0.2), 410
(0.3), 327 (1), 245 (2), 205 (17), 142 (19), 120 (68), 105 (86), 85
(100). MS [FAB(ϩ), Xenon]: m/z (%) ϭ 615 (0.6) [M ϩ Na]ϩ, 593
(4) [MHϩ], 472 (3), 245 (12), 207 (9), 120 (27), 105 (100), 91 (47).
C37H52O6 (592.82).
24b: 23b (712 mg, 802 µmol), DMP (852 mg, 2.01 mmol), DCM
(3 mL), purification by column chromatography (H/EE, 6:1). Yield:
639 mg (90%). M.p. 47 °C. Rf (H/EA, 5:1) ϭ 0.32. 1H NMR
(CDCl3, 250 MHz): δ ϭ 1.26 (br. s, 44 H), 1.55Ϫ1.63 (m, 12 H),
2.58 (t, J ϭ 7 Hz, 4 H), 3.46 (t, J ϭ 6.6 Hz, 8 H), 4.56 (s, 8 H),
5.21 (d, J ϭ 6.5 Hz, 4 H), 5.76 (t, J ϭ 6.5 Hz, 2 H), 7.24Ϫ7.29 (m,
4 H), 7.35Ϫ7.40 (m, 4 H) ppm. 13C NMR (CDCl3, 62.9 MHz): δ ϭ
24.41 (t, 2 C), 26.11 (t, 4 C), 29.03 (t, 2 C), 29.22 (t, 2 C), 29.29 (t,
2 C), 29.32 (t, 2 C), 29.35 (t, 2 C), 29.38 (t, 2 C), 29.42 (t, 2 C),
29.46 (t, 4 C), 29.65 (t, 4 C), 39.70 (t, 2 C), 70.28 (t, 4 C), 70.49 (t,
4 C), 79.11 (t, 2 C), 96.51 (d, 2 C), 127.39 (d, 4 C), 128.33 (d, 4 C),
136.55 (s, 4 C), 200.77 (s, 2 C), 216.43 (s, 2 C) ppm. IR (neat): ν˜ ϭ
3065 (ArϪH), 3025 (ArϪH), 2926, 2854, 1934 (CϭCϭC), 1683
(CϭO), 1459, 1411, 1361, 1158, 1096, 850, 753 cmϪ1. MS (70 eV):
m/z (%) ϭ 883 (0.8) [Mϩ], 644 (3), 578 (6), 442 (14), 406 (11), 341
(33), 340 (100), 274 (49), 197 (12), 183 (17), 135 (49), 120 (74), 105
(90); [FABϩ] m/z (%) ϭ 884 (0.2) [MHϩ], 645 (0.2), 406 (0.4), 341
(5), 207 (6), 154 (14), 136 (14), 119 (44), 105 (100). C58H90O6
(883.35): calcd. C 78.86, H 10.27; found C 78.99, H 10.19.
24a: 23a (641 mg, 1.08 mmol), DMP (1.38 mg, 3.25 mmol), DCM
(3 mL), purification by HPLC (H/EE, 10:4.33 ϩ 30% DMC).
Yield: 244 mg (38%). Rf (H/EA, 1:1) ϭ 0.42. 1H NMR (CDCl3,
250 MHz): δ ϭ 1.41Ϫ1.51 (m, 2 H), 1.54Ϫ1.76 (m, 12 H),
2.59Ϫ2.64 (m, 4 H), 3.47 (t, J ϭ 6.2 Hz, 8 H), 4.54 (s, 8 H), 5.19
(d, J ϭ 6.6 Hz, 4 H), 5.75 (t, J ϭ 6.5 Hz, 2 H), 7.24Ϫ7.29 (m, 4
H), 7.34Ϫ7.39 (m, 4 H) ppm. 13C NMR (CDCl3, 62.9 MHz): δ ϭ
21.23 (t, 2 C), 22.80 (t), 29.04 (t, 2 C), 29.46 (t, 2 C), 38.65 (t, 2
C), 69.99 (t, 2 C), 70.28 (t, 6 C), 79.21 (t, 2 C), 96.48 (d, 2 C),
127.41 (d, 2 C), 127.43 (d, 2 C), 128.33 (d, 4 C), 136.41 (s, 2 C),
136.47 (s, 2 C), 200.27 (s, 2 C), 261.41 (s, 2 C) ppm. IR (neat): ν˜ ϭ
3064 (ArϪH), 3028 (ArϪH), 2936, 2861, 1934 (CϭCϭC), 1680
(CϭO), 1453, 1412, 1361, 1160, 1094, 857, 754 cmϪ1. MS (70 eV):
11. Cyclization/Macrocyclization of 15a,b and 16a,b to 20a,b/21a,b
and 25a,b/26a,b
m/z (%) ϭ 588 (0.3) [Mϩ], 488 (0.5), 324 (2), 242 (13), 206 (13), The conditions for the cyclizations are similar to the conditions
183 (13), 135 (43), 119 (81), 104 (100), 91 (53), 81 (5). C37H48O6 described for the cyclization of the diallenyl diketones 8 (details
(588.72): calcd. C 75.48, H 8.22; found C 75.27, H 8.19.
listed in Table 2).
Eur. J. Org. Chem. 2004, 1923Ϫ1935
www.eurjoc.org
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
1933

A. S. K. Hashmi, L. Schwarz, M. Bolte
FULL PAPER
H), 7.23Ϫ7.30 (m, 2 H), 7.31Ϫ7.41 (m, 2 H), 7.55 (d, J ϭ 0.7 Hz,
1 H) ppm. 13C NMR (CDCl3, 62.9 MHz): δ ϭ 16.53 (q), 24.72 (t),
25.92 (t), 26.13 (t), 27.03 (t), 27.54 (t), 28.42 (t), 28.77 (t), 28.86 (t),
28.92 (t), 29.01 (t), 29.06 (t, 2 C), 29.16 (t, 3 C), 29.19 (t), 29.25 (t),
29.59 (t, 2 C), 44.76 (t), 70.35 (t), 70.43 (t), 70.48 (t), 70.57 (t),
102.25 (d), 120.43 (d), 127.38 (d), 127.52 (d), 128.39 (d), 128.58 (d),
128.97 (s), 136.45 (s), 136.77 (s), 141.41 (d), 144.84 (s), 158.05 (s),
201.76 (s) ppm. IR (neat): ν˜ ϭ 3124, 3029, 2926, 2854, 1765, 1678
Table 2. Amount of substrates 19, 24 and catalyst
Starting
material
Quantity
Quantity of catalyst
19a
19b
24a
24b
95.6 mg (250 µmol)
147 mg (250 µmol)
145 mg (247 µmol)
220 mg (249 µmol)
3.1 mg (11.9 µmol, 5 mol%)
3.2 mg (12.3 µmol, 5 mol%)
3.3 mg (12.7 µmol, 5 mol%)
3.3 mg (12.7 µmol, 5 mol%)
(CϭO), 1591, 1459, 1364, 1186, 1128, 1096, 942, 801, 752 cmϪ1
.
MS (70 eV): m/z (%) ϭ 578 (16) [Mϩ], 459 (14), 379 (100), 135 (50).
C38H58O4 (578.88). HRMS calcd. 578.433510, found 578.433140
(MS).
25a: 24a (25.1 mg, 42.5 µmol), AgNO3 (5.0 mg, 29 µmol), acetone
20a: 19a (90.0 mg, 235 µmol), AgNO3 (2.7 mg, 15.9 µmol), acetone
(2 mL), column chromatography (H/EE, 6:1). Yield: 19.0 mg
(1 mL), column chromatography (H/EE, 5:1). Yield: 17.7 mg
1
1
(76%). Rf (H/EA, 2:1) ϭ 0.48. H NMR (CDCl3, 250 MHz): δ ϭ
(20%). Rf (H/EA, 5:1) ϭ 0.46. H NMR (CDCl3, 250 MHz): δ ϭ
1.45Ϫ1.51 (m, 2 H), 1.58Ϫ1.76 (m, 12 H), 2.61Ϫ2.67 (m, 4 H),
3.44Ϫ3.50 (m, 8 H), 4.56 (s, 8 H), 5.97 (dd, J ϭ 0.8, 3.1 Hz, 2 H),
6.27 (d, J ϭ 1.9 Hz, 3.1 Hz, 2 H), 7.25Ϫ7.30 (m, 6 H), 7.35Ϫ7.40
(m, 4 H) ppm. 13C NMR (CDCl3, 62.9 MHz): δ ϭ 22.81 (t), 24.65
(t, 2 C), 27.57 (t, 2 C), 29.10 (t, 2 C), 29.47 (t, 2 C), 70.00 (t, 2 C),
70.32 (t, 6 C), 104.62 (d, 2 C), 109.88 (d, 2 C), 127.44 (d, 2 C),
127.47 (d, 2 C), 128.38 (d, 4 C), 136.42 (s, 2 C), 136.52 (s, 2 C),
140.56 (d, 2 C), 155.95 (s, 2 C) ppm. IR (neat): ν˜ ϭ 3114 (ArϪH),
3067 (ArϪH), 3029 (ArϪH), 2937, 2860, 1596, 1505, 1453, 1360,
1094, 1010, 920, 794, 751 cmϪ1. MS (70 eV): m/z (%) ϭ 588 (0.3)
[Mϩ], 448 (2), 344 (5), 242 (27), 206 (17), 183 (32), 123 (45), 104
(100), 81 (56). C37H48O6 (588.79): calcd. 588.34509, found
588.34561 (MS).
1.61Ϫ1.78 (m, 8 H), 2.62Ϫ2.68 (m, 4 H), 3.48Ϫ3.52 (m, 4 H), 4.57
(s, 4 H), 5.98Ϫ5.99 (m, 2 H), 6.27Ϫ6.29 (m, 2 H), 7.29Ϫ7.30 (m,
2 H), 7.26Ϫ7.32 (m, 2 H), 7.36Ϫ7.41 (m, 2 H) ppm. 13C NMR
(CDCl3, 62.9 MHz): δ ϭ 24.65 (t, 2 C), 27.58 (t, 2 C), 29.10 (t, 2
C), 70.01 (t, 2 C), 70.34 (t, 2 C), 104.63 (d, 2 C), 109.89 (d, 2 C),
127.49 (d, 2 C), 128.40 (d, 2 C), 136.45 (s, 2 C), 140.57 (d, 2 C),
155.95 (s, 2 C) ppm. IR (neat): ν˜ ϭ 3115 (ArϪH), 3067 (ArϪH),
3029 (ArϪH), 2938, 2861, 1596, 1506, 1454, 1362, 1095, 1008, 921,
797 cmϪ1. MS (70 eV): m/z (%) ϭ 382 (0.5) [Mϩ], 242 (15), 183
(45), 139 (46), 121 (57), 104 (100), 81 (64). C24H30O4: calcd.
382.21441, found 382.21425 (MS). C24H30O4 (382.50): calcd. C
75.36, H 7.91; found C 75.35, H 8.12.
21a: Yield: 30.1 mg (31%). Rf (H/EA, 5:1) ϭ 0.24. 1H NMR
(CDCl3, 250 MHz): δ ϭ 1.54Ϫ1.78 (m, 8 H), 2.32 (s, 3 H), 2.32 (t,
J ϭ 7.2 Hz, 2 H), 2.58 (m, 2 H), 3.39Ϫ3.48 (m, 4 H), 4.52 (s, 2 H),
4.56 (s, 2 H), 6.28 (s, 1 H), 6.47 (s, 1 H), 7.18Ϫ7.23 (m, 2 H),
7.26Ϫ7.37 (m, 2 H), 7.46 (s, 1 H) ppm. 13C NMR (CDCl3,
62.9 MHz): δ ϭ 16.36 (q), 22.74 (t), 22.85 (t), 26.85 (t), 28.01 (t),
28.83 (t), 44.34 (t), 69.61 (t), 69.63 (t), 69.94 (t), 70.64 (t), 102.72
(d), 119.93 (d), 127.48 (d), 127.50 (d), 128.43 (d), 128.51 (d), 129.20
(s), 136.33 (s), 136.43 (s), 141.44 (d), 145.09 (s), 157.68 (s), 202.06
(s) ppm. IR (neat): ν˜ ϭ 3125 (ArϪH), 3065 (ArϪH), 3029 (ArϪH),
2936, 2862, 1764, 1674 (CϭO), 1589, 1447, 1365, 1130, 1095, 945,
804, 752 cmϪ1. MS (70 eV): m/z (%) ϭ 382 (100) [Mϩ], 281 (49),
277 (77), 233 (53), 104 (83). C24H30O4 (382.50). HRMS calcd.
382.214410, found 382.214240 (MS).
26a: Yield: 40.0 mg (27%). Rf (H/EA, 2:1) ϭ 0.34. 1H NMR
(CDCl3, 250 MHz): δ ϭ 1.44Ϫ1.80 (m, 14 H), 2.41 (d, J ϭ 1.0 Hz,
3 H), 2.48Ϫ2.54 (m, 2 H), 2.61Ϫ2.66 (m, 2 H), 3.44Ϫ3.53 (m, 8
H), 4.57 (s, 4 H), 4.58 (s, 4 H), 6.21 (s, 1 H), 6.40 (s, 1 H), 7.25Ϫ7.32
(m, 4 H), 7.33Ϫ7.41 (m, 4 H), 7.54 (s, 1 H) ppm. 13C NMR
(CDCl3, 62.9 MHz): δ ϭ 16.61 (q), 21.55 (t), 22.83 (t), 24.23 (t),
27.40 (t), 28.87 (t, 2 C), 29.47 (t, 2 C), 44.35 (t), 69.76 (t, 2 C),
70.35 (t, 4 C), 70.54 (t), 70.70 (t), 102.46 (d), 120.38 (d), 127.43 (d),
127.49 (d), 127.60 (d), 127.66 (d), 128.40 (d), 128.51 (d), 128.69 (d,
2 C), 128.98 (s), 136.21 (s), 136.32 (s), 136.65 (s), 136.77 (s), 141.42
(d), 144.99 (s), 157.73 (s), 201.24 (s) ppm. IR (neat): ν˜ ϭ 3066
(ArϪH), 3029 (ArϪH), 2936, 2861, 1763, 1678 (CϭO), 1590, 1452,
1363, 1187, 1096, 914, 801, 752 cmϪ1. MS (70 eV): m/z (%) ϭ 588
(16) [Mϩ], 487 (10), 469 (12), 397 (14), 381 (10), 119 (63), 105 (100).
C37H48O6 (588.79). calcd. 588.34509, found 588.345610 (MS).
20b: 19b (90.0 mg, 155 µmol), AgNO3 (2.8 mg, 16.5 µmol), acetone
(1 mL), column chromatography (H/EE, 20:1). Yield: 71.0 mg
(79%). M.p. 30Ϫ35 °C. Rf (H/EA, 10:1) ϭ 0.50. 1H NMR (CDCl3,
250 MHz): δ ϭ 1.28 (br. s, 28 H), 1.58Ϫ1.66 (m, 8 H), 2.62 (t, J ϭ
7.5 Hz, 4 H), 3.48 (t, J ϭ 6.6 Hz, 4 H), 4.57 (s, 4 H), 5.97 (dd, J ϭ
0.7, 3.1 Hz, 2 H), 6.28 (dd, J ϭ 2.0, 3.0 Hz, 2 H), 7.26Ϫ7.31 (m, 4
H), 7.36Ϫ7.41 (m, 2 H) ppm. 13C NMR (CDCl3, 62.9 MHz): δ ϭ
26.14 (t, 2 C), 27.84 (t, 2 C), 27.91 (t, 2 C), 29.05 (t, 2 C), 29.23 (t,
2 C), 29.35 (t, 2 C), 29.40 (t, 2 C), 29.44 (t, 4 C), 29.68 (t, 2 C),
70.32 (t, 2 C), 70.52 (t, 2 C), 104.36 (d, 2 C), 109.86 (d, 2 C), 127.42
(d, 2 C), 128.38 (d, 2 C), 136.59 (s, 2 C), 140.45 (d, 2 C), 156.44 (s,
2 C) ppm. IR (neat): ν˜ ϭ 3114 (ArϪH), 3066 (ArϪH), 3028
(ArϪH), 2926, 2854, 1596, 1507, 1460, 1360, 1096, 1008, 928, 794
cmϪ1. MS (70 eV): m/z (%) ϭ 578 (0.8) [Mϩ], 340 (100), 237 (12),
197 (6), 183 (11), 169 (10), 120 (8), 105 (6). C38H58O4 (578.88):
calcd. C 78.85, H 10.10; found C 78.54, H 10.06.
25b: 24b (93.0 mg, 105 µmol), AgNO3 (2.5 mg, 15 µmol), acetone
(2 mL), column chromatography (H/EE, 20:1). Yield: 57.8 mg
1
(62%). Rf (H/EA, 5:1) ϭ 0.64. H NMR (CDCl3, 250 MHz): δ ϭ
1.27 (br. s, 44 H), 1.56Ϫ1.63 (m, 12 H), 2.61 (t, J ϭ 7.6 Hz, 4 H),
3.47 (t, J ϭ 6 Hz, 8 H), 4.57 (s, 8 H), 5.96Ϫ5.97 (m, 2 H),
6.26Ϫ6.28 (m, 2 H), 7.24Ϫ7.31 (m, 6 H), 7.36Ϫ7.41 (m, 4 H) ppm.
13C NMR (CDCl3, 62.9 MHz): δ ϭ 26.14 (t, 4 C), 27.84 (t, 2 C),
27.90 (t, 2 C), 29.05 (t, 2 C), 29.23 (t, 2 C), 29.35 (t, 2 C), 29.39 (t,
4 C), 29.44 (t, 4 C), 29.49 (t, 4 C), 29.68 (t, 4 C), 70.31 (t, 4 C),
70.52 (t, 4 C), 104.36 (d, 2 C), 109.86 (d, 2 C), 127.42 (d, 4 C),
128.37 (d, 4 C), 136.58 (s, 4 C), 140.44 (d, 2 C), 156.44 (s, 2 C)
ppm. IR (neat): ν˜ ϭ 3113 (ArϪH), 3066 (ArϪH), 3028 (ArϪH),
2926, 2854, 1596, 1506, 1459, 1361, 1096, 1008, 917, 794, 749 cmϪ1
.
MS (70 eV): m/z (%) ϭ 883 (0.4) [Mϩ], 644 (6), 442 (14), 340 (100),
304 (12), 237 (13), 120 (33), 105 (25). C58H90O6 (883.35): calcd. C
78.86, H 10.27; found C 78.69, H 10.23.
21b: Yield: 34.2 mg (26%). Rf (H/EA, 5:1) ϭ 0.42. 1H NMR
(CDCl3, 250 MHz): δ ϭ 1.28 (br. s, 28 H), 1.55Ϫ1.68 (m, 8 H),
2.41 (d, J ϭ 1.1 Hz, 3 H), 2.44Ϫ2.50 (m, 2 H), 2.58Ϫ2.64 (m, 2
26b: Yield: 44.2 mg (20%). Rf (H/EA, 5:1) ϭ 0.30. 1H NMR
H), 3.46 (t, J ϭ 6.4 Hz, 2 H), 3.48 (t, J ϭ 6.5 Hz, 2 H), 4.57 (s, 2 (CDCl3, 250 MHz): δ ϭ 1.28 (br. s, 44 H), 1.57Ϫ1.65 (m, 12 H),
H), 4.58 (s, 2 H), 6.21 (d, J ϭ 0.8 Hz, 1 H), 6.43 (d, J ϭ 1.1 Hz, 1 2.41 (d, J ϭ 1.0 Hz, 3 H), 2.49 (t, J ϭ 7 Hz, 2 H), 2.61 (t, J ϭ
1934
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
Eur. J. Org. Chem. 2004, 1923Ϫ1935

Synthesis of 2,4-Furanophanes by Palladium-Catalyzed Macrocyclization Reactions
FULL PAPER
[12]
X.-T. Chen, S. K. Bhattacharya, B. Zhou, C. E. Gutteridge,
T. R. R. Pettus, S. J. Danishefsky, J. Am. Chem. Soc. 1999,
121, 6563Ϫ6579.
S. Leclercq, J. C. de Biseau, D. Daloze, J.-C. Braekman, Y.
Quinet, J. M. Pasteels, Tetrahedron Lett. 2000, 41, 633Ϫ637.
J. A. Marshall, E. D. Robin, J. Org. Chem. 1990, 55,
3450Ϫ3451.
J. A. Marshall, X. Wang, J. Org. Chem. 1991, 56, 960Ϫ969.
J. A. Marshall, X. Wang, J. Org. Chem. 1992, 57, 3387Ϫ3396.
J. A. Marshall, G. S. Bartley, J. Org. Chem. 1994, 59,
7169Ϫ7171.
J. A. Marshall, E. M. Wallace, P. S. Coan, J. Org. Chem. 1995,
60, 796Ϫ797.
J. A. Marshall, C. A. Sehon, J. Org. Chem. 1995, 60,
5966Ϫ5968.
J. A. Marshall, E. A. van Devender, J. Org. Chem. 2001, 66,
8037Ϫ8041.
7.4 Hz, 2 H), 3.48 (t, J ϭ 6.5 Hz, 8 H), 4.57 (s, 4 H), 4.58 (s, 4 H),
6.21 (s, 1 H), 6.41 (d, J ϭ 1.0 Hz, 1 H), 7.25Ϫ7.30 (m, 4 H),
7.35Ϫ7.41 (m, 4 H), 7.55 (s, 1 H) ppm. 13C NMR (CDCl3,
62.9 MHz): δ ϭ 17.16 (q), 24.98 (t), 26.59 (t, 1 C), 26.65 (t, 2 C),
27.94 (t), 28.26 (t), 29.29 (t), 29.60 (t, 2 C), 29.64 (t), 29.72 (t, 3 C),
29.75 (t, 3 C), 29.79 (t, 2 C), 29.85 (t, 4 C), 29.97 (t, 3 C), 30.11 (t,
2 C), 30.17 (t, 2 C), 45.30 (t), 70.91 (t, 2 C), 70.98 (t, 4 C), 71.04
(t, 2 C), 102.82 (d), 121.11 (d), 127.95 (d, 2 C), 128.00 (d, 2 C),
128.96 (d, 2 C), 129.04 (d, 2 C), 129.51 (s), 137.09 (s, 2 C), 137.22
(s, 2 C), 141.80 (d), 145.26 (s), 158.63 (s), 202.01 (s) ppm. IR (neat):
ν˜ ϭ 3065 (ArϪH), 3029 (ArϪH), 2926, 2854, 1765, 1680 (CϭO),
1592, 1458, 1362, 1186, 1097, 944, 800, 752 cmϪ1. MS (70 eV):
m/z (%) ϭ 882 (36) [Mϩ], 683 (36), 577 (29), 379 (80), 119 (58), 105
(100). C58H90O6 (883.35). calcd. 882.67374, found 882.67336 (MS).
[13]
[14]
[15]
[16]
[17]
[18]
[19]
[20]
[21]
12. Transformation of 27b to 28b
J. A. Marshall, G. S. Bartley, E. M. Wallace, J. Org. Chem.
1996, 61, 5729Ϫ5735.
J. Leonard, G. Ryan, Tetrahedron Lett. 1987, 28, 2525Ϫ2528.
W. Eberbach, N. Laber, Tetrahedron Lett. 1992, 33, 57Ϫ60.
F. Hadj-Abo, S. Bienz, M. Hesse, Tetrahedron 1994, 50,
8665Ϫ8672.
[Cl2(PCy3)2RuϭCHϪCϭCPh2] (16.1 mg, 20.1 µmol) was added to
27b (143 mg, 401 µmol) in DCM (40 mL). The solution was stirred
at room temperature until TLC demonstrated the complete con-
sumption of the starting material. Evaporation of the solvent and
column chromatography of the crude product on silica gel delivered
28b (44.3 mg, 31%) as a colorless oil.
28b: Rf(H/EA, 10:1) ϭ 0.29. 1H NMR (CDCl3, 250 MHz): δ ϭ
1.20 (m, 16 H), 1.55Ϫ1.70 (m, 4 H), 1.92Ϫ2.01 (m, 4 H), 2.35Ϫ2.41
(m, 5 H), 2.58 (t, J ϭ 6.7 Hz, 2 H), 5.28Ϫ5.32 (m, 2 H), 6.15 (br.
s, 1 H), 6.39 (br. s, 1 H), 7.51 (br. s, 1 H) ppm. 13C NMR (CDCl3,
62.9 MHz): δ ϭ 16.4/16.5, (25.7, 25.8, 26.2, 26.8, 26.9, 27.3, 27.6,
27.7, 27.9, 28.0, 28.3, 28.4, 28.5, 28.6, 28.7, 29.0, 29.2, 29.2, 29.3),
32.1/32.2, 44.6/44.8, 102.4/102.5, 120.2/120.6, 129.0/129.7, 130.2/
130.3, 141.5/141.6, 145.2, 157.7/157.8, 202.5/202.3 ppm. C24H36O2
(356.6).
[22]
[23]
[24]
[25]
[26]
[27]
W. Tochtermann, K. Luttmann, Tetrahedron Lett. 1987, 28,
2521Ϫ2524.
W. Tochtermann, K. Luttmann, N. Sdunnus, E.-M. Peters, K.
Peters, H. G. von Schnering, Chem. Ber. 1992, 125, 1485Ϫ1494.
P. J. Garratt, K. C. Nicolaou, F. Sondheimer, J. Org. Chem.
1973, 38, 864Ϫ868.
A. S. K. Hashmi, Angew. Chem. 1995, 107, 1749Ϫ1751.
A. S. K. Hashmi, L. Schwarz, Chem. Ber./Recueil 1997, 130,
1449Ϫ1456.
A. S. K. Hashmi, T. L. Ruppert, T. Knöfel, J. W. Bats, J. Org.
Chem. 1997, 62, 7295Ϫ7304.
A. S. K. Hashmi, J.-H. Choi, J. W. Bats, J. Prakt. Chem. 1999,
341, 342Ϫ357.
[28]
[29]
[30]
[31]
[32]
Acknowledgments
A. S. K. Hashmi, L. Schwarz, J. W. Bats, J. Prakt. Chem. 2000,
342, 40Ϫ51.
We thank the Deutsche Forschungsgemeinschaft (Ha, 1932/3Ϫ1
and 3Ϫ2) and the Fonds der Chemischen Industrie for their gen-
erous support. Palladium salts were donated by Umicore AG &
Co. KG.
[33]
[34]
[35]
D. B. Dess, J. C. Martin, J. Org. Chem. 1983, 48, 4155Ϫ4156.
R. E. Ireland, L. Liu, J. Org. Chem. 1993, 58, 2899Ϫ2899.
S. D. Meyer, S. L. Schreiber, J. Org. Chem. 1994, 59,
7549Ϫ7552.
[36]
[37]
[38]
[39]
A. Speicher, V. Bomm, T. Eicher, J. Prakt. Chem. 1996, 338,
[1]
588Ϫ590.
H. Scheytza, H.-U. Reissig, O. Rademacher, Tetrahedron 1999,
M. Frigerio, M. Santagostino, S. Sputore, J. Org. Chem. 1999,
64, 4537Ϫ4538.
A. S. K. Hashmi, J. W. Bats, J.-H. Choi, L. Schwarz, Tetra-
hedron Letters 1998, 39, 7491Ϫ7494.
CCDC-208302 (for 10g) and -208303 (for 12c) contain the sup-
plementary crystallographic data for this paper. These data can
be obtained free of charge via www.ccdc.cam.ac.uk/conts/
retrieving.html (or from the Cambridge Crystallographic Data
Centre, 12 Union Road, Cambridge CB2 1EZ, UK; Fax: ϩ 44-
1223-336-033, E-mail: deposit@ccdc.cam.ac.uk).
Different authors in: Top. Organomet. Chem., vol. 1: Alkene
Metathesis in Organic Synthesis, (Ed.: A. Fürstner), Springer-
Verlag, Heidelberg, 1998.
S. Sternhell, C. W. Tansey, Y. Tobe, K. Kakiuchi, K. Kobiro,
Magn. Reson. Chem. 1990, 28, 902Ϫ907.
Y. Fukazawa, M. Kodama, J. Tsuchiya, Y. Fujise, S. Ito, Tetra-
hedron Lett. 1986, 27, 1929Ϫ1932.
M. Lautens, E. Fillion, J. Org. Chem. 1997, 62, 4418Ϫ4427.
C. Benoit, Bull. Soc. Chim. Fr. 1975, 1302Ϫ1306.
L. S. Hegedus, in Organometallics in Synthesis (Ed.: M.
Schlosser), Wiley, Chichester, 1994, 448Ϫ448.
Received December 18, 2003
55, 4709Ϫ4720 and references cited therein.
[2]
M. de Sousa Healy, A. J. Rest, J. Chem. Soc., Chem. Commun.
1981, 149Ϫ150.
F. H. Kohnke, G. L. la Torre, M. F. Parisi, S. Menzer, D. J.
[3]
Williams, Tetrahedron Lett. 1996, 37, 4593Ϫ4596.
[4]
J. F. Haley, S. M. Rosenfeld, P. M. Keehn, J. Org. Chem. 1977,
42, 1379Ϫ1386.
[5]
Y. Ito, S. Miyata, M. Nakatsuka, T. Saegusa, J. Org. Chem.
1981, 46, 1043Ϫ1044.
[6]
T. Shinmyozu, Y. Hirai, T. Inazo, J. Org. Chem. 1986, 51,
[40]
1551Ϫ1555.
[7]
D. C. Miller, M. R. Johnson, J. A. Ibers, J. Org. Chem. 1994,
59, 2877Ϫ2879.
P. Fonte, F. H. Kohnke, M. F. Parisi, S. Menzer, D. J. Williams,
[41]
[42]
[8]
Tetrahedron Lett. 1996, 37, 6205Ϫ6208 and references cited
therein.
[9]
´
A. Toro, Y. Wang, P. Deslongchamps, Tetrahedron Lett. 1999,
[43]
[44]
[45]
40, 2765Ϫ2768.
[10]
[11]
´
A. Toro, Y. Wang, M. Drouin, P. Deslongchamps, Tetrahedron
Lett. 1999, 40, 2769Ϫ2772.
´
A. Toro, P. Deslongchamps, J. Org. Chem. 2003, 68,
6847Ϫ6852.
Eur. J. Org. Chem. 2004, 1923Ϫ1935
www.eurjoc.org
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
1935