Photochemical Synthesis of Both Strained and Macrocyclic (1,7)Naphthalenophanes

Article abstract of DOI:10.1021/acs.joc.6b01707

Naphthalenophanes are a special type of cyclophanes. While in the past (1,5)-, (1,6)-, and (1,8)naphthalenophanes were successfully prepared by using the photo-dehydro-Diels-Alder (DDA) reaction, access to (1,7)naphthalenophanes by this method was hitherto unknown. After numerous unsuccessful attempts to prepare these compounds by thermal DDA, we found that the photoinitiated variant (PDDA) represents a very efficient method to [k](1,7)naphthalenophanes 13. The scope ranged from highly strained (k = 11, 12) to macrocyclic products (k = 22, 24). The extraordinary reactivity could be explained by folded ground-state geometries of diketones 12 used as reactants of the PDDA. Furthermore, we calculated the ring-strain energies with the help of an isodesmic reaction and evaluated structural and spectroscopic (NMR) consequences of ring strain.

Full text of DOI:10.1021/acs.joc.6b01707

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Article
Photochemical Synthesis of both Strained
and Macrocyclic (1,7)Naphthalenophanes
Pablo Wessig, Maciej Czarnecki, Dominik Badetko, Uwe Schilde, and Alexandra Kelling
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.6b01707 • Publication Date (Web): 12 Sep 2016
Downloaded from http://pubs.acs.org on September 16, 2016
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Photochemical Synthesis of both Strained and Macrocyclic
(1,7)Naphthalenophanes
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Pablo Wessig*, Maciej Czarnecki, Dominik Badetko, Uwe Schilde, and Alexandra Kelling
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Institut für Chemie, Universität Potsdam, KarlꢀLiebknechtꢀStr. 24ꢀ25, Dꢀ14476 Potsdam,
Germany
wessig@uniꢀpotsdam.de
KEYWORDS: Cyclophanes, Naphthalenophanes, Ring strain, Photochemistry, Photoꢀ
DehydroꢀDielsꢀAlder Reaction, DFT calculations, Anisotropy effects
Abstract:
Naphthalenophanes are a special type of cyclophanes. While in the past (1,5), (1,6) and
(1,8)Naphthalenoꢀphanes were successfully prepared by using the (Photo)ꢀDehydroꢀDielsꢀ
Alder (DDA) reaction, the access to (1,7)Naphthalenophanes by this method was hitherto
unknown. After numerous unsuccessful attempts to prepare these compounds by thermal
DDA, we found that the photoinitiated variant (PDDA) represents a very efficient method to
[k](1,7)Naphthalenophanes 13. The scope ranged from highly strained (k = 11, 12) to
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macrocyclic products (k = 22, 24). The extraordinary reactivity could be explained by folded
ground state geometries of diketones 12 used as reactants of the PDDA. Furthermore, we
calculated the ring strain energies with the help of an isodesmic reaction and evaluated
structural and spectroscopic (NMR) consequences of ring strain.
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Introduction
Although the arsenal of synthetic methods is enormous today and seemingly every thinkable
molecule can be prepared, there is still a number of challenging tasks. One of them is the
synthesis of highly strained molecules due to their intrinsic reactivity and pronounced
tendency to reduce the strain by rearrangement and decomposition reactions. Another
challenge is the efficient synthesis of macrocyclic compounds, which are widely distributed in
nature. Here, the difficulties arise mainly from entropically disfavored formation of large
rings compared with the competing polymerization. Common strategies to overcome these
problems are using either large dilution (RuggliꢀZiegler dilution principle) or template effects.
The synthesis of cyclophanes, i.e. molecules consisting of an aromatic core and a chain
forming a bridge between two nonadjacent atoms of this core, is often associated with one or
both of the problems mentioned above.1 If the aromatic core is a naphthalene scaffold, this
type of cyclophanes is called naphthalenophane.2 There are basically two strategies to
synthesize naphthalenophanes: either the bridging chain is tethered at a naphthalene moiety
already present, or the naphthalene moiety is formed in the cyclization reaction. Pursuing the
latter approach we recently reported on the preparation of a series of naphthalenophanes3
based on the application of the DehydroꢀDielsꢀAlder (DDA) reaction.4 The DDA reaction
differs from the classical DielsꢀAlder (DA) reaction in that at least one double bond of the
diene moiety is replaced by a triple bond.
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Figure 1. Formation of Naphthalenophanes 2 from diynes 1.
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As a result, the DDA reaction proceeds in contrast to the DA reaction stepwise and diradicals
and highly strained cycloallenes are assumed to be intermediates of the DDA reaction.
Furthermore, the DDA reaction can be initiated both thermally and photochemically (with
regard to the mechanistic details we refer to previous publications4).
The synthetic strategy toward naphthalenophanes 2 applied in our previous work is outlined in
figure 1. Thus, two 3ꢀarylynones 1a (R=alkyl),3aꢀc 3ꢀarylpropiolic esters 1b (R=alkoxy),3c or
3ꢀarylpropiolic acids (R=hydroxy)3c are connected by a variable linker unit X. Whereas
ketones 1a and esters 1b undergo the DDA reaction upon irradiation (Photo DehydroꢀDielsꢀ
Alder reaction, PDDA), the ring closure of carboxylic acids 1c proceeds by preceding
formation of cyclic anhydrides 3 mediated by carbodiimides. By this way we already prepared
(1,5), (1,6) and (1,8)naphthalenophanes A-C while (1,7)naphthalenophanes D are still a
“missing link” in this array (Figure 2).
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Figure 2. Structure of (1,5), (1,6), (1,8), and (1,7)Naphthalenophanes A-D.
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Herein we report on the efficient synthesis of (1,7)naphthalenophanes as well as on their
properties.
Results and Discussion
1. Attempted thermal synthesis of (1,7)Naphthalenophanes.
Based on the good results we previously achieved for the synthesis of other
naphthalenophanes (cf. figure 1) we first explored the thermal synthesis of
(1,7)naphthalenophanes. The established method for mild DDA to arylnaphthalenes
comprises the in situ preparation of 3ꢀsubstituted propiolic anhydrides by treatment with
reagents activating the carboxylic group. In most cases carbodiimides were used for this task.
In these anhydrides the alkyne moieties are brought in spatial proximity lowering the
activation barrier of the DDA. To apply this approach to (1,7)naphthalenophanes we chose a
medium linker length (10 atoms) to rule out the prevention of product formation by too small
(ring strain) or too large (macrocycles) ring sizes. We started with 3ꢀ(4ꢀiodophenyl)propanoic
acid 4c,5 which was converted into the diester 5i by treatment with diisopropyl carbodiimide
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(DIC)/DMAP6 in good yield. The subsequent Sonogashira coupling with propiolic acid
furnished the dicarboxylic acid 6 in nearly quantitative yield.7
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Surprisingly, all attempts using various reagents and conditions (for details see the SI) failed
to convert compound 6 into the desired naphthalenophane 8 via the cyclic anhydride 7
(Scheme 1).
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Scheme 1. Attempted thermal synthesis of (1,7)naphthalenophane 8.
i DIC, DMAP, DCM, 50°C, 72h, 70%. ii PdCl2(PPh3)2, DMSO, DBU, dppb, propiolic acid, 50°C, 5h, 96%. iii
various conditions (see SI).
In cases where DIC was used as activating agent, we always isolated the diureide 9 as main
product. The formation of ureides as byproducts upon activation of carboxylic acids with
carbodiimides is a longꢀstanding problem. It is the result of a 1,3ꢀacyl migration in the
primarily formed Oꢀacyl isourea (the adduct of a carboxylic acid on the carbodimide) that
occur if this species does not react fast enough with the nucleophile (in our case the second
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carboxylate) or no nucleophile is available. From this outcome we concluded that the
conformational equilibrium of diacid 6 is dominated by straight conformation with a large
distance between the carboxylic groups preventing any reaction to the anhydride 7 and
subsequent DDA to 8.
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2. Photochemical synthesis of (1,7)Naphthalenophanes.
Assuming that the reaction centers point to diametrically oriented directions, we doubted
whether a synthesis of (1,7)naphthalenophanes starting from pꢀsubstituted arylalkynes such as
6 is possible at all. Nevertheless, the significant mechanistic differences between the thermal
and photochemical variant of the DDA4a gave rise to the assumption that
(1,7)naphthalenophanes could be accessible by the PDDA reaction. To verify this we
prepared a library of twelve diketones 12 in a threeꢀstep sequence. For this purpose we
combined three
ωꢀ(4ꢀiodophenyl)carboxylic acids 4a-c with six diols 10a-f. Steglich
esterification6 of 4 with 10 afforded diiodides 5.
Scheme 2. Synthesis of diketones 13.
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i DIC, DMAP, DCM, 50°C, 72h. ii butꢀ3ꢀynꢀ2ꢀol, PdCl2(PPh3)2, CuI, Et3N, THF, r.t., 24h. iii DMSO, Ac2O, r.t.,
24 h.
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Table 1. Yields of diiodides 5, diols 11 and diketones 12.
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n
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m
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Na
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5b
11b
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j
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l
a N= m + 2n + 4. b Yields in percent.
By subsequent Sonogashira coupling with butꢀ3ꢀynꢀ2ꢀol we obtained the diols 11. In the third
step compounds 11 were converted into diketones 12 by an AlbrightꢀGoldman oxidation
(Scheme 2).8 The yields of 5, 11, and 12 are summarized in Table 1.
With diketones 12 in hand we investigated the photochemical reactivity of these compounds.
The UV spectra of all compounds 12 exhibit a broad structured absorption band with a
maximum at 276 nm (log ε = 4.54 – 4.70, for details see the SI). Compared with the parent
compound 4ꢀphenylbutꢀ3ꢀynꢀ2ꢀone 144a, 9 the absorption maxima of diones 12 are slightly (3
nm) but significantly redꢀshifted. Furthermore, the molar extinction coefficients ε of 12f-l (n >
0) are consistently higher by 16ꢀ30%, compared with 14. (The ε values for 12a-e are not
directly comparable with 14, because the chromophor is extended by an ester group). These
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findings strongly suggest an interaction of the two chromophors in 12 in the ground state (see
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Section 3).
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Scheme 3. PDDA reaction to (1,7)naphthalenophanes 13 and dimerization of the parent
compound 14 to 15.
Table 2. Yields of [k](1,7)Naphthalenophanes 13a-l.
ka
Yields [%]b
ka
Yields [%]b
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13e
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13k
13l
a k = N + 4. bStarting concentration for irradiation: 1.0 mM.
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To our great surprise most of the diketones 12 exhibit a remarkable photochemical reactivity
(excitation wavelength > 300 nm) and smoothly react to the corresponding [k](1,7)naphthaꢀ
lenophanes 13 (Scheme 3, k is the total number of atoms in the linker connecting positions 1
and 7 of naphthalene). As already mentioned above the PDDA reaction proceeds stepwise via
biradicals BR and cycloallenes CA, which are also depicted in Scheme 3 for the reaction from
12 to 13.
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For k > 12 we obtained the target compounds in almost all cases with yields > 50% (except
13e). With decreasing length of the linker (13b,c) the yields decreased and 13a bearing the
shortest linker was not accessible by PDDA of 12a (Table 2).
The structure of (1,7)naphthalenophanes 13 was unambiguously proven with the xꢀray
structure of 13i (Figure 3).10
Figure 3. X-ray crystal structure of 13i.
2. Mechanism of the PDDA to (1,7)Naphthalenophanes.
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As mentioned above we felt that diketones 12 exhibit an unusually high photochemical
reactivity. To substantiate this impression, we compared their photokinetics with previously
investigated oꢀ and mꢀsubstituted systems. For this purpose we measured the decay rate of
12h as well as of oꢀsubstituted precursor 163a and of mꢀsubstituted precursor 173b. The
degradation curves of these three compounds are depicted in Figure 4. It is clearly discernable
that the decay rate of 12h is more than twice the decay rates of 16 and 17 (for kREL the decay
rate of 16 was set to unity). Although the exact cause of the increased reactivity of ketones 12
is still unclear we hypothesized that a “folded” groundꢀstate conformation of 12, which
facilitates the PDDA, is responsible for this behavior. In the preceding section we have
already mentioned conspicuous changes in the UV spectra of 12 compared with the parent
compound 14. Indeed, a comparative conformational analysis of 12h, 16, and 17 (force field
MMFF94x11, for details see the SI) revealed a folded conformation for 12h as the global
minimum, but not for 16 and 17. The stabilization of this conformation originates from headꢀ
toꢀtail dipoleꢀdipole interactions between the ketocarbonyl groups resulting in a relatively
short distance between the alkyne moieties. To verify these findings at a higher level of theory
we optimized both the folded and the stretched geometry using a DFT method (B3LYP12/6ꢀ
31G*13). The geometry of the folded conformer is depicted in figure 5. We found that this
structure is more stable by about 3 kcal/mol compared with the stretched conformation. A
similar result was obtained for 12i. The close proximity of the photoreactive ynone moieties
in these folded conformers could be the explanation for the high reactivity of compounds 12.
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Figure 4. Degradation curves of the irradiation of 12h, 16, 17.
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Figure 5. DFT-optimized ground-state geometry of 12h.
3. Ring strain and structural strain indicators.
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Some of the (1,7)naphthalenophanes 13 should be considerably strained14 and we were
interested in the corresponding ring strain energies as well as possible structural and
spectroscopic consequences of the strain.
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For the determination of strain energy by means of quantum chemical calculations, the
definition of an isodesmic reaction is the method of choice.15 This is understood to be a
hypothetic reaction in which the type and number of bonds cleaved in the reactants are the
same as the type and number of bonds formed in the products. Recently, we successfully
applied this approach for calculating the ring strain of (1,5)naphthalenophanes.3a In analogy to
this work we defined the isodesmic reaction shown in Scheme 4 for even values of m (this
applies to all cases except 13b where two different cuts from E to G are possible, for details
see the SI). Starting from the naphthalenophane E the central CꢀC bond of the diol linker is
cleaved to the 1ꢀarylnaphthalene G, releasing potential ring strain. The simultaneous cleavage
of a CꢀC bond and the formation of two CꢀH bonds are compensated by the reaction between
two alkyl acetates F to diol diacetate H. Here, the value of p is given in eq. 1 and the strain
energy ESTR is defined by eq. 2 (Scheme 4).
Scheme 4. Isodesmic reaction for the calculation ring strain of (1,7)Naphthalenophanes
13.
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ꢀ = ꢁ − 1
(1)
ꢂ
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ꢇ ꢉ
ꢇ ꢉ
ꢇ ꢉ
ꢃꢄꢅꢆ = ꢃ ꢈ + ꢃ ꢊ − ꢃ ꢋ − 2ꢃꢇꢌꢉ
(2)
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The resulting strain energies are summarized in Table 3 (3rd col.). The highest value (25.4
kcal/mol) was obtained for the inaccessible compound 13a (k = 10). 13b with the next larger
linker (k = 11), which was obtained with 33% yield, exhibits a ring strain energy of 19.3
kcal/mol. Obviously, products with strain energies above about 20 kcal/mol cannot be
obtained with this method. The strain energies of [12](1,7)naphthalenophanes 13c and 13f are
quite different (13.2 kcal/mol vs. 3.7 kcal/mol). This can be explained by the conjugation of
the ester groups with the πꢀsystems of the aromatic rings (n = 0) in the case of 13c, resulting
in conformational stiffening. Most of the other (1,7)naphthalenophanes are only moderately
strained and the strain energies range from 1 to 4 kcal/mol (Table 3).
In our previous work on (1,5)naphthalenophanes we observed an increasing twist of
naphthalene moiety with increasing ring strain.3a
Table 3. Strain energy ESTR, deformation angle γPh (see Figure 6) and selected 1H-NMR
shifts of [k](1,7)Naphthalenophanes 13.
b
ka
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22
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16
ESTR
c
γPh
δ(H-8)d
ꢀ
δ(Ac-2)e
ꢀ
13
25.4
19.3
13.2
6.0
29.01
25.63
19.16
10.03
1.74
a
b
c
6.34
6.74
7.46
ꢀf
2.60
2.55
2.41
2.08
2.37
2.14
2.09
d
e
3.5
3.7
9.46
6.83
ꢀf
ꢀf
f
1.0
3.75
g
h
1.1
1.23
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3.0
2.7
3.9
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ꢀf
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ak = N+4 = m + 1n + 8. bStrain energy in kcal/mol. cdeformation angle of the phenyl ring in °. dChemical shift of
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Hꢀ8 in ppm. Chemical shift of Acꢀ2. signal could not be unambiguously determined due to superposition of
signals in NMR spectra.
Figure 6. (a) Definition of the deformation angle γPh. (b) Effects of increasing ring strain
on the chemical shifts of H-8 (blue) and the methyl group of Ac-2 (red).
In order to find out whether in the case of (1,7)naphthalophanes 13 the naphthalene part is
also the “weakest link” we carefully explored the optimized geometries. The first striking
detail was the nearly perpendicular orientation of the phenyl ring relative to the naphthalene
system in all cases (cf. figure 3). In contrast to the previously investigated
(1,5)naphthalenophanes the naphthalene moiety is virtually planar even for highly strained
cases.
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By contrast, the two CꢀC bonds connecting the phenyl ring with the rest of the
naphthalenophane are considerably inclined from the πꢀplane in these cases. This effect can
be expressed by a deformation angle γPh, which is defined by the difference between 180 and
the arithmetic average of two pseudoꢀvalance angles, α and β (Figure 6a). The values for γPh,
which correlate well with ESTR, are listed in Table 3 (4th col.).
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The bending of the phenyl ring should significantly influence the H NMR spectra of
compounds 13. Caused by the aromatic ring current in a static magnetic field, each phenyl
ring exhibits an anisotropy cone. The chemical shift values of all protons inside this cone are
decreased (upfield), whereas signals of protons outside the cone are shifted downfield.16
Looking at the geometries of naphthalenophanes 13 the positions both of Hꢀ8 (blue) and of
the methyl group of Acꢀ2 (red) regarding the anisotropy cone (green) are altered upon
bending of the phenyl ring (Figure 6). Whereas Hꢀ8 is moved towards the interior of the cone,
1
the aforementioned methyl group is moved out of the cone. The measured H NMR shift
values of Hꢀ8 and Acꢀ2, which are also summarized in Table 3, excellently reflect the
forecasted trend. Comparing highly strained 13b and moderately strained 13i, the signal of Hꢀ
8 is downfieldꢀshifted by 0.70 ppm and the signal of Acꢀ2 is upfieldꢀshifted by 0.49 ppm.
Conclusion
Based on our previous successful synthesis of naphthalenophanes3c by thermal DDA reaction
we first examined whether this approach is also an appropriate way to
(1,7)naphthalenophanes. Unfortunately, all attempts in this direction failed. On the other
hand, the photochemical variant (PDDA reaction) using diketones 12 smoothly provided the
[k](1,7)naphthalenophanes 13 even in highly strained (k = 11, 12) and macrocyclic (k up to
24) cases. The photochemical reactivity of compounds 12 is unusually high, compared with
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previously investigated systems, and could be explained by folded ground state geometries of
the reactants bringing the ynone moieties in close proximity. The ring strain energies ESTR of
naphthalenophanes 13 were determined with the help of an isodesmic reaction. The most
strained product 13b (k = 11) exhibits a strain energy of about 19 kcal/mol, whereas 13a (k =
10, ESTR = 25.4 kcal/mol) was not accessible. The most conspicuous change in the geometry
of highly strained (1,7)naphthalenophanes is a bending of the phenyl ring, expressed by the
deformation angle γPh. This bending causes distinct changes of the NMR signals of protons,
which are located near the anisotropy cone of the phenyl ring. Finally, it should be noted that,
according to our experience, the cyclization of diketones 12 to (1,7)naphthalenophanes 13 is
one of the most efficient PDDA systems known to date. Currently, we are investigating
applications as peptide mimetic and in supramolecular assemblies.
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Experimental Section
General Information. All reactions were conducted in heatꢀgunꢀdried and nitrogen flushed glassware using
Schlenk techniques. Solvents and reagents were purchased in highest available purity and used without
additional purification, if not stated elsewhere. Solvents were dried and distilled prior to use. Reaction
monitoring was performed by thin layer chromatography (TLC) until the starting material was completely
consumed indicated at the appropriate sections. Crude mixtures were purified by flash column chromatography
(FSC). For the visualization of the products UVꢀ and/or dark light (254/366 nm) was used. The individual
solvent mixtures for the elution of the product and the corresponding retardation factors (Rf) were noted in the
appropriate sections. Melting points of solids were recorded and not corrected. NMR spectra were recorded on a
300 MHz spectrometer with appropriate deuterated solvents and used as internal standard: CDCl3 (1H: δ = 7.26
ppm, 13C: δ = 77.2 ppm); CD3OD (1H: δ = 3.31 ppm, 13C: δ = 49.0 ppm). Coupling constants (J) are given in
Hertz (Hz). Fine structure analysis was performed and multiplicities were abbreviated as follows: broad singlet
(br s), doublet (d), triplet (t), quartet (q), multiplet (m). FTꢀIR measurements were performed on ATR crystals
and the characteristic intensities of absorption bands (υꢍ, cmꢀ1) were abbreviated as follows: weak (w), medium
(m), strong (s), very strong (vs). High resolution mass spectrometry (HRMS) was performed with impact
ionization (EI) and were recorded on a Mass spectrometer equipped with a quadrupol. UVꢀVis spectra were
recorded in a twoꢀcuvette spectrometer in the range of 200ꢀ500 nm. Phosphorescence spectra were recorded in
an EPA (diethyl ether, isoꢀpentane, ethanol, 5:5:2, v/v/v) matrix at 77 K. Photochemical reactions were
performed in a standard (semi)preparative batch apparatus equipped with an internal cooling jacket (quartz) and
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external pyrex vessel water cooling system. For efficient stirring of the reaction medium a gentle stream of
nitrogen was needed and bubbled 15 min before the reaction was initiated with a highꢀpressure mercury arc lamp
(150 W; excitation λ > 300 nm). 2ꢀ(4ꢀIodophenyl)acetic acid17 and 3ꢀ(4ꢀIodophenyl)propionic5 acid were
synthesized according to literature.
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General Procedures
General procedure 1 (GP1) for the synthesis of diiodides 5: To a suspension containing the diol 10 (1.0
equiv) and the carboxylic acid 4 (2.67 equiv) in dry DCM (10 mL/mmol) were added N,N‘ꢀdiisopropylꢀ
carbodiimide (DIC, 2.5 equiv) and DMAP (20 mol%). Stirring at 50 °C was continued until TLC indicated the
complete consumption of the starting material. The heterogeneous reaction mixture was washed three times with
brine and the combined organic phases were dried with magnesium sulfate. Before removing the solvent under
reduced pressure the suspension was filtered over Celite®. The purification of compounds 5 was accomplished
by FSC.
General procedure 2 (GP2) for the synthesis of diols 11: The diiodide 5 (1.0 equiv) was dissolved in a
mixture of triethylamine (Et3N) and THF (10 mL/ mmol, 3:1, v/v). The solution was degassed three times and
flushed with nitrogen. Bis(triphenylphosphine) palladium(II)dichloride (Pd(PPh3)2Cl2, 10 mol%) and copper
iodide (CuI, 5 mol%) were added and stirred for five minutes. 3ꢀButyneꢀ2ꢀol (97%, 4.0 equiv) was added and the
reaction mixture was stirred until TLC indicated complete consumption of the starting material. The
heterogeneous mixture was poured into diethyl ether and washed subsequently (each two times) with water, aq
tartaric acid (20%), sodium bicarbonate and brine. The combined organic phases were dried with magnesium
sulfate and filtered over Celite®. After removing the solvent under reduced pressure the crude product 11 was
purified by FSC.
General procedure 3 (GP3) for the synthesis of diketones 12: The diol 11 (1.0 equiv) was dissolved in anhyd
DMSO (10 mL/mmol). Acetic anhydride (10.0 equiv) was added and stirring was continued until TLC indicated
the complete consumption of the starting material. The solvent was removed in vacuo. The pure product 12 was
isolated after FSC.
General procedure 4 (GP4) for the PDDA reaction to (1,7)Naphthalenophanes 13. The diketone 12 was
dissolved in DCM (380 mL) using a standard photochemical batch apparatus for (semi)preparative scale
reactions. The solution was purged 15 min with nitrogen and irradiated with a highꢀpressure mercury arc lamp
until TLC indicated the complete consumption of the starting material. The solvent was removed under reduced
pressure. The crude material 13 was purified by FSC.
3,3'-{Ethane-1,2-diylbis[oxy(3-oxopropane-3,1-diyl)benzene-4,1-diyl]}bisprop-2-ynoic acid 6. Bisꢀ(3ꢀ(4ꢀ
Iodophenyl)propionic acid)ꢀethaneꢀ1,2ꢀdiylꢀester (0.60 g, 1.04 mmol) (5i) was dissolved in dry DMSO (40 mL)
and DBU (1.60 mL, 10.38 mmol), 1,4ꢀBis(diphenylphosphino)butane (dppb, 0.089 g, 0.21 mmol) and
bis(triphenylphosphine)palladium (II)dichloride (Pd(PPh3)2Cl2, 0.057 g, 0.10 mmol) were added subsequently.
Before adding propiolic acid (0.13 mL, 2.08 mmol) dropwise the heterogenous reaction mixture was degassed
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three times and flushed with nitrogen. Stirring at 50 °C was continued until TLC indicated the complete
consumption of the starting material (5h). The dark mixture was diluted with ethyl acetate (100 mL) and
extracted three times (3 x 80) with saturated aq NaHCO3 solution. The combined aq phases were acidified with
iceꢀcold HCl (aq, 6 M, 50 mL) up to pH 2. The resulting precipitate was extracted five times (5 x 50 mL) with
DCM. The combined phases were dried over magnesium sulfate and the solvent was removed under reduced
pressure. After FSC compound 6 was isolated as light yellowish solid (0.46 g, 96%). Rf 0.48 (EtOAc + 1%
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formic acid); m.p. 159ꢀ160 °C; H NMR (300 MHz, CD3OD, ppm): δ 7.48 (d, J = 8.2 Hz, 4H), 7.27 (d, J = 8.2
Hz, 4H), 4.20 (s, 4H), 2.92 (t, J = 7.4 Hz, 4H, 2.61 (t, J = 7.4 Hz, 4H; 13C NMR (75 MHz, MeOD, ppm): δ
173.9, 156.7, 145.3, 134.0, 130.0, 118.8, 86.7, 63.5, 35.9, 31.7; IR: 3436 (w), 2972 (m), 2569 (m), 2201 (s),
1681 (vs), 1606 (m), 1367 (m), 1282 (m), 1216 (s), 1173 (s), 830 (m) cmꢀ1; HRMS (m/z) [M+] calcd for
C26H22O8 462.1315; found 462.1320.
Ethane-1,2-diyl bis[3-(4-{3-oxo-3-[propan-2-yl(propan-2-ylcarbamoyl)amino]prop-1-yn-1-yl}phenyl)-
propanoate] (9). According to table SIꢀ1 (see conditions), the Diureide 9 was isolated as a vitreous oil, Rf 0.60
(PE/EtOAc 1:1); 1H NMR 300 MHz, CDCl3) δ 8.48 (br s, 2H), 7.53 (d, J = 8.1 Hz, 4H), 7.32 – 7.25 (m, 4H),
4.98 (dt, J = 13.7, 6.8 Hz, 2H), 4.29 (s, 4H), 4.03 (dq, J = 13.3, 6.6 Hz, 2H), 3.02 (t, J = 7.5 Hz, 4H), 2.69 (t, J =
7.6 Hz, 4H), 1.59 (d, J = 6.8 Hz, 12H, 1.24 (d, J = 6.5 Hz, 12H; 13C NMR (75 MHz, CDCl3, ppm) δ 172.2,
156.9, 152.9, 143.7, 132.9, 128.9, 118.0, 93.8, 82.3, 62.4, 51.9, 42.7, 35.2, 30.9, 22.8, 21.2. HRMS (m/z) [M+]
calcd for C40H50N4O8 714.3629; found 714.3634.
Bis-(4-Iodobenzoic acid)-ethane-1,2-diyl-ester (5a). 1,2ꢀEthanediol (0.77 mL, 13.69 mmol) and 4ꢀIodobenzoic
acid (9.07 g, 36.56 mmol), were subjected to the reaction conditions described in GP1. The reaction was finished
after 43 h, yielding the title compound as colorless solid (6.79 g, 95%). Rf = 0.38 (PE/EtOAc 1:1); m.p. 142 –
143 °C; 1H NMR (300 MHz, CDCl3, ppm): δ 7.81 – 7.72 (m 8H), 4.64 (s, 4H; 13C NMR (75 MHz, CDCl3, ppm):
δ 166.0, 137.9, 131.2, 129.3, 101.3, 63.0; IR (υꢍ): 3077 (w), 2857 (w), 1713 (vs), 1581 (s), 1454 (m), 1393 (m),
1291 (m), 1255 (s), 1176 (m), 1101 (s), 1009 (s), 837 (m), 751 (s), 680 (m) cmꢀ1; HRMS (m/z) [M+] calcd for
C16H12I2O4 521.8820; found 521.8821.
Bis-(4-iodobenzoic acid)-propane-1,3-diyl-ester (5b). 1,3ꢀPropanediol (0.67 mL, 9.25 mmol) and 4ꢀ
Iodobenzoic acid (6.12 g, 24.68 mmol) were subjected to the reaction conditions described in GP1. The reaction
was finished after 38 h, yielding the title compound as colorless solid (3.31 g, 67%). Rf 0.58 (PE/EtOAc 3:1);
m.p. 116ꢀ117 °C; 1H NMR (300 MHz, CDCl3, ppm): δ 7.79 – 7.69 (m, 8H), 4.48 (t, J = 6.2 Hz, 4H), 2.24 (p, J =
6.1 Hz, 2H; 13C NMR (75 MHz, CDCl3, ppm): δ 166.1, 137.9, 131.1, 129.6, 101.0, 62.1, 28.3; IR (υꢍ): 2980 (m),
1709 (vs), 1586 (s), 1393 (s), 1272 (vs), 1122 (vs), 1008 (s), 840 (m), 748 (s)cmꢀ1; HRMS (m/z) [M+] calcd for
C17H14I2O4 535.8982; found 535. 8985 .
Bis-(4-Iodobenzoic acid)-butane-1,4-diyl-ester (5c). 1,4ꢀButanediol (1.0 g, 11.1 mmol) and 4ꢀIodobenzoic acid
(7.35 g, 29.63 mmol), were subjected to the reaction conditions described in GP1. The reaction was finished
after 47 h yielding the title compound as colorless solid (4.2 g, 69%). Rf 0.25 (PE/EtOAc 10:1); m.p. 134ꢀ135
°C; 1H NMR (300 MHz, CDCl3, ppm): δ 7.80 – 7.71 (m, 8H, HꢀAr), 4.38 (s, 4H, CH2), 1.92 (s, 4H,
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CH2);13C NMR (75 MHz, CDCl3, ppm): δ 166.2 (C=O), 137.9 (CArH), 131.1 (CArH), 129.8 (CAr), 100.9 (CAr),
64.8 (CH2), 25.6 (CH2); IR (υꢍ
): 1703 (vs), 1585 (m), 1267 (vs), 1102 (s), 915 (m), 757 (m), 745 (m) cmꢀ1; HRMS
(m/z) [M+] calcd for C18H16I2O4 549.9138; found 549.9150.
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Bis-(4-Iodobenzoic acid)-hexane-1,6-diyl-ester (5d). 1,6ꢀHexanediol (0.71 g, 6.0 mmol) and 4ꢀIodobenzoic
acid (3.97 g, 16.02 mmol), were subjected to the reaction conditions described in GP1. The reaction was finished
after 44 h yielding the title compound as colorless solid (2.41 g, 70%). Rf 0.61 (PE/EtOAc 1:1); m.p. 85ꢀ86 °C;
1H NMR (300 MHz, CDCl3, ppm): δ 7.83 – 7.67 (m, 8H), 4.31 (t, J = 6.6 Hz, 4H), 1.88 – 1.68 (m, 4H), 1.56 –
1.44 (m, 4H); 13C NMR (75 MHz, CDCl3, ppm): δ 166.2, 137.8, 131.1, 130.0, 100.8, 65.3, 28.7, 25.9; IR (υꢍ):
2941 (m), 1710 (s), 1584 (s), 1264 (vs), 1103 (s), 1004 (s), 753 (w) cmꢀ1; HRMS (m/z) [M+] calcd for C20H20I2O4
577.9446; found 577.9436.
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Bis-(4-Iodobenzoic acid)-dodecane-1,12-diyl-ester (5e). 1,12ꢀDodecanediol (1.00 g, 4.94 mmol) and 4ꢀ
Iodobenzoic acid (3.27 g, 13.20 mmol) were subjected to the reaction conditions described in GP1. The reaction
was finished after 65 h yielding the title compound as colorless solid (3.27 g, 99%). Rf 0.51 (PE/EtOAc 10:1);
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m.p. 55ꢀ57 °C; H NMR (300 MHz, CDCl3, ppm): δ 7.76 (q, J = 8.5 Hz, 8H), 4.30 (t, J = 6.7 Hz, 4H), 1.89 –
1.60 (m, 4H, Hꢀ7), 1.51 – 1.10 (m, 16H); 13C NMR (75 MHz, CDCl3, ppm): δ 166.3, 137.8, 131.1, 130.1, 100.7,
65.5, 29.6,29.4, 28.8, 26.1; IR (υꢍ): 2916 (s), 2849 (s), 1716 (vs), 1584 (m), 1392 (m), 1314 (m), 1272 (m), 1181
(m), 1104 (m), 1007 (m), 845 (m), 750 (m) cmꢀ1; HRMS (m/z) [M+] calcd for C26H32I2O4 662.0385; found
662.0395.
Bis-(2-(4-Iodophenyl)acetic acid)-ethane-1,2-diyl-ester (5f). 1,2ꢀEthanediol (0.46 mL, 8.22 mmol) and 2ꢀ(4ꢀ
Iodophenyl)acetic acid (5.76 g, 21.96 mmol) were subjected to the reaction conditions described in GP1. The
reaction was finished after 48 h yielding the title compound as colorless solid (3.62 g, 80%). Rf 0.47 (PE/EtOAc
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1:1); m.p.: 60ꢀ61 °C; H NMR (300 MHz, CDCl3, ppm): δ 7.65 (d, J = 8.3 Hz, 4H), 7.01 (d, J = 8.2 Hz, 4H),
4.29 (s, 4H), 3.54 (s, 4H; 13C NMR (75 MHz, CDCl3, ppm): δ 170.8, 137.8, 133.4, 131.4, 92.9, 62.6, 40.7; IR
(υꢍ): 2982 (w), 2921 (w), 1729 (vs), 1483 (s), 1338 (m), 1251 (s), 1159 (s), 1136 (vs), 1043 (s), 1007 (s), 976
(s),737(s), 485 (s) cmꢀ1; HRMS (m/z) [M+] calcd for C18H16I2O4 549.9138; found 549.9136.
Bis-(2-(4-Iodophenyl)acetic acid)-butane-1,4-diyl-ester (5g). 1,4ꢀButanediol (0.99 mL, 11.15 mmol) and 2ꢀ(4ꢀ
Iodophenyl)acetic acid (7.8 g, 29.77 mmol), were subjected to the reaction conditions described in GP1. The
reaction was finished after 63 h yielding the title compound as colorless solid (4.53 g, 70%). Rf 0.35 (PE/EtOAc
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1:1); m.p. 71–72 °C; H NMR (300 MHz, CDCl3, ppm): δ 7.65 (d, J = 8.4 Hz, 4H), 7.02 (d, J = 8.4 Hz, 4H),
4.08 (t, J = 5.6 Hz, 4H), 3.55 (s, 4H), 1.69 – 1.59 (m, 4H); 13C NMR (75 MHz, CDCl3, ppm): δ 171.0, 137.8,
133.7, 131.4, 92.7, 64.5, 41.0, 25.3; IR (υꢍ): 2956 (w), 1722 (vs), 1485 (m), 1348 (m), 1216 (m), 1164 (m), 800
(m) cmꢀ1; HRMS (m/z) [M+] calcd for C20H20I2O4 577.9451, found 577.9442.
Bis-(2-(4-Iodophenyl)acetic acid)-hexane-1,6-diyl-ester (5h). 1,6ꢀHexanediol (0.86 g, 8.46 mmol) and 2ꢀ(4ꢀ
Iodophenyl)acetic acid (5.0 g, 19.08 mmol) were subjected to the reaction conditions described in GP1. The
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reaction was finished after 71 h yielding the title compound as colorless solid (2.94 g, 67%). Rf 0.52 (PE/EtOAc
3:1); m.p. 97ꢀ98 °C; 1H NMR (300 MHz, CDCl3, ppm): δ 7.64 (d, J = 8.2 Hz, 4H), 7.03 (d, J = 8.2 Hz, 4H), 4.06
(t, J = 6.6 Hz, 4H), 3.55 (s, 4H, 4H), 1.57 (d, J = 6.5 Hz, 4H), 1.35 – 1.21 (m, 4H); 13C NMR (75 MHz, CDCl3,
ppm): δ 171.2, 137.8, 133.9, 131.4, 92.7, 65.0, 41.1, 28.5, 25.5; IR (υꢍ): 2935 (w), 2886 (w), 1723 (vs), 1484 (m),
1218 (m), 1170 (s), 981 (m), 800 (m), 733 (m) cmꢀ1; HRMS (m/z) [M+] calcd for C22H24I2O4 605.9764; found
605.9745.
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Bis-(3-(4-Iodophenyl)propionic acid)-ethane-1,2-diyl-ester (5i). Ethyleneglycol (0.31 mL, 5.55 mmol) and 3ꢀ
(4ꢀIodophenyl)propionic acid (4.0 g, 14.49 mmol) were subjected to the reaction conditions described in GP1.
The reaction was finished after 46 h yielding the title compound as colorless solid (1.84 g, 57%). Rf 0.38
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(PE/EtOAc 1:1); m.p. 55ꢀ56 °C; H NMR (300 MHz, CDCl3, ppm): δ 7.59 (d, J = 8.3 Hz, 4H), 6.95 (d, J = 8.4
Hz, 4H), 4.24 (s, 4H), 2.88 (t, J = 7.6 Hz, 4H), 2.61 (t, J = 7.7 Hz, 4H); 13C NMR (75 MHz, CDCl3, ppm): δ
172.3, 140.1, 137.6, 130.5, 91.6, 62.3, 35.4, 30.4; IR (υꢍ): 2932 (w), 1745 (m), 1726 (vs), 1484 (m), 1152 (s),
1006 (m), 805 (m) cmꢀ1; HRMS (m/z) [M+] calcd for C20H20I2O4 577.9451; found 577.9446.
Bis-(3-(4-Iodophenyl)propionic acid)-hexane-1,6-diyl-ester (5j). 1,6ꢀHexanediol (1.00 g, 8.46 mmol) and 3ꢀ
(4ꢀIodophenyl)propionic acid (6.24 g, 22.59 mmol) were subjected to the reaction conditions described in GP1.
The reaction was finished after 48 h yielding the title compound as colorless solid (4.41 g, 82%). Rf 0.50
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(PE/EtOAc 3:1); m.p. 77ꢀ78 °C; H NMR (300 MHz, CDCl3, ppm): δ 7.59 (d, J = 8.3 Hz, 4H), 6.95 (d, J = 8.3
Hz, 4H), 4.04 (t, J = 6.6 Hz, 4H), 2.88 (t, J = 7.6 Hz, 4H), 2.59 (t, J = 7.6 Hz, 4H), 1.58 (dd, J = 11.6, 4.9 Hz,
4H), 1.30 (d, J = 7.0 Hz, 4H); 13C NMR (75 MHz, CDCl3, ppm): δ 172.8, 140.3, 137.6, 130.6, 91.5, 64.6, 35.7,
30.6, 28.6, 25.7; IR (υꢍ): 2935 (m), 2854 (w), 1721 (vs), 1484 (m), 1288 (m), 1172 (s), 981 (m), 834 (m), 801 (m)
cmꢀ1; HRMS (m/z) [M+] calcd for C24H28I2O4 634.0077; found 634.0089.
Bis-(3-(4-Iodophenyl)propionic acid)-decane-1,10-diyl-ester (5k). 1,10ꢀDecanediol (0.50 g, 2.87 mmol) and
3ꢀ(4ꢀIodophenyl)propionic acid (11.64 g, 7.66 mmol) were subjected to the reaction conditions described in
GP1. The reaction was finished after 66 h yielding the title compound as colorless solid (1.32 g, 66%). Rf 0.35
1
(PE/EtOAc 5:1); m.p. 56ꢀ57 °C; H NMR (300 MHz, CDCl3) δ 7.59 (d, J = 8.1 Hz, 4H), 6.95 (d, J = 8.0 Hz,
4H), 4.04 (t, J = 6.7 Hz, 4H), 2.89 (t, J = 7.6 Hz, 4H), 2.59 (t, J = 7.6 Hz, 4H), 1.72 – 1.43 (m, 4H), 1.23 (m,
12H); 13C NMR (75 MHz, CDCl3) δ 172.8, 140.3, 137.6, 130.6, 91.5, 64.8, 35.7, 30.6, 29.5, 28.7, 26.0; IR (υꢍ): ꢎꢍ
2958 (m), 2928 (m), 2852(m), 1731 (vs), 1480 (m), 1356 (m), 1203 (m), 1193 (s), 1176 (m), 1040 (w), 1007 (m),
947 (w), 806 (m) cmꢀ1;HRMS (m/z) [M+] calcd for C28H36I2O4 690. 0703; found 690.0708.
Bis-(3-(4-Iodophenyl)propionic acid)-dodecane-1,12-diyl-ester (5l). 1,12ꢀDodecanediol (1.00 g, 4.94 mmol)
and 3ꢀ(4ꢀIodophenyl)propionic acid (3.64 g, 13.20 mmol) were subjected to the reaction conditions described in
GP1. The reaction was finished after 72 h yielding the title compound as colorless solid (3.52 g, 99%). Rf 0.63
1
(PE/EtOAc 3:1); m.p. 59ꢀ61 °C; H NMR (300 MHz, CDCl3, ppm): δ 7.59 (d, J = 8.2 Hz, 4H), 6.95 (d, J = 8.2
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Hz, 4H), 4.04 (t, J = 6.7 Hz, 4H), 2.89 (t, J = 7.6 Hz, 4H), 2.59 (t, J = 7.6 Hz, 4H), 1.58 (dd, J = 12.2, 6.0 Hz,
4H), 1.22 (m, 16H); 13C NMR (75 MHz, CDCl3, ppm): δ 172.8, 140.3, 137.6, 130.6, 91.5, 64.9, 35.7, 30.6, 29.7,
29.4, 28.7, 26.0; IR (υꢍ): 2958 (w), 2919 (m), 2850 (m), 1731 (vs), 1480 (m), 1358 (m), 1204 (m), 1193 (m), 1149
(s), 1007 (m), 806 (m) cmꢀ1;HRMS (m/z) [M+] calcd for C30H40I2O4 718.1016; found 718.0992.
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Bis (4-(2-(3-hydroxybut-1-inyl)benzoic acid))-ethane-1,2-diyl-ester (11a). Bisꢀ(4ꢀIodobenzoic acid)ꢀethaneꢀ
1,2ꢀdiylꢀester (5a) (2.46 g, 4.71 mmol) was subjected to the reaction conditions described in GP2. The reaction
was finished after 24 h yielding the title compound as light brown solid (1.58 g, 82%). Rf 0.5 (PE/EtOAc 1:1);
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m.p. 136ꢀ138 °C; H NMR (300 MHz, CDCl3, ppm): δ 7.96 (d, J = 8.2 Hz, 4H), 7.45 (d, J = 8.2 Hz, 4H), 4.76
(q, J = 6.6 Hz, 2H), 4.64 (s, 4H), 2.28 (br s, 2H), 1.55 (d, J = 6.6 Hz, 6H; 13C NMR (75 MHz, CDCl3, ppm): δ
165.9, 131.7, 129.7, 129.3, 127.8 , 94.3, 83.3, 63.0, 58.9, 24.3; IR (υꢍ): 3296 (m), 2977 (w), 1714 (vs), 1605 (m),
1466 (w), 1407 (w), 1343 (m), 1271 (s), 1176 (m), 1097 (m), 1077 (m), 1033 (m), 1018 (m), 935 (w), 859 (m),
767 (m), 696 (m) cmꢀ1; HRMS (m/z) [M+] calcd for C24H22O6 406.1411; found 406.1421.
Bis(4-(3-hydroxybut-1-inyl)benzoic acid)-propane-1,3-diyl-ester (11b). Bisꢀ(4ꢀIodobenzoic acid)ꢀpropaneꢀ
1,3ꢀdiylꢀester (5b) (2.27 g, 4.24 mmol) was subjected to the reaction conditions described in GP2. The reaction
was finished after 23 h yielding the title compound as light brown solid (1.48 g, 83%). Rf 0.43 (PE/EtOAc 1:2);
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m.p. 140ꢀ141 °C; H NMR (300 MHz, CDCl3, ppm): δ 7.93 (d, J = 8.3 Hz, 4H), 7.43 (d, J = 8.3 Hz, 4H), 4.78
(q, J = 6.6 Hz, 2H), 4.50 (t, J = 6.1 Hz, 4H), 2.34 – 2.15 (m, 2H), 1.94 (br s, 2H), 1.57 (d, J = 6.6 Hz, 6H);
13C NMR (75 MHz, CDCl3, ppm): δ 165.9, 131.5, 129.5, 129.4, 127.6, 94.0, 83.2, 62.2, 58.8, 28.2, 24.2; IR (υꢍ):
3324 (m), 2979 (m), 1706 (vs), 1607 (m), 1470 (m), 1407 (m), 1275 (vs), 1094 (s) cmꢀ1; HRMS (m/z) [M+] calcd
for C25H24O6 420.1573; found 420.1565.
Bis-(4-(3-hydroxybut-1-inyl)benzoic acid)-butane-1,4-diyl-ester (11c). Bisꢀ(4ꢀIodobenzoic acid)ꢀbutaneꢀ1,4ꢀ
diylꢀester (5c) (2.73 g, 4.96 mmol) was subjected to the reaction conditions described in GP2. The reaction was
finished after 23 h yielding the title compound as light brown solid (1.83 g, 85%). Rf 0.35 (PE/EtOAc 1:1); m.p.
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119ꢀ120 °C; H NMR (300 MHz, CDCl3) δ 7.96 (d, J = 8.4 Hz, 4H), 7.45 (d, J = 8.4 Hz, 4H), 4.77 (q, J = 6.6
Hz, 2H), 4.38 (s, 4H), 2.18 (br s, 2H), 1.93 (s, 4H), 1.56 (d, J = 6.6 Hz, 6H); 13C NMR (75 MHz, CDCl3, ppm): δ
166.1, 131.7, 129.8, 129.5, 127.5, 94.1, 64.8, 58.9, 25.6, 24.4; IR (υꢍ): 3353 (w), 2977 (w), 1713 (vs), 1606 (m),
1266 (s), 1255 (s), 1099 (m) cmꢀ1; HRMS (m/z) [M+] calcd for C26H26O6 434.1729; found 434.1745.
Bis-(4-(3-hydroxybut-1-inyl)benzoic acid)-hexane-1,6-diyl-ester (11d). Bisꢀ(4ꢀIodobenzoic acid)ꢀhexaneꢀ1,6ꢀ
diylꢀester (5d) (1.88 g, 3.25 mmol) was subjected to the reaction conditions described in GP2. The reaction was
finished after 24 h yielding the title compound as light yellowish solid (1.41 g, 88%). Rf 0.5 (PE/EtOAc 1:1);
m.p. 80ꢀ82 °C; 1H NMR (300 MHz, CDCl3) δ 7.95 (d, J = 8.6 Hz, 4H), 7.44 (d, J = 8.6 Hz, 4H), 4.77 (q, J = 6.6
Hz, 2H), 4.32 (t, J = 6.5 Hz, 4H), 2.14 (br s, 2H), 1.89 – 1.68 (m, 4H), 1.56 (d, J = 6.6 Hz, 6H), 1.53 – 1.44 (m,
4H); 13C NMR (75 MHz, CDCl3, ppm): δ 166.2, 131.7, 130.0, 129.5, 127.4, 94.0, 83.4, 65.3, 58.9, 28.7, 26.0,
24.4; IR (υ
(m/z) [M+] calcd for C28H30O6 462.2042 ; found 462.2044 .
ꢍ
): 3327 (m) , 2950 (m), 2906 (m), 2852 (m), 1707 (vs), 1606 (m), 1271 (s), 1096 (s) cmꢀ1; HRMS
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Bis-(4-(3-hydroxybut-1-inyl)benzoic acid)-dodecane-1,12-diyl-ester (11e). Bisꢀ(4ꢀIodobenzoic acid)ꢀ
dodecaneꢀ1,12ꢀdiylꢀester (5e) (2.0o g, 3.02 mmol) was subjected to the reaction conditions described in GP2.
The reaction was finished after 24 h yielding the title compound as light brown solid (1.37 g, 83%). Rf 0.47
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(PE/EtOAc 1:1); m.p. 94ꢀ96 °C; H NMR (300 MHz, CDCl3, ppm): δ 7.96 (d, J = 8.3 Hz, 4H), 7.45 (d, J = 8.2
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Hz, 4H), 4.76 (q, J = 9.9 Hz, 2H), 4.30 (t, J = 6.6 Hz, 4H), 2.21 (bs, 2H), 1.83 – 1.66 (m, 4H), 1.54 (t, J = 10.7
Hz, 6H), 1.44 – 1.19 (m, 16H2); 13C NMR (75 MHz, CDCl3, ppm): δ 166.3, 131.7, 130.1, 129.5, 127.3, 94.0,
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83.4, 65.5, 58.8, 29.5, 28.8, 26.1, 24.4; IR (υꢍ): 3332 (m), 2913 (vs), 2848 (s), 1706 (vs), 1605 (m), 1470 (m),
1407 (m), 1316 (m), 1273 (s), 1175 (m), 1097 (s), 1019 (m), 933 (w), 862 (m), 769 (m), 697 (m) cmꢀ1; HRMS
(m/z) [M+] calcd for C34H42O6 546.2976; found 546.2978.
Bis-(2-(4-(3-hydroxybut-1-inyl)phenyl) acetic acid-ethane-1,2-diyl-ester (11f). Bisꢀ(2ꢀ(4ꢀIodophenyl)acetic
acid)ꢀethaneꢀ1,2ꢀdiylꢀester (5f) (2.50 g, 4.55 mmol) was subjected to the reaction conditions described in GP2.
The reaction was finished after 19 h yielding the title compound as light brown solid (1.52 g, 77%). Rf 0.53
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(PE/EtOAc 1:2); m.p. 71ꢀ73 °C; H NMR (300 MHz, CDCl3, ppm) δ 7.36 (d, J = 8.0 Hz, 4H), 7.17 (d, J = 8.0
Hz, 4H), 4.74 (q, J = 6.5 Hz, 2H), 4.27 (s, 4H), 3.57 (s, 4H), 2.33 (br s, 2H), 1.54 (d, J = 6.6 Hz, 6H); 13C NMR
(75 MHz, CDCl3, ppm) δ 171.0, 134.0, 132.0, 129.3, 121.7, 91.4, 83.7, 62.6, 58.9, 41.1, 24.5; IR (υꢍ): 3391 (m),
2984 (w), 1730 (vs), 1511 (w), 1353 (m), 1215 (m), 1158 (m), 1102 (m), 1035 (m) cmꢀ1; HRMS (m/z) [M+]
calcd for C34H42O6 546.2976; found 546.2978.
Bis-(2-(4-(3-hydroxybut-1-inyl)phenyl)acetic acid)-butane-1,4-diyl-ester (11g). Bisꢀ(2ꢀ(4ꢀIodophenyl)acetic
acid)ꢀbutaneꢀ1,4ꢀdiylꢀester (5g) (2.00 g, 3.46 mmol) was subjected to the reaction conditions described in GP2.
The reaction was finished after 26 h yielding the title compound as light brown solid (1.41 g, 88%). Rf 0.28
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(PE/EtOAc 1:1); m.p. 75ꢀ76 °C; H NMR (300 MHz, CDCl3) δ 7.37 (d, J = 8.2 Hz, 4H), 7.20 (d, J = 8.2 Hz,
4H), 4.74 (q, J = 6.6 Hz, 2H), 4.14 – 3.99 (m, 4H), 3.59 (s, 4H), 2.20 (br s, 2H), 1.65 – 1.58 (m, 4H), 1.54 (d, J =
6.6 Hz, 6H); 13C NMR (75 MHz, CDCl3, ppm): δ 171.2, 134.4, 132.0, 129.3, 121.6, 91.3, 83.8, 64.5, 58.9, 41.4,
25.2, 24.5; IR (υꢍ): 3322 (m), 2981 (m), 1726 (vs), 1510 (m), 1318 (m), 1296 (m), 1239 (m), 1098 (m), 1039 (m)
cmꢀ1; HRMS (m/z) [M+] calcd for C28H30O6 462.2042; found 462.2026.
Bis-(2-(4-(3-hydroxybut-1-inyl)phenyl)acetic acid)-hexane-1,6-diyl-ester (11h). Bisꢀ(2ꢀ(4ꢀIodophenyl)acetic
acid)ꢀhexaneꢀ1,6ꢀdiylꢀester (5h) (2.00 g, 3.30 mmol) was subjected to the reaction conditions described in GP2.
The reaction was finished after 23 h yielding the title compound as highly viscous oil (1.28 g, 80%). Rf 0.48
(PE/EtOAc 1:2); 1H NMR (300 MHz, CDCl3, ppm): δ 7.37 (d, J = 8.1 Hz, 4H), 7.21 (d, J = 8.0 Hz, 4H), 4.74 (q,
J = 6.5 Hz, 2H), 4.05 (t, J = 6.5 Hz, 4H), 3.59 (s, 4H), 2.14 (br s, 2H), 1.55 (s, 6H, Hꢀ1), 1.53 (s, 4H), 1.24 (s,
4H); 13C NMR (75 MHz, CDCl3, ppm): δ 171.2, 124.4, 131.8, 129.2, 121.4, 91.2, 83.7, 64.9, 58.8, 41.4, 28.4,
25.4, 24.4; IR (υꢍ): 3416 (m), 2934 (m), 1729 (vs), 1510 (m), 1250 (m), 1157 (s), 1103 (m), 1034 (m) cmꢀ1;
HRMS (m/z) [M+] calcd for C30H34O6 490.2355; found 490.2366.
Bis-(3-(4-(3-hydroxybut-1-inyl)phenyl)propionic
acid)-ethane-1,2-diyl-ester
(11i).
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Iodophenyl)propionic acid)ꢀethaneꢀ1,2ꢀdiylꢀester (5i) (0.70 g, 1.21 mmol) was subjected to the reaction
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conditions described in GP2. The reaction was finished after 23 h yielding the title compound as light brown
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solid (0.39 g, 70%). Rf 0.23 (PE/EtOAc 1:1); m.p. 48ꢀ49 °C; H NMR (300 MHz, CDCl3) δ 7.31 (d, J = 8.0 Hz,
4H), 7.10 (d, J = 8.0 Hz, 4H), 4.72 (q, J = 6.5 Hz, 2H), 4.21 (s, 4H), 2.90 (t, J = 7.6 Hz, 4H), 2.60 (t, J = 7.6 Hz,
4H), 2.50 (br s, 2H), 1.52 (d, J = 6.6 Hz, 6H); 13C NMR (75 MHz, CDCl3, ppm): δ 172.5, 140.9, 131.9, 128.4,
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ꢍ): 3414 (m), 2980 (m), 1733 (vs), 1509 (m), 1371 (m), 1254
(m), 1147 (s), 1104 (s), 1034 (m) cmꢀ1; HRMS (m/z) [M+] calcd for C28H30O6 462.2042; found 462.2063.
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Bis-(3-(4-(3-hydroxybut-1-inyl)phenyl)propionic
acid)-hexane-1,6-diyl-ester
(11j).
Bisꢀ(3ꢀ(4ꢀIodoꢀ
phenyl)propionic acid)ꢀhexaneꢀ1,6ꢀdiylꢀester (5j) (2.05 g, 3.23 mmol) was subjected to the reaction conditions
described in GP2. The reaction was finished after 24 h yielding the title compound as light brown solid (1.44 g,
86%). Rf 0.6 (PE/EtOAc 1:2); m.p. 32ꢀ33 °C; 1H NMR (300 MHz, CDCl3, ppm): δ 7.33 (d, J = 8.1 Hz, 4H), 7.13
(d, J = 8.0 Hz, 4H), 4.73 (q, J = 6.5 Hz, 2H), 4.04 (t, J = 6.5 Hz, 4H), 2.93 (t, J = 7.5 Hz, 4H), 2.6 (t, J = 7.5 Hz,
4H), 2.27 (br s, 2H), 1.54 (s, 4H, Hꢀ14), 1.52 (s, 6H), 1.23 (s, 4H); 13C NMR (75 MHz, CDCl3, ppm): δ 173.0,
141.0, 131.9, 128.4, 120.7, 90.9, 83.9, 64.7, 58.9, 35.7, 31.0, 28.6, 25.7, 24.5; IR (υꢍ): 3423 (m), 2933 (m), 1729
(vs), 1509 (m), 1180 (m), 1155 (m), 1104 (s), 1034 (m) cmꢀ1; HRMS (m/z) [M+] calcd for C32H38O6 518.2668;
found 518.2685.
Bis-(3-(4-(3-hydroxybut-1-inyl)phenyl)propionic acid)-decane-1,10-diyl-ester (11k). Bisꢀ(3ꢀ(4ꢀIodoꢀ
phenyl)propionic acid)ꢀdecaneꢀ1,10ꢀdiylꢀester (5k) (0.388 g, 0.562 mmol) was subjected to the reaction
conditions described in GP2. The reaction was finished after 23 h yielding the title compound as light brown
solid (0.234 g, 73%). Rf 0.5 (PE/EtOAc 1:1); m.p. 48ꢀ50 °C; 1H NMR (300 MHz, CDCl3, ppm) δ 7.33 (d, J = 8.0
Hz, 4H), 7.13 (d, J = 8.0 Hz, 4H), 4.74 (q, J = 6.6 Hz, 2H), 4.04 (t, J = 6.7 Hz, 4H), 2.93 (t, J = 7.7 Hz, 4H), 2.60
(t, J = 7.7 Hz, 4H), 2.04 (br s, 2H), 1.57 – 1.45 (m, 10H), 1.26 (s, 12H); 13C NMR (75 MHz, CDCl3, ppm) δ
173.0, 141.2, 131.9, 128.4, 120.6, 90.8, 84.0, 64.9, 58.9, 35.7, 31.0, 29.4, 28.7, 26.0, 24.6, 24.0; IR (υꢍ): 3326
(m), 2959 (m), 2922 (s), 2855 (m), 1726 (vs), 1510 (w), 1478 (w), 1446 (w), 1428 (w), 1369 (m), 1323 (m),
1296 (m), 1169 (m), 1152 (m), 1106 (m), 1078 (m), 1037 (m), 931 (w), 832 (m) cmꢀ1; HRMS (m/z) [M+] calcd
for C36H46O6 574.3294; found 574.3300.
Bis-(3-(4-(3-hydroxybut-1-inyl)phenyl)propionic acid)-dodecane-1,12-diyl-ester (11l). Bisꢀ(3ꢀ(4ꢀIodoꢀ
phenyl)propionic acid)ꢀdodecaneꢀ1,12ꢀdiylꢀester (2.5 g, 3.48mmol) was subjected to the reaction conditions
described in GP2. The reaction was finished after 20 h yielding the title compound as light brown solid (1.32 g,
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63%). Rf 0.48 (PE/EtOAc 1:1); m.p. 59ꢀ61 °C; H NMR (300 MHz, CDCl3, ppm): δ 7.32 (d, J = 8.1 Hz, 4H),
7.12 (d, J = 8.0 Hz, 4H), 4.73 (q, J = 6.6 Hz, 2H), 4.04 (t, J = 6.7 Hz, 4H), 2.92 (t, J = 7.7 Hz, 4H), 2.59 (t, J =
7.7 Hz, 4H), 2.27 (br s, 2H), 1.62 – 1.46 (m, 10H), 1.25 (s, 16H); 13C NMR (75 MHz, CDCl3, ppm): δ 173.0,
141.1, 131.9, 128.4, 120.6, 90.8, 84.0, 64.9, 58.8, 35.7, 30.9, 29.6, 29.3, 28.7, 26.0, 24.5, 24.0; IR (υꢍ): 3340 (m),
2916 (vs), 2851 (s), 1725 (vs), 1510 (w), 1472 (w), 1445 (w), 1419 (w), 1396 (w), 1320 (m), 1296 (m), 1266
(m), 1178 (m), 1169 (m), 1106 (m), 1077 (m), 1037 (m), 933 (w), 833 (m) cmꢀ1; HRMS (m/z): [M+] calcd for
C38H50O6 602.3602; found 602.3600.
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Bis-(4-(3-oxobut-1-inyl)benzoic acid)-ethane-1,2-diyl-ester (12a). Bis(4ꢀ(3ꢀhydroxybutꢀ1ꢀinyl)benzoic acid))ꢀ
ethaneꢀ1,2ꢀdiylꢀester (11a) (1.00 g, 2.46 mmol) was subjected to the reaction conditions described in GP3. The
reaction was finished after 23 h yielding the title compound as light yellowish solid (0.72 g, 73%). Rf 0.6
(PE/EtOAc 1:1); m.p. 160ꢀ162 °C; 1H NMR (300 MHz, CDCl3, ppm): δ 8.04 (d, J = 8.2 Hz, 4H), 7.62 (d, J = 8.2
Hz, 4H), 4.68 (s, 4H), 2.46 (s, 6H); 13C NMR (75 MHz, CDCl3, ppm): δ 184.3, 165.4, 133.0, 131.3, 129.9, 124.9,
90.1, 88.3, 63.1, 32.9; IR (υꢍ): 2962 (w), 2200 (s), 1711 (vs), 1664 (s), 1604 (m), 1403 (m), 1366 (m), 1258 (vs),
1178 (m), 1118 (s), 1106 (s), 1010 (m) cmꢀ1; HRMS (m/z) [M+] calcd for C24H18O6 402.1103; found 402.1100 ;
UVꢀVis (ACN): λmax (nm) = 276 (ε = 42506 Mꢀ1ꢁcmꢀ1).
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Bis-(4-(3-oxobut-1-inyl)benzoic acid)-propane-1,3-diyl-ester (12b). Bisꢀ(4ꢀ(3ꢀhydroxybutꢀ1ꢀinyl)benzoic
acid)ꢀpropaneꢀ1,3ꢀdiylꢀester (11b) (1.00 g, 2.38 mmol) was subjected to the reaction conditions described in
GP3. The reaction was finished after 24 h yielding the title compound as light yellowish solid (0.72 g, 73%).
Rf 0.32 (PE/EtOAc 3:1); m.p. 118ꢀ119 °C; 1H NMR (300 MHz, CDCl3, ppm): δ 8.01 (d, J = 8.2 Hz, 4H), 7.59 (d,
J = 8.2 Hz, 4H), 4.51 (t, J = 6.1 Hz, 4H), 2.46 (s, 6H), 2.27 (d, J = 5.8 Hz, 2H); 13C NMR (75 MHz, CDCl3,
ppm): δ 184.4, 165.5, 132.9, 131.6, 129.7, 124.7, 90.0, 88.4, 62.3, 32.9, 28.2; IR (υꢍ): 2914 (w), 2205 (s), 1710
(s), 1668 (vs), 1405 (w), 1361 (s), 1269 (vs), 1178 (s), 1123 (s), 1108 (s) cmꢀ1; HRMS (m/z) [M+] calcd for
C25H20O6 416.1260; found 416.1266; UVꢀVis (ACN): λmax (nm) = 276 (ε = 48978 Mꢀ1ꢁcmꢀ1),
Bis-(4-(3-oxobut-1-inyl)benzoic acid)-butan-1,4-diyl-ester (12c). Bisꢀ(4ꢀ(3ꢀhydroxybutꢀ1ꢀinyl)benzoic acid)ꢀ
butaneꢀ1,4ꢀdiylꢀester (11c) (1.5 g, 3.45 mmol) was subjected to the reaction conditions described in GP3. The
reaction was finished after 23 h yielding the title compound as light yellowish solid (0.82 g, 55%). Rf 0.15
(PE/EtOAc 3:1); m.p. 127.128 °C; 1H NMR (300 MHz, CDCl3, ppm): δ 8.03 (d, J = 8.4 Hz, 4H), 7.61 (d, J = 8.4
Hz, 4H), 4.41 (s, 4H), 2.46 (s, 6H), 1.95 (s, 4H); 13C NMR (75 MHz, CDCl3, ppm): δ 184.4, 165.6, 132.9, 131.9,
129.7, 124.6, 90.0, 88.5, 65.0, 32.9, 25.6; IR (υꢍ): 2959 (w), 2198 (s), 1714 (s), 1667 (s), 1266 (vs), 1239 (s),
1108 (s) cmꢀ1; HRMS (m/z) [M+] calcd for C26H22O6 430.1416; found 430.1408; UVꢀVis (ACN): λmax (nm) =
276 (ε = 47245 Mꢀ1ꢁcmꢀ1).
Bis-(4-(3-oxobut-1-inyl)benzoic acid)-hexane-1,6-diyl-ester (12d). Bisꢀ(4ꢀ(3ꢀhydroxybutꢀ1ꢀinyl)benzoic acid)ꢀ
hexaneꢀ1,6ꢀdiylꢀester (11d) (0.935 g, 2.02 mmol) was subjected to the reaction conditions described in GP3. The
reaction was finished after 20 h yielding the title compound as light yellowish solid (0.78 g, 86%). Rf 0.43
(PE/EtOAc 3:1); m.p. 101ꢀ102 °C; 1H NMR (300 MHz, CDCl3, ppm): δ 8.02 (d, J = 8.7 Hz, 4H), 7.60 (d, J = 8.7
Hz, 4H), 4.33 (t, J = 6.6 Hz, 4H), 2.45 (s, 6H), 1.92 – 1.69 (m, 4H), 1.58 – 1.45 (m, 4H); 13C NMR (75 MHz,
CDCl3, ppm): δ 184.3, 165.7, 132.9, 132.1, 129.7, 124.4, 89.9, 88.6, 65.4, 32.8, 28.7, 25.8; IR (υꢍ): 2945 (w),
2205 (m), 1707 (s), 1668 (s), 1269 (vs), 1105 (s), 771 (s), 697 (s) cmꢀ1; HRMS (m/z) [M+] calcd for C28H26O6
458.1729; found 458.1725; UVꢀVis (ACN): λmax (nm) = 276 (ε = 47904 Mꢀ1ꢁcmꢀ1).
Bis-(4-(3-oxobut-1-inyl)benzoic acid)-dodecane-1,12-diyl-ester (12e). Bisꢀ(4ꢀ(3ꢀhydroxybutꢀ1ꢀinyl)benzoic
acid)ꢀdodecaneꢀ1,12ꢀdiylꢀester (11e) (1.10 g, 2.01 mmol) was subjected to the reaction conditions described in
GP3. The reaction was finished after 22 h yielding the title compound as orange solid (0.77 g, 71%). Rf 0.5
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(PE/EtOAc 3:1); m.p. 78ꢀ79 °C; 1H NMR (300 MHz, CDCl3, ppm): δ 8.04 (d, J = 8.3 Hz, 4H, HꢀAr), 7.61 (d, J
= 8.3 Hz, 4H, HꢀAr), 4.31 (t, J = 6.7 Hz, 4H, CH2), 2.46 (s, 6H, CH3), 1.87 – 1.64 (m, 4H, CH2), 1.53 – 1.16 (m,
16H, CH2); 13C NMR (75 MHz, CDCl3, ppm): δ 184.4, 165.7, 132.9, 132.2, 129.7, 124.4, 89.9, 88.6, 65.7, 32.9,
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29.9 – 29.2, 28.8, 26.1; IR (υꢍ): 2918 (s), 2850 (m), 2208 (m), 1709 (vs), 1670 (s), 1604 (w), 1408 (w), 1359 (w),
1271 (s), 1181 (m), 1122 (m), 1015 (w) cmꢀ1; HRMS (m/z) [M+] calcd for C34H38O6 542.2668; found 542.2641;
UVꢀVis (ACN): λmax (nm) = 276 (ε = 50282 Mꢀ1ꢁcmꢀ1).
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Bis-(4-(2-(3-oxobut-1-inyl)phenyl)acetic acid)-ethane-1,2-diyl-ester (12f). Bisꢀ(2ꢀ(4ꢀ(3ꢀhydroxybutꢀ1ꢀ
inyl)phenyl)acetic acid)ꢀethaneꢀ1,2ꢀdiylꢀester (11f) (1.00 g, 2.3 mmol) was subjected to the reaction conditions
described in GP3. The reaction was finished after 24 h yielding the title compound as light yellowish solid (0.7
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g, 71%). Rf 0.55 (PE/EtOAc 1:1); m.p. 79ꢀ80 °C; H NMR (300 MHz, CDCl3, ppm): δ 7.52 (d, J = 8.1 Hz, 4H),
7.27 (d, J = 8.2 Hz, 4H), 4.30 (s, 4H), 3.62 (s, 4H), 2.44 (s, 6H); 13C NMR (75 MHz, CDCl3, ppm): δ 184.6,
170.5, 136.7, 133.4, 129.8, 119.0, 90.0, 88.6, 62.7, 41.1, 32.8; IR (υꢍ): 2986 (w), 200 (vs), 1738 (vs), 1664 (vs),
1362 (m), 1149 (s) cmꢀ1; HRMS (m/z) [M+] calcd for C26H22O6 430.1416; found 430.1424; UVꢀVis (ACN): λmax
(nm) = 276 (ε = 37840 Mꢀ1ꢁcmꢀ1).
Bis-(4-(2-(3-oxobut-1-inyl)phenyl)acetic acid)-butane-1,4-diyl-ester (12g). Bisꢀ(2ꢀ(4ꢀ(3ꢀhydroxybutꢀ1ꢀ
inyl)phenyl)acetic acid)ꢀbutaneꢀ1,4ꢀdiylꢀester (11g) (0.20 g, 0.432 mmol) was subjected to the reaction
conditions described in GP3. The reaction was finished after 23 h yielding the title compound as light yellowish
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solid (0.14 g, 70%). Rf 0.67 (PE/EtOAc 1:1); m.p. 62ꢀ63 °C; H NMR (300 MHz, CDCl3, ppm): δ 7.53 (d, J =
8.3 Hz, 4H), 7.30 (d, J = 8.4 Hz, 4H), 4.09 (t, J = 5.0 Hz, 4H), 3.64 (s, 4H), 2.44 (s, 6H), 1.67 – 1.61 (m, 4H);
13C NMR (75 MHz, CDCl3, ppm): δ 184.7, 170.8, 137.1 ,133.5, 129.8, 118.9, 90.1, 88.6, 64.6, 41.4, 32.9, 25.3;
IR (υꢍ
): 2962 (w), 2201 (vs), 1721 (vs), 1670 (vs), 1224 (s), 1146 (s), 970 (m) cmꢀ1; HRMS (m/z) [M+] calcd for
C28H26O6 458.1729; found 413.1726 ; UVꢀVis (ACN): λmax (nm) = 276 (ε = 35073 Mꢀ1ꢁcmꢀ1).
Bis-(4-(2-(3-oxobut-1-inyl)phenyl)acetic acid)-hexane-1,6-diyl-ester (12h). Bisꢀ(2ꢀ(4ꢀ(3ꢀhydroxybutꢀ1ꢀ
inyl)phenyl)acetic acid)ꢀhexaneꢀ1,6ꢀdiylꢀester (11h) (1.14 g, 2.32 mmol) was subjected to the reaction conditions
described in GP3. The reaction was finished after 24 h yielding the title compound as light yellowish solid (0.77
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g, 68%). Rf 0.35 (PE/EtOAc 3:1); m.p. 52ꢀ53 °C; H NMR (300 MHz, CDCl3, ppm): δ 7.53 (d, J = 8.2 Hz, 4H),
7.30 (d, J = 8.1 Hz, 4H), 4.07 (t, J = 6.6 Hz, 4H), 3.63 (s, 4H), 2.44 (s, 6H), 1.67 – 1.49 (m, 4H), 1.29 (t, J = 10.1
Hz, 4H); 13C NMR (75 MHz, CDCl3, ppm): δ 184.7, 170.9, 137.2, 133.4, 129.8, 118.8, 90.2, 88.6, 65.1, 41.5,
32.9, 28.5, 25.5; IR (υꢍ): 2958 (w), 2199 (s), 1730 (vs), 1668 (vs), 1215 (m), 1153 (s), 986 (m) cmꢀ1; HRMS (m/z)
[M+] calcd for C30H30O6 486.2042; found 486.2044; UVꢀVis (ACN): λmax (nm) = 276 (ε = 37412 Mꢀ1ꢁcmꢀ1).
Bis-(3-(4-(3-oxobut-1-inyl)phenyl)propionic acid)-ethane-1,2-diyl-ester (12i). Bisꢀ(3ꢀ(4ꢀ(3ꢀhydroxybutꢀ1ꢀ
inyl)phenyl)propionic acid)ꢀethaneꢀ1,2ꢀdiylꢀester (11i) (1.00 g, 2.16 mmol) was subjected to the reaction
conditions described in GP3. The reaction was finished after 22 h yielding the title compound as light yellowish
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solid (0.6 g, 60%). Rf 0.4 (PE/EtOAc 3:1); m.p. 54ꢀ55 °C; H NMR (300 MHz, CDCl3, ppm): δ 7.49 (d, J = 8.2
Hz, 4H), 7.21 (d, J = 8.1 Hz, 4H), 4.24 (s, 4H), 2.96 (t, J = 7.6 Hz, 4H), 2.63 (t, J = 7.6 Hz, 4H), 2.43 (s, 6H);
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13C NMR (75 MHz, CDCl3, ppm): δ 184.7, 172.3, 143.7, 133.4, 128.8, 118.0, 90.5, 88.4, 62.4, 35.1, 32.9, 30.9;
IR (υꢍ): 2919 (w), 2197 (vs), 1733 (s), 1657 (vs), 1605 (w), 1356 (m), 1282 (m), 1150 (s), 978 (m), 836 (m) cmꢀ1;
HRMS (m/z) [M+] calcd for C28H26O6 458.1729; found 458.1714; UVꢀVis (ACN): λmax (nm) = 276 (ε = 36700
Mꢀ1ꢁcmꢀ1).
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Bis-(3-(4-(3-oxobut-1-inyl)phenyl)propionic acid)-hexane-1,6-diyl-ester (12j). Bisꢀ(3ꢀ(4ꢀ(3ꢀhydroxybutꢀ1ꢀ
inyl)phenyl)propionic acid)ꢀhexaneꢀ1,6ꢀdiylꢀester (11j) (1.00 g, 2.62 mmol) was subjected to the reaction
conditions described in GP3. The reaction was finished after 23 h yielding the title compound as orange solid
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(1.0 g, 74%). Rf 0.45 (PE/EtOAc 3:1); m.p. 62ꢀ63 °C; H NMR (300 MHz, CDCl3, ppm): δ 7.48 (d, J = 8.1 Hz,
4H), 7.22 (d, J = 8.1 Hz, 4H), 4.04 (t, J = 6.6 Hz, 4H), 2.95 (d, J = 7.6 Hz, 4H), 2.62 (t, J = 7.6 Hz, 4H), 2.43 (s,
6H), 1.57 (m, 4H,), 1.28 (s, 4H); 13C NMR (75 MHz, CDCl3, ppm): δ 184.7, 172.6, 144.0, 133.4, 128.8, 117.9,
90.6, 88.4, 64.6, 35.4, 32.8, 31.0, 28.6, 25.6; IR (υꢍ): 2929 (w), 2197 (vs), 1718 (s), 1670 (vs), 1355 (m), 1278
(m), 1151 (s) cmꢀ1; HRMS (m/z) [M+] calcd for C32H34O6 514.2355; found 514.2363; UVꢀVis (ACN): λmax (nm)
= 276 (ε = 36707 Mꢀ1ꢁcmꢀ1).
Bis-(3-(4-(3-oxobut-1-inyl)phenyl)propionic acid)-decane-1,10-diyl-ester (12k). Bisꢀ(3ꢀ(4ꢀ(3ꢀhydroxybutꢀ1ꢀ
inyl)phenyl)propionic acid)ꢀdecaneꢀ1,10ꢀdiylꢀester (11k) (0.211 g, 0.367 mmol) was subjected to the reaction
conditions described in GP3. The reaction was finished after 25 h yielding the title compound as light yellowish
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solid (0.163 g, 78%). Rf 0.25 (PE/EtOAc 3 : 1); m.p. 38ꢀ40 °C; H NMR (300 MHz, CDCl3, ppm) δ 7.49 (d, J =
8.0 Hz, 4H), 7.22 (d, J = 8.0 Hz, 4H), 4.04 (t, J = 6.7 Hz, 4H), 2.97 (t, J = 7.6 Hz, 4H), 2.62 (t, J = 7.6 Hz, 4H),
2.43 (s, 6H), 1.63 – 1.49 (m, 4H), 1.26 (s, 12H); 13C NMR (75 MHz, CDCl3, ppm) δ 184.7, 172.6, 144.0, 133.4,
128.8, 117.9, 90.6, 88.3, 64.9, 35.4, 32.8, 31.1, 29.4, 28.7, 26.0; IR (υꢍ): 2958(m), 2920 (m), 2850 (m), 2202 (s),
1725 (vs), 1668 (vs), 1509 (w), 1413 (w), 1360 (m), 1281 (m), 1180 (m), 1152 (s), 983 (w), 834 (w), 641 (w)
cmꢀ1; HRMS (m/z) [M+] calcd for C36H42O6 570.2981; found 570.2983; UVꢀVis (ACN): λmax (nm) = 276 (ε =
37243 Mꢀ1ꢁcmꢀ1).
Bis-(3-(4-(3-oxobut-1-inyl)phenyl)propionic acid)-dodecane-1,12-diyl-ester (12l). Bisꢀ(3ꢀ(4ꢀ(3ꢀhydroxybutꢀ1ꢀ
inyl)phenyl)propionic acid)ꢀdodecaneꢀ1,12ꢀdiylꢀester (11l) (1.08 g, 1.79 mmol) was subjected to the reaction
conditions described in GP3. The reaction was finished after 23 h yielding the title compound as light yellowish
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solid (0.71 g, 66%). Rf 0.32 (PE/EtOAc 3 : 1); m.p. 51ꢀ53 °C; H NMR (300 MHz, CDCl3, ppm): δ 7.49 (d, J =
8.1 Hz, 4H), 7.22 (d, J = 8.1 Hz, 4H), 4.04 (t, J = 6.7 Hz, 4H), 2.97 (t, J = 7.6 Hz, 4H), 2.62 (t, J = 7.6 Hz, 4H),
2.43 (s, 6H), 1.67 – 1.46 (m, 4H), 1.25 (s, 16H).; 13C NMR (75 MHz, CDCl3, ppm): δ 184.7, 172.6, 144.0, 133.4,
128.8, 117.9, 90.6, 88.4, 64.9, 35.4, 32.8, 31.1, 29.6, 29.3, 28.7, 26.0; IR (υꢍ): 2960 (m), 2921 (m), 2851 (m),
2203 (vs), 1725 (vs), 1668 (s), 1510 (w), 1426 (w), 1360 (m), 1282 (m), 1185 (s), 1151 (s), 1051 (w) cmꢀ1;
HRMS (m/z) [M+] calcd for C38H46O6 598.3294; found 598.3307; UVꢀVis (ACN): λmax (nm) = 276 (ε = 39223
Mꢀ1ꢁcmꢀ1).
Bisꢀ(4ꢀ(3ꢀoxobutꢀ1ꢀinyl)benzoic acid)ꢀethaneꢀ1,2ꢀdiylꢀester (12a) (0.132 g, 0.32 mmol) was subjected to the
reaction conditions described in GP4. The starting material was recovered completely (0.131 g, 99%).
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14,15-Diacetyl-6,7-dihydro-5H,9H-2,17-(ethanediylidene)-10,13-etheno-4,8 benzodioxacyclopenta-decine-
3,9-dione (13b). Bisꢀ(4ꢀ(3ꢀoxobutꢀ1ꢀinyl)benzoic acid)ꢀpropaneꢀ1,3ꢀdiylꢀester (12b) (0.141 g, 0.34 mmol) was
subjected to the reaction conditions described in GP4. The reaction was finished after 70 min yielding the title
compound as yellowish solid (0.047 mg, 33%). The starting material 12b was recovered (45 mg, 32%). Rf 0.39
(PE/EtOAc 1:1); m.p. 200ꢀ201 °C; 1H NMR (300 MHz, CDCl3) δ 8.41 (s, 1H), 8.04 – 7.91 (m, 2H), 7.74 (d, J =
8.2 Hz, 2H), 7.45 (d, J = 8.2 Hz, 2H), 6.34 (s, 1H), 4.38 (t, J = 7.0 Hz, 2H), 4.28 – 4.16 (m), 2.79 (s, 3H), 2.60 (s,
3H), 2.11 – 1.97 (m, 2H); 13C NMR (75 MHz, CDCl3) δ 204.1, 198.3, 169.6, 164.9, 141.0, 136.8, 136.5, 136.0,
135.1, 133.8, 132.5, 131.0, 130.1, 129.1, 127.7, 126.5, 66.9, 62.9, 32.5, 29.5, 27.1; IR (υꢍ): 2925 (w), 1720 (vs),
1703 (vs), 1677 (s), 1383 (m), 1259 (s), 1237 (s), 1125 (m), 1100 (m), 1076 (m) cmꢀ1; HRMS (m/z) [M+] calcd
for C25H20O6 416.1260; found 416.1279.
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15,16-Diacetyl-5,6,7,8-tetrahydro-10H-2,18-(ethanediylidene)-11,14-etheno-4,9-benzodioxacyclohexa-
decine-3,10-dione (13c). Bisꢀ(4ꢀ(3ꢀoxobutꢀ1ꢀinyl)benzoic acid)ꢀbutaneꢀ1,4ꢀdiylꢀester (12c) (0.124 g, 0.27 mmol)
was subjected to the reaction conditions described in GP4. The reaction was finished after 60 min yielding the
title compound as yellowish solid (0.058 g, 47%). The starting material 12c was recovered (0.029 g, 23%). Rf
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0.43 (PE/EtOAc 1:1); m.p. 216ꢀ217 °C; H NMR (300 MHz, CDCl3) δ 8.42 (s, 1H), 8.07 (dd, J = 10.8, 4.6 Hz,
3H), 7.98 (d, J = 8.5 Hz, 1H), 7.41 (d, J = 8.2 Hz, 2H), 6.74 (s, 1H), 4.56 – 4.34 (m, 2H), 4.17 – 4.06 (m, 2H),
2.79 (s, 3H), 2.55 (s, 3H), 1.87 – 1.76 (m, 2H), 1.70 – 1.57 (m, 2H); 13C NMR (75 MHz, CDCl3) δ 204.6, 198.5,
179.7, 168.7, 166.0, 141.4, 137.5, 136.9, 135.6, 134.2, 133.2, 132.2, 131.4, 130.7, 129.9, 129.7, 129.5, 127.2,
66.6, 66.0, 32.8, 29.5, 27.4, 26.3; IR (υꢍ): 2965 (w), 1709 (vs), 1673 (s), 1382 (m), 1262 (s), 1239 (s), 1111 (m),
1092 (s),1016 (m) cmꢀ1; HRMS (m/z) [M+] calcd for C26H22O6 430.1416; found 430.1424.
17,18-Diacetyl-5,6,7,8,9,10-hexahydro-12H-2,20-(ethanediylidene)-13,16-etheno-4,11
benzodioxacyclo-
octadecine-3,12-dione (13d). Bisꢀ(4ꢀ(3ꢀoxobutꢀ1ꢀinyl)benzoic acid)ꢀhexaneꢀ1,6ꢀdiylꢀester (12d) (0.106 g, 0.23
mmol) was subjected to the reaction conditions described in GP4. The reaction was finished after 50 min
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yielding the title compound as yellowish solid (0.074 g, 70%). Rf 0.50 (PE/EtOAc 1:1); m.p. 169ꢀ170 °C; H
NMR (300 MHz, CDCl3) δ 8.44 (s, 1H), 8.21 – 8.10 (m, 3H), 8.02 (d, J = 8.5 Hz, 1H), 7.46 (s, 1H), 7.40 (d, J =
8.1 Hz, 2H), 4.53 (t, J = 5.2 Hz, 2H), 4.24 – 4.11 (m, 2H), 2.79 (s, 3H), 2.41 (s, 3H), 1.87 – 1.76 (m, 2H), 1.59 –
1.46 (m, 4H), 1.40 – 1.29 (m, 2H); 13C NMR (75 MHz, CDCl3, ppm) δ 204.7, 198.3, 166.5, 166.0, 140.7, 136.7,
134.7, 134.4, 134.0, 131.3, 131.1, 130.7, 129.6, 129.5, 129.0, 127.2, 66.7, 32.4, 30.4, 29.5, 29.1, 28.2, 27.2; IR
(υꢍ): 2930 (m), 2857 (w), 1715 (vs), 1681 (s), 1383 (m), 1266 (vs), 1101 (s), 1018 (m), 761 (m) cmꢀ1; HRMS
(m/z) [M+] calcd for C28H26O6 458.1729; found 458.1734.
23,24-Diacetyl-5,6,7,8,9,10,11,12,13,14,15,16-dodecahydro-18H-2,26-(ethanediylidene)-19,22-etheno-4,17-
benzodioxacyclotetracosine-3,18-dione (13e). Bisꢀ(4ꢀ(3ꢀoxobutꢀ1ꢀinyl) benzoic acid)ꢀdodecaneꢀ1,12ꢀdiylꢀester
(0.130 g, 0.24 mmol) was subjected to the reaction conditions described in GP4. The reaction was finished after
60 min yielding the title compound as yellowish solid (0.051 g, 39%). Rf 0.52 (PE/EtOAc 1:1); m.p. 95ꢀ97 °C;
1H NMR (300 MHz, CDCl3) δ 8.44 (s, 1H), 8.21 (dd, J = 12.6, 8.4 Hz, 4H), 8.08 (d, J = 8.4 Hz, 1H), 7.42 (d, J =
8.0 Hz, 2H), 4.51 – 4.39 (m, 2H), 4.24 (t, J = 6.2 Hz, 2H), 2.76 (s, 3H), 2.08 (s, 3H), 1.56 (ddd, J = 20.9, 12.9,
6.7 Hz, 4H), 1.38 – 1.15 (m, 16H); 13C NMR (75 MHz, CDCl3, ppm) δ 13C NMR (75 MHz, CDCl3) δ 205.2,
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198.5, 166.4, 166.1, 140.4, 140.0, 136.8, 135.2, 134.3, 133.1, 131.2, 131.1, 129.8, 129.6, 128.4, 127.5, 65.5,
65.5, 64.9, 31.9, 28.7, 28.6, 28.4, 28.1, 27.8, 27.5, 27.3, 27.0, 25.6, 24.9; IR (υꢍ): 2926 (s), 2855 (m), 1716 (vs),
1684 (s), 1383 (m), 1266 (vs), 1177 (m), 1106 (m), 1019 (w) cmꢀ1; HRMS (m/z) [M+] calcd for C34H38O6
542.2668; found 542.2640.
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15,16-Diacetyl-6,7-dihydro-2,18-(ethanediylidene)-11,14-etheno-5,8-benzodioxacyclohexadecine-
4,9(3H,10H)-dione (13f). Bisꢀ(2ꢀ(4ꢀ(3ꢀoxobutꢀ1ꢀinyl)phenyl)acetic acid)ꢀethaneꢀ1,2ꢀdiylꢀester (12f) (0.121 g,
0.28 mmol) was subjected to the reaction conditions described in GP4. The reaction was finished after 50 min
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yielding the title compound as yellowish solid (0.063 g, 52%). Rf 0.24 (PE/EtOAc 1:1); m.p. 219ꢀ220 °C; H
NMR (300 MHz, CDCl3) δ 8.39 (s, 1H), 7.92 (d, J = 8.3 Hz, 1H), 7.43 – 7.30 (m, 3H), 7.20 (d, J = 8.0 Hz, 2H),
6.83 (s, 1H), 4.41 – 4.24 (m, 2H), 4.16 – 4.01 (m, 2H), 3.80 (s, 2H), 3.66 (s, 2H), 2.75 (s, 3H), 2.37 (s, 3H); 13
C
NMR (75 MHz, CDCl3) δ 205.4, 198.2, 170.8, 170.7, 138.1, 135.9, 135.6, 134.4, 132.6, 131.3, 131.1, 130.8,
129.6, 126.5, 129.4, 125.3, 64.3, 62.2, 42.0, 41.7, 32.5, 26.9; IR (υꢍ): 2924 (w), 1728 (vs), 1699 (s), 1675 (s),
1427 (m), 1309 (m), 1260(m), 1232 (s), 1134 (m) cmꢀ1; HRMS (m/z) [M+] calcd for C26H22O6 430.1416; found
430.1411.
17,18-Diacetyl-6,7,8,9-tetrahydro-2,20-(ethanediylidene)-13,16-etheno-5,10-benzodioxacycloocta-decine-
4,11(3H,12H)-dione (13g). Bisꢀ(2ꢀ(4ꢀ(3ꢀoxobutꢀ1ꢀinyl)phenyl)acetic acid)ꢀbutaneꢀ1,4ꢀdiylꢀester (12g) (0.137 g,
0.29 mmol) was subjected to the reaction conditions described in GP4. The reaction was finished after 40 min
yielding the title compound as yellowish solid (0.072 g, 53%). Rf 0.54 (PE/EtOAc 1:1); m.p. 186ꢀ187 °C;
1H NMR (300 MHz, CDCl3, ppm) δ 8.40 (s, 1H), 7.97 (d, J = 8.2 Hz, 1H), 7.45 (dd, J = 12.4, 5.8 Hz, 4H), 7.26
(d, J = 8.1 Hz, 2H), 4.22 (t, J = 5.4 Hz, 2H), 3.95 (t, J = 7.0 Hz, 2H), 3.72 (s, 4H), 2.76 (s, 3H), 2.16 (s, 3H), 1.60
(dt, J = 10.0, 5.7 Hz, 2H), 1.51 – 1.37 (m, 2H); 13C NMR (75 MHz, CDCl3, ppm) δ 205.8, 198.5, 171.1, 170.6,
139.5, 135.8, 135.1, 134.6, 133.0, 131.1, 129.8, 129.5, 129.4, 125.5, 65.0, 63.9, 42.4, 41.9, 32.1 , 27.1 , 25.5,
25.4; IR (υꢍ): 2959 (w), 1728 (vs), 1699 (s), 1678 (s), 1426 (m), 1246 (s), 1155 (m), 1140 (m), 1020 (w) cmꢀ1;
HRMS (m/z) [M+] calcd for C28H26O6 458.1729; found 458.1732.
19,20-Diacetyl-6,7,8,9,10,11-hexahydro-2,22-(ethanediylidene)-15,18-etheno-5,12-benzodioxacycloico-sine-
4,13(3H,14H)-dione (13h). Bisꢀ(2ꢀ(4ꢀ(3ꢀoxobutꢀ1ꢀinyl)phenyl)acetic acid)ꢀhexaneꢀ1,6ꢀdiylꢀester (12h) (0.119 g,
0.24 mmol) was subjected to the reaction conditions described in GP4. The reaction was finished after 40 min
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yielding the title compound as yellowish solid (0.084 g, 70%). Rf 0.54 (PE/EtOAc 1:1); m.p. 149ꢀ150 °C; H
NMR (300 MHz, CDCl3) δ 8.38 (s, 1H), 7.96 (d, J = 8.3 Hz, 1H), 7.50 (d, J = 8.4 Hz, 1H), 7.47 – 7.41 (m, 3H),
7.25 (d, J = 7.6 Hz, 2H), 4.18 (t, J = 5.4 Hz, 2H), 3.97 (t, J = 5.5 Hz, 2H), 3.67 (d, J = 7.3 Hz, 4H), 2.73 (s, 3H),
2.09 (s, 3H), 1.62 (dd, J = 11.7, 5.8 Hz, 2H), 1.52 – 1.42 (m, 2H), 1.41 – 1.33 (m, 2H), 1.31 – 1.22 (m, 2H);
13C NMR (75 MHz, CDCl3, ppm) δ 205.9, 198.5, 171.4, 170.9, 139.6, 135.9, 135.8, 135.0, 134.6, 134.5, 133.1,
131.2, 131.1, 129.8, 129.5, 129.3, 127.1, 65.2, 64.2, 42.4, 32.0, 28.6, 28.3, 27.1, 25.6, 25.3; IR (υꢍ): 2926 (m),
2858 (m), 1733 (s), 1715 (vs), 1698 (vs), 1682 (vs), 1431 (m), 1381 (m), 1301 (m), 1247 (s), 1133 (m), 983 (m)
cmꢀ1; HRMS (m/z) [M+] calcd for C30H30O6 486.2042; found 486.2059.
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The Journal of Organic Chemistry
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17,18-Diacetyl-3,4,7,8,11,12-hexahydro-5H,10H-2,20-(ethanediylidene)-13,16-etheno-6,9-
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benzodioxacyclooctadecine-5,10-dione (13i). Bisꢀ(3ꢀ(4ꢀ(3ꢀoxobutꢀ1ꢀinyl)phenyl)propionic acid)ꢀethaneꢀ1,2ꢀ
diylꢀester (12i) (0.115 g, 0.25 mmol) was subjected to the reaction conditions described in GP4. The reaction
was finished after 55 min yielding the title compound as yellowish solid (0.068 g, 59%). Rf 0.40 (PE/EtOAc 1:1);
m.p. 186ꢀ187 °C; 1H NMR (300 MHz, CDCl3, ppm) δ 8.34 (s, 1H), 7.90 (d, J = 8.4 Hz, 1H), 7.42 (d, J = 8.3 Hz,
1H), 7.30 (d, J = 7.9 Hz, 2H), 7.17 (d, J = 8.0 Hz, 2H), 7.04 (s, 1H), 4.32 (dd, J = 5.1, 2.7 Hz, 2H), 4.05 – 3.96
(m, 2H), 3.19 – 3.10 (m, 2H), 3.05 (dd, J = 7.6, 4.4 Hz, 2H), 2.81 – 2.75 (m, 2H), 2.73 (s, 3H), 2.70 – 2.64 (m,
2H), 2.11 (s, 3H); 13C NMR (75 MHz, CDCl3, ppm) δ 206.1, 198.6, 172.9, 172.3, 141.5, 140.3, 139.4, 136.0,
134.9, 134.5, 132.6, 131.0, 130.9, 130.6, 129.4, 129.2, 128.8, 122.9, 63.8, 62.1, 36.4, 32.0, 31.6, 29.9, 29.5, 27.1;
IR (υꢍ): 2921 (w), 1727 (vs), 1676 (s), 1434 (w), 1345 (w), 1294 (m), 1243 (m), 1196 (m), 1148 (m) cmꢀ1; HRMS
(m/z) [M+] calcd for C28H26O6 458.1729; found 458.1711.
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21,22-Diacetyl-3,4,7,8,9,10,11,12,15,16-decahydro-5H,14H-2,24-(ethanediylidene)-17,20-etheno-6,13-
benzodioxacyclodocosine-5,14-dione (13j). Bisꢀ(3ꢀ(4ꢀ(3ꢀoxobutꢀ1ꢀinyl)phenyl)propionic acid)ꢀhexaneꢀ1,6ꢀdiylꢀ
ester (12j) (0.114 g, 0.22 mmol) was subjected to the reaction conditions described in GP4. The reaction was
finished after 45 min yielding the title compound as yellowish solid (0.084 g, 74%). Rf 0.38 (PE/EtOAc 1:1);
m.p. 146ꢀ147 °C; 1H NMR (300 MHz, CDCl3, ppm) δ 8.35 (s, 1H), 7.93 (d, J = 8.4 Hz, 1H), 7.45 (d, J = 8.3 Hz,
1H), 7.34 (d, J = 7.8 Hz, 2H), 7.26 (s, 1H), 7.19 (d, J = 7.9 Hz, 2H), 4.08 (t, J = 6.4 Hz, 2H), 4.01 (t, J = 5.5 Hz,
2H), 3.11 – 2.94 (m, 4H), 2.81 – 2.74 (m, 2H), 2.72 (s, 3H), 2.66 – 2.55 (m, 2H), 2.08 (s, 3H), 1.68 – 1.49 (m,
4H), 1.37 (d, J = 3.3 Hz, 4H); 13C NMR (75 MHz, CDCl3, ppm) δ 206.3, 198.6, 173.0, 172.3, 141.7, 140.8,
139.5, 136.0, 134.7, 134.1, 132.8, 131.0, 130.9, 130.8, 129.7, 128.7, 128.2, 125.4, 64.7, 64.0, 35.4, 35.4, 31.9,
30.4, 28.2, 28.0, 27.1, 25.6, 25.0; IR (υꢍ): 2923 (m), 2855 (m), 1717 (vs), 1698 (s), 1678 (vs), 1432 (m), 1388
(m), 1353 (m), 1289 (m), 1248 (s), 1150 (s), 1105 (m) cmꢀ1; HRMS (m/z) [M+] calcd for C32H34O6 514.2355;
found 514.2365.
25,26-Diacetyl-3,4,7,8,9,10,11,12,13,14,15,16,19,20-tetradecahydro-5H,18H-2,28-(ethanediylidene)-21,24-
etheno-6,17-benzodioxacyclohexacosine-5,18-dione (13k). Bisꢀ(3ꢀ(4ꢀ(3ꢀoxobutꢀ1ꢀinyl)phenyl)propionic acid)ꢀ
decaneꢀ1,10ꢀdiylꢀester (12k) (0.093 g, 0.16 mmol) was subjected to the reaction conditions described in GP4.
The reaction was finished after 30 min yielding the title compound as yellowish solid (0.061 g, 66%). Rf 0.6
(PE/EtOAc 1:1); m.p. 126ꢀ128 °C; 1H NMR (300 MHz, CDCl3) δ 8.34 (s, 1H), 7.92 (d, J = 8.3 Hz, 1H), 7.44 (d,
J = 8.3 Hz, 1H), 7.34 – 7.27 (m, 3H), 7.20 (d, J = 7.9 Hz, 2H), 4.15 (t, J = 5.6 Hz, 2H), 4.01 (t, J = 6.2 Hz, 2H),
3.04 (dt, J = 11.1, 8.3 Hz, 4H), 2.74 (d, J = 11.5 Hz, 5H), 2.61 – 2.54 (m, 2H), 2.09 (s, 3H), 1.66 – 1.51 (m, 4H),
1.37 – 1.19 (m, 12H); 13C NMR (75 MHz, CDCl3) δ 206.2, 198.6, 173.0, 172.6, 142.0, 140.8, 139.5, 135.8,
134.7, 134.1, 132.8, 131.1, 130.8, 129.7, 128.7, 128.4, 125.0, 65.0, 64.9, 36.2, 35.5, 31.9, 31.6, 30.9, 29.2, 28.8,
28.7, 28.5, 28.2, 27.12, 26.3, 25.8; IR (υꢍ): 2924 (s), 2851 (m), 1731 (vs), 1699 (s), 1670 (s), 1621 (w), 1435 (m),
1350 (m), 1256 (m), 1229 (m), 1135 (m), 1104 (m), 1048 (w), 1022 (m), 965 (w), 929 (w), 836 (w) cmꢀ1; HRMS
(m/z) [M+] calcd for C36H42O6 570.2981; found 570.2968.
27,28-Diacetyl-3,4,7,8,9,10,11,12,13,14,15,16,17,18,21,22-hexadecahydro-5H,20H-2,30-(ethanediylidene)-
23,26-etheno-6,19-benzodioxacyclooctacosine-5,20-dione (13l). Bisꢀ(3ꢀ(4ꢀ(3ꢀoxobutꢀ1ꢀinyl)phenyl)propionic
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