Synthesis of bicyclic dioxetanes bearing a 2-hydroxy-1,1′-binaphthyl-5-yl moiety active toward intramolecular charge-transfer-induced chemiluminescent decomposition

Article abstract of DOI:10.1016/j.tet.2006.09.108

Five pairs of diastereoisomeric dioxetanes, cis- and trans-2a-2e, were synthesized. These dioxetanes underwent intramolecular charge-transfer-induced decomposition with accompanying emission of orange light in TBAF in DMSO (system A) as a complete homogen

Full text of DOI:10.1016/j.tet.2006.09.108

Tetrahedron 62 (2006) 12424–12437
Synthesis of bicyclic dioxetanes bearing a 2-hydroxy-1,10-
binaphthyl-5-yl moiety active toward intramolecular
charge-transfer-induced chemiluminescent decomposition
*
Naoyuki Hoshiya, Nobuko Watanabe, Hisako K. Ijuin and Masakatsu Matsumoto
Department of Chemistry, Kanagawa University, Tsuchiya, Hiratsuka, Kanagawa 259-1293, Japan
Received 24 August 2006; accepted 25 September 2006
Available online 27 October 2006
Abstract—Five pairs of diastereoisomeric dioxetanes, cis- and trans-2a–2e, were synthesized. These dioxetanes underwent intramolecular
charge-transfer-induced decomposition with accompanying emission of orange light in TBAF in DMSO (system A) as a complete homoge-
neous system and in [K3(18C6)]+t-BuOꢀ in PhH–THF (system B) as a sterically anisotropic environment. Maximum wavelength (lmCTaxICL) of
chemiluminescence did not vary practically with the triggering system. The lCmTaxICL was little affected also by substituents on the upper-Nap of
dioxetanes 2, nor by the difference in their stereochemistry, namely, cis- or trans-isomer. On the other hand, chemiluminescent efficiency was
found to split up depending on stereochemistry of 2. Dioxetane 2b bearing a methoxycarbonyl group on the upper-Nap gave significantly
weak light, while its free carboxylic acid analog 2c afforded light effectively.
Ó 2006 Elsevier Ltd. All rights reserved.
1. Introduction
synthesized from a precursor of 2b (Fig. 1). The CTICL
decomposition of these dioxetanes 2a–2e was examined
by the use of tetrabutylammonium fluoride (TBAF) in
DMSO as a complete homogeneous system and by the use
of a potassium t-butoxide complex of 18-crown-6 ether
as a sterically anisotropic microenvironment in benzene
(PhH)–THF.
A 2-substituted 1,10-binaphthyl is a most promising func-
tionality to construct optically active molecules and its fluo-
rescence properties, which vary depending on the change of
the dihedral angle between the two naphthyl groups is of
much interest.1 Such binaphthyl functionality should be-
come a unique electron donor as well as the most influential
part of an emitter, when introduced into a dioxetane active
toward intramolecular charge-transfer-induced chemilumi-
nescence (CTICL).2–5 Thus, we attempted here to synthesize
racemic dioxetanes bearing a 2-hydroxy-1,10-binaphthyl-5-
yl moiety and examined their CTICL decomposition as a fun-
damental investigation leading to studies of optically active
dioxetanes.6,7 Our design was based on an idea that a naph-
thyl group was introduced to the 2-hydroxynaphthyl moiety
in a parent dioxetane, namely, 5-tert-butyl-1-(2-hydroxy-
naphthalen-5-yl)-4,4-dimethyl-2,6,7-trioxabicyclo[3.2.0]-
heptane 1, which has very recently been found to exhibit
chemiluminescence in high efficiency.8 The thus-realized
substrates were dioxetane 2a bearing a rather simple
2-hydroxy-1,10-binaphthyl-5-yl, dioxetane 2b bearing a 2-
hydroxy-20-methoxy-30-methoxycarbonyl-1,10-binaphthyl,
dioxetane 2c bearing a 30-carboxy-2-hydroxy-20-methoxy-
1,10-binaphthyl moiety, and two 20,30-disubstituted 2-hy-
droxy-1,10-binaphthyl analogs, 2d and 2e, which were
CO2R
OH
OMe
OH
OH
O
O
O
O
O
t-Bu
O
O
t-Bu
O
O
t-Bu
1
2a
2b: R = Me
2c: R = H
OH
O
O
O
OH
O
OH
O
O
t-Bu
O
O
t-Bu
O
O
Keywords: Dioxetane; Chemiluminescence; Binaphthyl; Crown ether.
* Corresponding author. Tel.: +81 463 59 4111; fax: +81 463 58 9684;
e-mail: matsumo-chem@kanagawa-u.ac.jp
2e
2d
Figure 1.
0040–4020/$ - see front matter Ó 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2006.09.108

N. Hoshiya et al. / Tetrahedron 62 (2006) 12424–12437
12425
CO2Me
OR
2. Results and discussion
3)
4)
1)
2.1. Synthesis of bicyclic dioxetanes bearing a
2-hydroxy-1,10-binaphthyl-5-yl moiety
5
3c
3b
O
Ts
5)
Synthesis of dioxetanes 2a–2e was based on singlet
oxygenation of the corresponding binaphthyl-substituted 4-
tert-butyl-3,3-dimethyl-2,3-dihydrofurans 3a–3e. Since 5-
aryl-4-tert-butyl-3,3-dimethyl-2,3-dihydrofurans have been
known to undergo effectively 1,2-cycloaddition of singlet
oxygen,4,5 the synthesis of precursor dihydrofurans 3a–3e
was the step to be contrived carefully. Our synthetic strategy
was to utilize dihydrofuran 5 bearing a 2,20-dihydroxy-
30-methoxycarbonyl-1,10-binaphthyl-5-yl moiety as a key
intermediate, since 5 has very recently been found to
be effectively produced from 2-hydroxynaphthalen-5-yl-
substituted dihydrofuran 4 by means of copper-catalyzed
oxidative cross-coupling with methyl 3-hydroxynaphtha-
lene-2-carboxylate (Scheme 1).9 Thus, dihydrofurans 3b–
3e except 3a were synthesized from 5 in several steps
(vide infra).
8: R = H
DHF
2)
9: R = Me
OH
OH
OMe
9)
O
6)
OH
OR
3d
OMe
3e
8)
2), 7)
DHF
DHF
10: R = H
11: R = Me
12
Scheme 2. Reagents and conditions: (1) TsCl/pyridine, (2) MeI/K2CO3,
(3) NaOH, (4) MeI/NaHCO3, (5) LiAlH4, (6) Me2C(OMe)2/PPTS, (7)
H2O/TsOH/THF, (8) MeOCH2CH2Br/K2CO3, (9) MeSNa/DMF.
On the other hand, dihydrofuran 5 was reduced with LiAlH4
to give dihydrofuran 10bearinga 2,20-dihydroxy-30-hydroxy-
methyl-1,10-binaphthyl-5-yl moiety, which was further
treated with 2,2-dimethoxypropane to afford cyclic acetal
3d. Williamson synthesis of 3d with MeI followed by hydro-
lysis of acetal group gave dihydrofuran 11, which was treated
with 2-methoxyethyl bromide–K2CO3 to give dihydrofuran
12 bearing a 30-hydroxymethyl-2-methoxy-20-(2-methoxy-
ethoxy)-1,10-binaphthyl-5-yl moiety.11 Demethylation of the
2-methoxy group with MeSNa gave dihydrofuran 3e bearing
a 2-hydroxy-30-hydroxymethyl-20-(2-methoxyethoxy)-1,10-
binaphthyl-5-yl moiety.
R2
R1
OH
t-Bu
O
DHF =
a: R1, R2 = H
b: R1 = -OMe, R2 = -CO2Me
c: R1 = -OMe, R2 = -CO2H
d: R1-R2 = -OC(CH3)2OCH2-
DHF
3a-3e
e: R1 = -OCH2CH2OMe, R2 = -CH2OH
CO2Me
CO2Me
OH
OH
OH
OH
oxidative cross coupling
All dihydrofurans 3a–3e synthesized here were obtained as
a mixture of diastereomers, which could not be separated
from each other. Therefore, 1,2-addition of singlet oxygen
to 3 should afford the corresponding dioxetanes 2 also as
a mixture of diastereomers, namely, cis-2 in which both
long wing of 10-naphthyl (called upper-Nap for the sake of
convenience) and O7 of dioxetane O–O lie in the same
side of the p-face of central hydroxynaphthyl ring, and
trans-2 in which the long wing of upper-Nap and the O7
lie in the opposite side of the p-face to each other (Fig. 2).
When a solution of dihydrofuran 3a in CH2Cl2 was irradi-
ated in the presence of a catalytic amount of tetraphenylpor-
phin (TPP) with Na lamp under O2 atmosphere at 0 ꢁC for
1 h, dioxetane 2a was selectively produced as a mixture of
diastereomers (cis:trans¼64:36), from which cis-2a, as the
first fraction, and trans-2a, as the second fraction, were sep-
arated in pure form by column chromatography (SiO2/hex-
ane–AcOEt). Similar singlet oxygenation of dihydrofurans
3b–3e gave the corresponding dioxetanes, 2b–2e as a mix-
ture of diastereomers (cis:trans¼42:58 for 2b, 48:52 for
2c, 43:57 for 2d, and 46:54 for 2e). Chromatographic sepa-
ration of the diastereomers afforded also cis-2b–2e and
trans-2b–2e in pure form. The structures of these dioxetanes
were determined by 1H NMR, 13C NMR, IR, mass spectral
analyses and elemental analysis. Furthermore, X-ray single
crystallographic analysis was successfully attained for cis-
2a, cis-2b, cis-2c, trans-2d, and cis-2e. ORTEP views
illustrated in Figure 3 show that two naphthyl rings lie in
seriously twisted conformation for all theseꢁ dioxetanes:
DHF
4
5
DHF
Br
OMe
OMe
MgBr
MeSNa
3a
DHF
Pd (0)
DHF
6
7
Scheme 1.
Dihydrofuran 3a substituted with a simple 2-hydroxy-1,10-
binaphthyl-5-yl group was synthesized by Pd-catalyzed
cross-coupling10 of dihydrofuran 6 bearing a 1-bromo-2-
methoxynaphthalen-5-yl group with 1-naphthylmagnesium
bromide giving dihydrofuran 7 bearing a 2-methoxy-1,10-bi-
naphthyl-5-yl group, and successive demethylation of the
2-methoxy group in 7 (Scheme 1).
The first step to synthesize 3b bearing a 2-hydroxy-20-
methoxy-30-methoxycarbonyl-1,10-binaphthyl-5-yl moiety
from 5 was selective protection of the 2-hydroxy group
into p-toluenesulfonate 8. Next, the 20-hydroxy group of 8
was methylated to give 20-methoxy-derivative 9, which
was hydrolyzed into dihydrofuran 3c bearing a 30-carboxy-
2-hydroxy-20-methoxy-1,10-binaphthyl-5-yl moiety. Finally,
3c was esterified with methyl iodide and NaHCO3 to afford
3b (Scheme 2).
0
0
dihedral angles q (C2–C1–C1 –C2 ) were 86.7 for cis-2a,

12426
N. Hoshiya et al. / Tetrahedron 62 (2006) 12424–12437
R2
R2
R1
R1
OH
OH
a: R1, R2 = H
b: R1 = -OMe, R2 = -CO2Me
c: R1 = -OMe, R2 = -CO2H
d: R1-R2 = -OC(CH3)2OCH2-
e: R1 = -OCH2CH2OMe, R2 = -CH2OH
7
1
O
O
t-Bu
O
2
3
O
O
4
6
O
5
t-Bu
cis-2
trans-2
Figure 2.
2.2. Base-induced chemiluminescent decomposition
of bicyclic dioxetanes bearing a 2-hydroxy-1,10-bi-
naphthyl-5-yl moiety
The parent dioxetane 1 bearing a 2-hydroxynaphthalen-5-yl
moiety has been reported to undergo CTICL decomposition
followed by a pseudo-first-order kinetics to give yellow light
CTICL
max
with maximum wavelength l
¼582 nm, when treated
with a large excess of TBAF in DMSO.8 Thus, we carried
out first the CTICL decomposition of dioxetanes 2a–2e in
the TBAF in DMSO system (system A) to evaluate their
chemiluminescent properties in comparison with those of di-
oxetane 1. When solutions of dioxetanes, cis-2a and trans-2a
in DMSO (1.0ꢂ10ꢀ5 mol cmꢀ3, 1 mL) were added to solu-
tions of TBAF in DMSO (1.0ꢂ10ꢀ2 mol cmꢀ3, 2 mL) at
25 ꢁC, these diastereomeric dioxetanes decomposed rapidly
to emit orange light with the same lCmTaxICL (597 nm), though
chemiluminescent efficiency (FCTICL) and pseudo-first-
order rate constant (kCTICL) were somewhat different from
each other. Then, the fluoride-induced chemiluminescent de-
composition of dioxetanes, cis-2b–2e and trans-2b–2e, were
carried out similarly. The results are summarized in Table 1,
which reveals characteristic features for CTICL of 2 as
follows. First, the introduction of the upper-Nap on the 2-hy-
droxynaphthyl ring of the parent dioxetane 1 caused a little
red-shift of lCmTaxICLs, which were observed at ca. 600 nm
regardless of substituents on the upper-Nap ring. Secondly,
cis-2a
cis-2b
cis-2c
R2
2'
R1
1'
1
OH
2
O
O
O
t-Bu
trans-2d
cis-2e
Figure 3. ORTEP views of dioxetane cis-2a, cis-2b, cis-2c, trans-2d, and
cis-2e.
F
CTICLs tended to decrease as substituent(s) was introduced
into the upper-Nap ring of 2, and the extreme was that for 2b,
CTICL of which was only 1/500–1/1000 of those for 1 and
109.1ꢁ for cis-2b, 75.1ꢁ for cis-2c, 96.5ꢁ for trans-2d, and
76.5ꢁ for cis-2e.
F
Table 1. Base-induced chemiluminescent decomposition of bicyclic dioxetanes bearing a 2-hydroxy-1,10-binaphthyl-5-yl moiety 2a
Dioxetane
System A
TBAF in DMSO
FCTICL b
System B
[K3(18C6)]+t-BuOꢀ in PhH–THF
lCmTaxICL/nm
kCTICL/sꢀ1
lCmTaxICL/nm
FCTICL b
kCTICL/sꢀ1
2a
2b
2c
2d
2e
cis
trans
cis
trans
cis
trans
cis
trans
cis
trans
597
597
600
600
609
609
600
600
600
600
582c
1.6ꢂ10ꢀ2
1.8ꢂ10ꢀ2
2.0ꢂ10ꢀ5
1.8ꢂ10ꢀ5
8.5ꢂ10ꢀ3
9.3ꢂ10ꢀ3
9.2ꢂ10ꢀ3
1.1ꢂ10ꢀ2
1.7ꢂ10ꢀ2
1.2ꢂ10ꢀ2
1.7ꢂ10ꢀ2
5.0ꢂ10ꢀ2
4.8ꢂ10ꢀ2
2.2ꢂ10ꢀ2
2.2ꢂ10ꢀ2
4.0ꢂ10ꢀ1
3.6ꢂ10ꢀ1
1.8ꢂ10ꢀ1
1.8ꢂ10ꢀ1
5.1ꢂ10ꢀ2
5.5ꢂ10ꢀ2
3.7ꢂ10ꢀ2
594
594
600
600
600
600
595
595
595
595
614
9.2ꢂ10ꢀ3
8.8ꢂ10ꢀ3
9.7ꢂ10ꢀ3
7.5ꢂ10ꢀ3
9.4ꢂ10ꢀ3
7.4ꢂ10ꢀ3
6.9ꢂ10ꢀ3
6.2ꢂ10ꢀ3
7.2ꢂ10ꢀ3
5.5ꢂ10ꢀ3
4.2ꢂ10ꢀ3
3.1ꢂ10ꢀ2
3.4ꢂ10ꢀ2
1.9ꢂ10ꢀ1
2.0ꢂ10ꢀ1
1.9ꢂ10ꢀ1
1.9ꢂ10ꢀ1
1.3ꢂ10ꢀ1
9.0ꢂ10ꢀ2
1.3ꢂ10ꢀ1
1.1ꢂ10ꢀ1
4.5ꢂ10ꢀ2
1
a
Base-induced decompositions were carried out at 25 ꢁC.
Chemiluminescent efficiencies (FCTICL) were based on the reported value for 3-(3-tert-butyldimethylsiloxyphenyl)-3-methoxy-4-(20-spiroadamantane)-1,2-
dioxetane (FCTICL¼0.29) (Ref. 12).
b
c
Chemiluminescent properties for 1 in TBAF in DMSO summarized here are the values reported (Ref. 8).

N. Hoshiya et al. / Tetrahedron 62 (2006) 12424–12437
12427
System A
Fluorescence of 13a
System B
Fluorescence of 13a
Chemiluminescence of cis-2a
Chemiluminescence of trans-2a
Chemiluminescence of cis-2a
Chemiluminescence of trans-2a
500
550
600
650
700
500
550
600
650
700
wavelength / nm
wavelength / nm
Figure 4. Chemiluminescent spectra of dioxetane 2a and fluorescence spectra of keto ester 13a.
the other dioxetanes 2a and 2c–2e. It should be noted that di-
oxetane 2c, which is simply a carboxylic acid analog of 2b,
displayed chemiluminescence as effective as 2a, 2d, and 2e.
Thirdly, difference in configuration of the dioxetane,
namely, cis- or trans-type, did not affect lCmTaxICL, but caused
apparently a split of FCTICL and kCTICL to some extent.
microenvironment to a ligand such as phenol and naphthol
as they coordinate to it.13–16 When dioxetane 1 was treated
as a reference with a large excess of [K3(18C6)]+t-BuOꢀ
in PhH–THF (1:1) (system B) at 25 ꢁC, 1 decomposed
CTICL
max
with accompanying emission of light with l
at
614 nm, though FCTICL decreased to 1/4 of the value in sys-
tem A. Chemiluminescent decomposition of 2a–2e was
examined similarly in system B. The results are summarized
in Table 1, which shows that the behavior of dioxetanes
2a–2e in system B was considerably different from the
case of 1. Thus, lCmTaxICLs did not change or rather shifted
slightly to blue for 2, whereas that for 1 shifted to red consid-
erably as the base system changed from system A to system
B. Decrease of FCTICLs was smaller for 2 than for 1 in system
B, and FCTICLs were rather higher than that of 1. Structural
All spent mixtures of fluoride-induced decomposition of 2
in DMSO gave the corresponding keto esters of 1,10-bi-
naphthyl-5-carboxylic acid 14a–14e in high isolated yields
after neutralization; both cis-2 and trans-2 gave the same
14. This fact shows that fluoride-induced decomposition of
2 produced undoubtedly oxido anion 13. For instance, 13a
generated from the corresponding authentic keto esters, 14a
in TBAF in DMSO displayed fluorescence (efficiency
Ffl¼5.9ꢂ10ꢀ2), the spectra of which coincided with the
chemiluminescence spectra of the corresponding dioxetanes,
cis-2aandtrans-2a(Fig.4). However, ketoester14bexhibited
little observable fluorescence under similar conditions. This is
a reason why FCTICL was extremely low for 2b, implying
that FCTICL is proportional to fluorescence efficiency of the
emitter produced. On the other hand, keto ester 14c would
exist in TBAF in DMSO as a dianion form, and displayed
fluorescence differently from 14b. Conclusively, an electron-
withdrawing ester function attached at the 30-position of
upper-Nap decreased fluorescence of 14b, so that decreased
significantly FCTICL of 2b, whereas its carboxylate anion did
not deteriorate the fluorescence property of 13c (Scheme 3).
difference between diastereomers, cis-2 and trans-2, caused
difference in FCTICL but not in l
also for system B. It
CTICL
max
should be noted here that difference in FCTICL tended to ex-
pand in system B, and its magnitude increased in the order of
2a, 2cꢃ2d<2e. Furthermore, weak diastereomeric recogni-
tion is apparently reflected in the singlet-chemiexcitation
process for CTICL decomposition of 2.
Table 1 shows that FCTICL of 2b appeared to increase
surprisingly when the triggering system changed from sys-
tem A to system B. However, the spent reaction mixture
after neutralization afforded free carboxylic acid 14c but
not ester 14b. This fact suggests that hydrolysis of 2b to
dianion of 2c took place far more rapidly than decomposi-
tion of 2b into excited 13b, and successive decomposition
of 2c occurred to emit light in system B. The hydrolysis is
presumably caused by a trace amount of water existing as
hydroxide anion, which could hardly be excluded from
system B in spite of careful experiment even under N2 atmo-
sphere, though such sensitivity was little observed for the
other CTICLs.
R2
R2
B:
B:
R1
OH
R1
O
cis-2
H
trans-2
O
O
t-Bu
O
O
t-Bu
O
O
Spent reaction mixtures from 2a–2e except 2b in system B
gave the corresponding keto esters 14a and 14c–14e in high
yields after neutralization. Therefore, emitters produced
from dioxetanes were believed to be anionic keto esters 13
as in the case of system A. However, all authentic anionic
keto esters 13 generated from 14 displayed fluorescence
spectra with lflmaxs at ca. 560 nm, which was considerably
shorter than lCmTaxICLs of chemiluminescent spectra from the
corresponding dioxetanes 2 in system B, as illustrated in
Figure 4, where the case of 2a and 13a is shown as a
14
13
a: R1, R2 = H
b: R1 = -OMe, R2 = -CO2Me
c: R1 = -OMe, R2 = -CO2H for 2 and 14, -CO2 for 13
d: R1-R2 = -OC(CH3)2OCH -
e: R1 = -OCH2CH2OMe, R22 = -CH2OH
Scheme 3.
A
complex of 18-crown-6 ether with t-BuOK,
[K3(18C6)]+t-BuOꢀ, provides a sterically anisotropic

12428
N. Hoshiya et al. / Tetrahedron 62 (2006) 12424–12437
tBuO
K
O
O
O
O
K
O
HO
2
O
tBuO
K
O
O
O
Light
O
K
HO
14
Isolation as neutral form
Scheme 4.
representative. ThediscrepancybetweenlCmTaxICL andlmfl ax sug-
gests that excited keto ester 13 produced from dioxetane 2
lies presumably in conformation different from that of
authentic 13 under the coordination to [K3(18C6)]+. That
is, dioxetane 2 produces most likely, in the coordination
sphere, excited 13 retaining afterimage of stereochemistry
of 2, which could never be reproduced from authentic 14,
as illustrated in Scheme 4.
(system A) and in [K3(18C6)]+t-BuOꢀ in PhH–THF (sys-
tem B) that lCmTaxICL of chemiluminescence was little affected
practically by the triggering system, the substituents on
upper-Nap, nor their stereochemistry, whereas FCTICL and
kCTICL split up depending on the stereochemistry of 2. The
bulk of substituents on upper-Nap was suggested to influ-
ence the magnitude of the split in FCTICL between diastereo-
isomeric dioxetanes 2. These findings provide a promising
possibility that structural modification of dioxetanes 2d and
2e should lead to optically active dioxetanes that undergo
CTICL decomposition responding to anisotropic micro-
environment. The rather unexpected finding that very rapid
hydrolysis of the ester function in 2b into 2c caused most
likely significant increase of FCTICL in system B may be
useful to monitor hydrolysis of the ester function.
An AM1 MO calculation was indicative for the change of
excitation energy depending on the conformational change
of binaphthyl. Figure 5 illustrates the relationship of energy
gap (DE¼ELUMOꢀEHOMO) with the dihedral angle (q) for 2-
oxido-1,10-binaphthyl-5-carboxylic acid methyl ester as a
model of 13a. The calculation suggested for the model emit-
ter that, as q decreased from ca. 100ꢁ, DE increased so that
emission shifted to blue more and more. Thus, the coordina-
tion to [K3(18C6)]+ causes most likely decrease of q larger
for authentic 13 generated from 14 than for excited 13
produced from 2.
4. Experimental
4.1. General
Melting points were measured with a Yanako MP-S3 melt-
ing point apparatus and are uncorrected. IR spectra were
taken on a JASCO FT/IR-300 infrared spectrometer. H
0
6.45
6.40
6.35
1
and 13C NMR spectra were recorded on JEOL EX-400 and
JEOL EPC-500 spectrometers. Mass spectra were obtained
by using JEOL JMS-AX-505H and JEOL JMS-T-100LC
mass spectrometers. Elemental analysis was performed by
means of Perkin–Elmer 2400II. Reagents were purchased
from Aldrich, Tokyo Chemical Industries, Wako Pure
Chemical Industries, and/or Kanto Chemical Industries.
Column chromatography was carried out with silica gel,
unless otherwise stated.
O
–6
CO2Me
–12
–18
4.1.1. Synthesis of 4-tert-butyl-5-(2-methoxy-1,10-bi-
naphthyl-5-yl)-3,3-dimethyl-2,3-dihydrofuran (7). A so-
lution of naphthalen-1-yl magnesium bromide, prepared
from 1-bromonaphthalene (0.61 mL, 4.4 mmol) in dry THF
(8 mL) was added dropwise to a suspension of 5-(5-bromo-
6-methoxynaphthalen-1-yl)-4-tert-butyl-3,3-dimethyl-2,3-
dihydrofuran (6) (1.42 g, 3.65 mmol) and Pd(PPh3)4
(380 mg, 0.33 mmol) in dry THF (14 mL) under a nitrogen
atmosphere for 20 min at refluxing temperature and then
stirred for 7.5 h. The mixture was worked up as usual and ex-
tracted with AcOEt. The organic layer was washed with satd
aq NaCl, dried over anhydrous MgSO4, and concentrated
25
60
90
125
Dihedral angle (deg)
Figure 5. Relationship between DE and dihedral angle q for 2-oxido-1,10-
binaphthyl-5-carboxylic acid methyl ester.
3. Conclusion
It was disclosed for CTICL decomposition of diastereo-
isomeric dioxetanes, cis-2 and trans-2, in TBAF in DMSO

N. Hoshiya et al. / Tetrahedron 62 (2006) 12424–12437
12429
in vacuo. The residuewas chromatographed on silica gel with
AcOEt–hexane (1:40) to give dihydrofuran 7 (510 mg,
32.1%, conversion: 61.9%) as a colorless solid. Compound
7: colorless plates melted at 137.0–137.5 ꢁC (from AcOEt–
hexane); (63:37 mixture of diastereomers) 1H NMR
(400 MHz, CDCl3): dH 1.07 (s, 9Hꢂ0.63), 1.08 (s, 9Hꢂ
4-tert-butyl-5-(2,20-dihydroxy-30-methoxycarbonyl-1,10-bi-
naphthyl-5-yl)-3,3-dimethyl-2,3-dihydrofuran (5)9 (2.03 g,
4.09 mmol) and triethylamine (2.9 mL, 21 mmol) in dry
THF (10 mL) under a nitrogen atmosphere at room tempera-
ture and stirred for 25 h. The reaction mixture was added to
satd aq NH4Cl and extracted with AcOEt. The organic layer
was washed with satd aq NaCl, dried over anhydrous
MgSO4, and concentrated in vacuo. The residue was chroma-
tographed on silica gel with CH2Cl2–hexane (1:1) to give
dihydrofuran 8 (2.00 g, 75.1%) as a pale yellow solid. Com-
pound 8: pale yellow amorphous solid; (64:36 mixture of
0.37), 1.43 (s, 3H), 1.51 (s, 3H), 3.72 (s, 3H), 4.01 (qAB
,
J¼6.4 Hz, 2Hꢂ0.37), 4.06 (qAB, J¼8.2 Hz, 2Hꢂ0.63),
7.09–7.16 (m, 2H), 7.20–7.46 (m, 6H), 7.56–7.61 (m, 1H),
7.89–7.93 (m, 2H), 8.10 (d with fine coupling, J¼9.2 Hz,
1H) ppm. 13C NMR (125 MHz, CDCl3): dC 27.3 and 27.4,
27.6 and 27.7, 32.1, 32.7, 47.4, 56.6, 83.3, 114.0 and 114.1,
123.2, 125.4 and 125.5, 125.6, 125.6 and 125.7, 125.8,
125.8 and 125.9, 126.2, 126.2 and 126.3, 127.4, 127.7,
127.7 and 127.8, 127.8 and 127.9, 128.1 and 128.2, 128.3
and 128.6, 132.9 and 133.0, 133.4 and 133.5, 133.6 and
133.7, 134.3 and 134.4, 134.5 and 134.6, 148.2, 154.5 ppm.
IR (KBr): ~n 2956, 2857, 1610, 1589, 1508, 1260, 1090,
1048 cmꢀ1. Mass (m/z, %): 436 (M+, 80), 422 (36), 421
(100), 406 (16), 375 (19), 365 (17), 239 (10), 57 (19).
HRMS (ESI): 459.2254, calcd for C31H32O2Na (M+Na+)
459.2300. Anal. Calcd for C31H32O2: C, 85.28; H, 7.39.
Found: C, 84.90; H, 7.29.
1
diastereomers) H NMR (500 MHz, CDCl3): dH 1.05 (s,
9H), 1.44 (s, 3H), 1.52 (s, 3H), 2.25 (s, 3Hꢂ0.64), 2.29 (s,
3Hꢂ0.36), 3.99 (d, J¼7.8 Hz, 1Hꢂ0.36), 4.00 (d, J¼
7.8 Hz, 1Hꢂ0.64), 4.04–4.07 (m, 1H), 4.05 (s, 3Hꢂ0.36),
4.07 (s, 3Hꢂ0.64), 6.72 (d, J¼8.7 Hz, 1Hꢂ0.64), 6.76–6.87
(m, 2H), 6.96 (d, J¼7.8 Hz, 1Hꢂ0.36), 7.10–7.14 (m, 4H),
7.18–7.23 (m, 1H), 7.27–7.33 (m, 1H), 7.38–7.41 (m, 1H),
7.79–7.84 (m, 2H), 8.12 (s, 1Hꢂ0.64), 8.14 (s, 1Hꢂ0.36),
8.53 (s, 1Hꢂ0.36), 8.55 (s, 1Hꢂ0.64), 10.1 (s, 1Hꢂ0.36),
10.5 (s, 1Hꢂ0.64) ppm. 13C NMR (125 MHz, CDCl3): dC
21.5, 27.2 and 27.3, 27.5 and 27.6, 32.0 and 32.1, 32.7,
47.3 and 47.4, 52.5 and 52.6, 83.3, 113.4 and 113.5, 115.6
and 115.7, 121.9 and 122.0, 123.6 and 123.7, 124.6 and
124.7, 124.9 and 125.2, 125.9 and 126.0, 126.4 and 126.5,
126.9 and 127.0, 127.4 and 127.6, 127.9 and 128.0, 128.2
and 128.3, 128.5, 128.9 and 129.0, 129.1 and 129.3, 129.2
and 129.4, 130.9 and 131.1, 132.9 and 133.0, 133.1 and
133.2, 133.2, 133.9 and 134.0, 136.8 and 136.9, 144.1 and
144.2, 145.9 and 146.1, 147.4 and 147.6, 154.0 and 154.1,
170.0 and 170.1 ppm. IR (KBr): ~n 3448, 2955, 2865, 1684,
1628, 1438, 1322, 1213, 1173, 1051 cmꢀ1. Mass (m/z, %):
650 (M+, 69), 637 (13), 636 (49), 635 (100), 603 (28), 547
(31), 496 (21), 482 (19), 481 (51), 480 (25), 465 (30), 433
(19), 393 (18), 363 (14), 226 (19), 91 (45), 57 (29). HRMS
(ESI): 673.2212, calcd for C39H38O7SNa (M+Na+)
673.2236. Anal. Calcd for C39H38O7S: C, 71.98; H, 5.89.
Found: C, 71.77; H, 5.77.
4.1.2. Synthesis of 4-tert-butyl-5-(2-hydroxy-1,10-binaph-
thyl-5-yl)-3,3-dimethyl-2,3-dihydrofuran (3a). Sodium
methanethiolate (95%, 145 mg, 1.97 mmol) was added to a
solution of 4-tert-butyl-5-(2-methoxy-1,10-binaphthyl-5-yl)-
3,3-dimethyl-2,3-dihydrofuran (7) (409 mg, 0.937 mmol) in
dry DMF (4 mL) under a nitrogen atmosphere at room tem-
perature and stirred for 1 h at 140 ꢁC. The reaction mixture
was poured into satd aq NH4Cl and extracted with AcOEt.
The organic layer was washed with satd aq NaCl, dried
over anhydrous MgSO4, and concentrated in vacuo. The resi-
due was chromatographed on silica gel with AcOEt–hexane
(1:4) to give dihydrofuran 3a (363 mg, 91.7%) as a colorless
solid. Compound 3a: colorless granules melted at 199.5–
200.0 ꢁC (from AcOEt–hexane); (63:37 mixture of diastereo-
1
mers) H NMR (400 MHz, CDCl3): dH 1.06 (s, 9Hꢂ0.63),
1.08 (s, 9Hꢂ0.37), 1.44 (s, 3H), 1.52 (s, 3H), 4.01 (qAB
,
4.1.4. Synthesis of 4-tert-butyl-5-[20-methoxy-30-methoxy-
carbonyl-2-(4-methyl-phenylsulfonyloxy)-1,10-binaphthyl-
5-yl]-3,3-dimethyl-2,3-dihydrofuran (9). MeI (0.10 mL,
1.6 mmol) was added to a solution of 4-tert-butyl-5-[20-hy-
droxy-30-methoxycarbonyl-2-(4-methylphenylsulfonyloxy)-
J¼7.8 Hz, 2Hꢂ0.37), 4.03 (qAB, J¼8.1 Hz, 2Hꢂ0.63), 4.86
(s, 1Hꢂ0.37), 4.90 (s, 1Hꢂ0.62), 7.04–7.08 (m, 1H), 7.15–
7.20 (m, 1H), 7.26 (d with fine coupling, J¼7.0 Hz, 1H),
7.30–7.41 (m, 3H), 7.47–7.55 (m, 1H), 7.58 (d with fine cou-
pling, J¼7.0 Hz, 1H), 7.63–7.68 (m, 1H), 7.96 (d, J¼7.8 Hz,
1H), 7.98–8.03 (m, 1H), 8.02 (d, J¼7.8 Hz, 1H) ppm. 13C
NMR (125 MHz, CDCl3): dC 27.3 and 27.4, 27.6 and 27.7,
32.1, 32.7, 47.4, 83.3, 117.7, 118.7 and 118.8, 125.6 and
125.7, 125.7, 125.7 and 125.9, 125.9 and 126.0, 126.4
and 126.5, 126.7 and 126.8, 127.6 and 127.7, 127.8,
127.8, 128.3 and 128.5, 129.1 and 129.2, 129.4 and 129.8,
131.5, 132.8, 132.9, 133.6 and 133.7, 133.9 and 134.0,
134.1, 148.1, 150.9 ppm. IR (KBr): ~n 3512, 2955, 2865,
1614, 1590, 1469, 1386, 1300, 1197, 1050 cmꢀ1. Mass
(m/z, %): 422 (M+, 61), 408 (34), 407 (100), 392 (22), 377
(14), 351 (17), 239 (13), 57 (22). HRMS (ESI): 423.2334,
calcd for C30H31O2 (M+H+) 423.2324. Anal. Calcd for
C30H30O2: C, 85.27; H, 7.16. Found: C, 85.06; H, 7.06.
1,10-binaphthyl-5-yl]-3,3-dimethyl-2,3-dihydrofuran
(8)
(204 mg, 0.313 mmol) and K2CO3 (65 mg, 0.47 mmol) in
dry DMF (2 mL) under a nitrogen atmosphere at room temper-
ature and stirred for 1.5 h. The reaction mixture was poured
into satd aq NH4Cl and extracted with AcOEt. The organic
layer was washed with satd aq NaCl, dried over anhydrous
MgSO4, and concentrated in vacuo. The residue was chroma-
tographed on silica gel with CH2Cl2 to give dihydrofuran 9
(193 mg, 92.6%) as a pale yellow solid. Compound 9: color-
less plates melted at 189.0–189.5 ꢁC (from EtOH–hexane);
(64:36 mixture of diastereomers) 1H NMR (500 MHz,
CDCl3): dH 1.02 (s, 9Hꢂ0.64), 1.08 (s, 9Hꢂ0.36), 1.44 (s,
3H), 1.53 (s, 3H), 2.23 (s, 3Hꢂ0.64), 2.26 (s, 3Hꢂ0.36),
3.32 (s, 3Hꢂ0.36), 3.41 (s, 3Hꢂ0.64), 3.99 (s, 3Hꢂ0.36),
4.00 (s, 3Hꢂ0.64), 4.01–4.09 (m, 2H), 6.71–6.91 (m, 3H),
7.02–7.25 (m, 5H), 7.35–7.43 (m, 2H), 7.83 (d, J¼8.7 Hz,
1H), 7.87 (d, J¼9.6 Hz, 1H), 8.16 (d, J¼9.6 Hz, 1H), 8.39
(s, 1Hꢂ0.36), 8.41 (s, 1Hꢂ0.64) ppm. 13C NMR (125 MHz,
CDCl3): dC 21.5, 27.3, 27.6, 31.9 and 32.1, 32.6 and 32.7,
4.1.3. Synthesis of 4-tert-butyl-5-[20-hydroxy-30-methoxy-
carbonyl-2-(4-methylphenylsulfonyloxy)-1,10-binaphthyl-
5-yl]-3,3-dimethyl-2,3-dihydrofuran (8). p-Toluenesulfonyl
chloride (944 mg, 4.95 mmol) was added to a solution of

12430
N. Hoshiya et al. / Tetrahedron 62 (2006) 12424–12437
47.5, 52.5, 61.8 and 61.9, 83.4 and 83.5, 121.8 and 121.9,
124.4 and 124.5, 124.6, 124.7 and 124.8, 125.2 and 125.3,
126.0 and 126.2, 126.3, 126.9 and 127.0, 127.1, 127.2,
128.2, 128.3 and 128.4, 128.5 and 128.6, 128.7, 129.0,
129.1 and 129.3, 130.7 and 130.8, 133.0 and 133.2, 133.4
and 133.5, 133.6, 134.0 and 134.1, 135.3, 144.2, 145.9 and
146.0, 147.3 and 147.4, 154.3 and 154.4, 166.8 ppm. IR
(KBr): ~n 2954, 2866, 1734, 1624, 1468, 1445, 1361, 1292,
1207, 1173, 1092 cmꢀ1. Mass (m/z, %): 664 (M+, 79), 651
(17), 650 (43), 649 (100), 617 (21), 561 (19), 510 (19), 469
(12), 495 (32), 463 (19), 448 (13), 447 (33), 407 (13).
HRMS (ESI): 687.2383, calcd for C40H40O7SNa (M+Na+)
687.2392. Anal. Calcd for C40H40O7S: C, 72.27; H, 6.06.
Found: C, 72.23; H, 6.09.
(58:42 mixture of diastereomers) 1H NMR (500 MHz,
CDCl3): dH 1.03 (s, 9Hꢂ0.58), 1.07 (s, 9Hꢂ0.42), 1.43 (s,
3H), 1.51 (s, 3H), 3.41 (s, 3Hꢂ0.42), 3.42 (s, 3Hꢂ0.58),
3.90 (s, 3Hꢂ0.42), 3.91 (s, 3Hꢂ0.58). 4.00 (d, J¼8.2 Hz,
1Hꢂ0.42), 4.01 (d, J¼7.8 Hz, 1Hꢂ0.58), 4.05 (d,
J¼7.8 Hz, 1Hꢂ0.58), 4.06 (d, J¼8.2 Hz, 1Hꢂ0.42), 5.37
(s, 1H), 7.00–7.04 (m, 1H), 7.14–7.20 (m, 2H), 7.27 (d,
J¼6.9 Hz, 1H), 7.29–7.35 (m, 1H), 7.36 (d, J¼9.2 Hz, 1H),
7.42–7.46 (m, 1H), 7.93 (d, J¼8.2 Hz, 1Hꢂ0.58), 7.94 (d,
J¼7.8 Hz, 1Hꢂ0.42), 8.06 (d, J¼9.2 Hz, 1H), 8.50 (s,
1H) ppm. 13C NMR (100 MHz, CDCl3): dC 27.3, 27.5 and
27.6, 31.8 and 32.0, 32.6 and 32.7, 47.3, 52.4, 61.7 and
62.0, 83.2 and 83.3, 114.5, 118.3, 124.2 and 124.2, 125.1
and 125.3, 125.3, 125.4, 125.6 and 125.7, 125.8 and 125.9,
125.9 and 126.0, 127.8, 127.9 and 127.9, 128.3, 128.9,
129.1 and 129.2, 129.9 and 130.0, 133.7 and 133.8, 133.8,
133.9, 135.5 and 135.6, 147.9 and 148.0, 151.4, 155.0 and
155.1, 166.6 and 166.7 ppm. IR (KBr): ~n 3427, 2954, 1678,
1618, 1452, 1365, 1307, 1237, 1052, 1006 cmꢀ1. Mass
(m/z, %): 510 (M+, 59), 496 (37), 495 (100), 480 (11), 407
(24). HRMS (ESI): 533.2292, calcd for C33H34O5Na
(M+Na+) 533.2304. Anal. Calcd for C33H34O5: C, 77.62; H,
6.71. Found: C, 77.32; H, 6.71.
4.1.5. Synthesis of 4-tert-butyl-5-(30-carboxy-2-hydroxy-
20-methoxy-1,10-binaphthyl-5-yl)-3,3-dimethyl-2,3-dihy-
drofuran (3c). NaOH (364 mg, 9.10 mmol) was added to a
solution of 4-tert-butyl-5-[20-methoxy-30-methoxycarbonyl-
2-(4-methylphenylsulfonyloxy)-1,10-binaphthyl-5-yl]-3,3-
dimethyl-2,3-dihydrofuran (9) (840 mg, 1.26 mmol) in
MeOH (5 mL) under a nitrogen atmosphere at room temper-
ature and stirred at refluxing temperature for 4 h. The reac-
tion mixture was poured into 1 N HCl and extracted with
CH2Cl2. The organic layer was dried over anhydrous
MgSO4 and concentrated in vacuo. The residue was chroma-
tographed on silica gel with AcOEt–hexane (1:1) to give
dihydrofuran 3c (577 mg, 92%) as a colorless solid. Com-
pound 3c: colorless granules melted at 235.5–236.5 ꢁC
(from AcOEt–hexane); (54:46 mixture of diastereomers)
1H NMR (500 MHz, CDCl3): dH 1.03 (s, 9Hꢂ0.54), 1.07
(s, 9Hꢂ0.46), 1.44 (s, 3H), 1.52 (s, 3H), 3.45 (s,
3Hꢂ0.46), 3.46 (s, 3Hꢂ0.54), 4.00 (d, J¼7.8 Hz, 1Hꢂ0.46),
4.01 (d, J¼7.3 Hz, 1Hꢂ0.54), 4.05 (d, J¼7.3 Hz, 1Hꢂ0.54),
4.06 (d, J¼7.8 Hz, 1Hꢂ0.46), 5.66 (br s, 1H), 7.00–7.03 (m,
1H), 7.21–7.31 (m, 3H), 7.37–7.53 (m, 3H), 7.99 (br s, 1H),
8.09 (d, J¼8.7 Hz, 1H), 8.81 (br s, 1H) ppm. 13C NMR
(125 MHz, CDCl3): dC 27.3, 27.6 and 27.7, 31.9 and 32.0,
32.7, 47.4, 62.1 and 62.4, 83.3 and 83.4, 113.5, 118.3 and
118.4, 120.9, 123.3, 125.1, 125.3 and 125.6, 126.1 and
126.2, 126.5, 126.6 and 126.7, 127.9, 128.2 and 128.3,
129.0, 129.8, 129.9, 130.3 and 130.4, 133.6, 134.0, 136.4,
136.4, 147.7, 151.7, 154.1 and 154.2, 166.3 ppm. IR
(KBr): ~n 3357, 3181, 2957, 2864, 1729, 1687, 1620, 1449,
1298, 1230, 1044 cmꢀ1. Mass (m/z, %): 496 (M+, 56), 495
(30), 482 (37), 481 (100), 466 (15), 453 (16), 407 (34), 371
(14), 277 (14), 266 (12), 57 (14). HRMS (ESI): 519.2166,
calcd for C32H32O5Na (M+Na+) 519.2147. Anal. Calcd for
C32H32O5: C, 77.40; H, 6.50. Found: C, 77.06; H, 6.41.
4.1.7. Synthesis of 4-tert-butyl-5-(2,20-dihydroxy-30-
hydroxymethyl-1,10-binaphthyl-5-yl)-3,3-dimethyl-2,3-
dihydrofuran (10). A solution of 4-tert-butyl-5-(2,20-
dihydroxy-30-methoxycarbonyl-1,10-binaphthyl-5-yl)-3,3-
dimethyl-2,3-dihydrofuran (5) (501 mg, 1.01 mmol) in dry
THF (2 mL) was added dropwise to a suspension of LiAlH4
(61.3 mg, 1.62 mmol) in dry THF (5 mL) under a nitrogen
atmosphere at 0 ꢁC and stirred for 2 h at room temperature.
The reaction mixture was poured into 2 N HCl and extracted
with AcOEt. The organic layer was washed with satd aq
NaCl, dried over anhydrous MgSO4, and concentrated
in vacuo. The residue was chromatographed on silica gel
with AcOEt–CH2Cl2 (20:1) to give dihydrofuran 10
(411 mg, 86.9%) as a colorless solid. Compound 10: color-
less granules melted at 233.0–233.5 ꢁC (from AcOEt);
(55:45 mixture of diastereomers) 1H NMR (500 MHz,
CDCl3): dH 1.06 (s, 9H), 1.43 (s, 3Hꢂ0.55), 1.44 (s, 3Hꢂ
0.45), 1.50 (s, 3Hꢂ0.55), 1.52 (s, 3Hꢂ0.45), 2.52 (m, 1H),
3.92 (d, J¼8.0 Hz, 1Hꢂ0.55), 3.97 (d, J¼8.0 Hz, 1Hꢂ
0.55), 4.00 (d, J¼7.8 Hz, 1Hꢂ0.45), 4.05 (d, J¼7.8 Hz,
1Hꢂ0.45), 4.84 (dd, J¼13.3 and 6.0 Hz, 1Hꢂ0.45), 4.89
(d, J¼10.1 Hz, 1Hꢂ0.55), 4.90 (d, J¼10.1 Hz, 1Hꢂ0.55),
4.94 (dd, J¼13.3 and 5.3 Hz, 1Hꢂ0.45), 5.16 (s,
1Hꢂ0.55), 5.19 (s, 1Hꢂ0.45), 7.04 (m, 2H), 7.21–7.24 (m,
2H), 7.28–7.38 (m, 2H), 7.38 (d, J¼9.2 Hz, 1Hꢂ0.55),
7.39 (d, J¼9.2 Hz, 1Hꢂ0.45), 7.82–7.85 (m, 1H), 7.86 (s,
1Hꢂ0.45), 7.88 (s, 1Hꢂ0.55), 8.08 (d, J¼9.2 Hz,
1Hꢂ0.55), 8.08 (d, J¼9.2 Hz, 1Hꢂ0.45) ppm. 13C NMR
(125 MHz, CDCl3): dC 27.3, 27.6 and 27.7, 32.0 and 32.1,
32.7, 47.4, 62.6 and 62.9, 83.2 and 83.3, 111.2 and 111.4,
111.6 and 112.0, 118.1 and 118.2, 124.1 and 124.3, 124.4
and 124.5, 124.9 and 125.0, 126.3 and 126.4, 126.6 and
126.7, 127.3, 128.1, 128.1 and 128.3, 128.2 and 128.4,
128.5, 129.0, 129.1 and 129.2, 129.3, 133.0 and 133.3,
133.5 and 133.6, 134.1 and 134.1, 147.6 and 147.8, 151.2
and 151.4, 152.5 and 152.6 ppm. IR (KBr): ~n 3405, 2957,
1618, 1391, 1208, 1047 cmꢀ1. Mass (m/z, %): 468
(M+, 60), 454 (36), 453 (100), 451 (13), 420 (14), 403
(14), 379 (26). HRMS (ESI): 491.2185, calcd for
4.1.6. Synthesis of 4-tert-butyl-5-(2-hydroxy-20-methoxy-
30-methoxycarbonyl-1,10-binaphthyl-5-yl)-3,3-dimethyl-
2,3-dihydrofuran (3b). MeI (0.10 mL, 1.6 mmol) was
added to a solution of 4-tert-butyl-5-(30-carboxy-2-hy-
droxy-20-methoxy-1,10-binaphthyl-5-yl)-3,3-dimethyl-2,3-
dihydrofuran (3c) (520 mg, 1.05 mmol) and NaHCO3
(94 mg, 1.1 mmol) in dry DMF (5 mL) under a nitrogen at-
mosphere at room temperature and stirred overnight. The re-
action mixture was poured into satd aq NH4Cl and extracted
with AcOEt. The organic layer was dried over anhydrous
MgSO4 and concentrated in vacuo to give dihydrofuran 3b
(486 mg, 90.8%) as a colorless solid. Compound 3b: color-
less needles melted at 178.5–179.5 ꢁC (from EtOH–hexane);

N. Hoshiya et al. / Tetrahedron 62 (2006) 12424–12437
12431
C31H32O4Na (M+Na+) 491.2198. Anal. Calcd for C31H32O4:
C, 79.46; H, 6.88. Found: C, 79.27; H, 6.75.
THF (40 mL) under a nitrogen atmosphere at room temper-
ature and refluxed for 3 h. The reaction mixture was poured
into satd aq NaHCO3 and extracted with AcOEt. The or-
ganic layer was washed with satd aq NaCl, dried over anhy-
drous MgSO4, and concentrated in vacuo. The residue was
chromatographed on silica gel with AcOEt–hexane (1:1) to
give dihydrofuran 11 (3.54 g, 92.8%) as a colorless solid.
Compound 11: pale yellow granules melted at 206.0–
207.0 ꢁC (from MeOH–CH2Cl2); (52:48 mixture of dia-
stereomers) 1H NMR (500 MHz, CDCl3): dH 1.06 (s,
9Hꢂ0.48), 1.07 (s, 9Hꢂ0.52), 1.43 (s, 3Hꢂ0.48), 1.44
(s, 3Hꢂ0.52), 1.50 (s, 3Hꢂ0.48), 1.52 (s, 3Hꢂ0.52), 2.65
4.1.8. Synthesis of 4-tert-butyl-5-[2-hydroxy-1-(2,2,-di-
methyl-1,3-dioxa-1,2,3,4-tetrahydroanthracen-9-yl)-
naphthalen-5-yl]-3,3-dimethyl-2,3-dihydrofuran
(3d).
Pyridinium p-toluenesulfonate (PPTS) (54.1 mg, 0.215 mmol)
was added to a solution of 4-tert-butyl-5-(2,20-dihydroxy-
30-hydroxymethyl-1,10-binaphthyl-5-yl)-3,3-dimethyl-2,3-
dihydrofuran (10) (1.01 g, 2.16 mmol) and acetone dimethyl
acetal (0.32 mL, 2.6 mmol) in acetone (10 mL) under a nitro-
gen atmosphere at 0 ꢁC and stirred for 1 h at refluxing tem-
perature. The reaction mixture was poured into satd aq
NaHCO3 and extracted with AcOEt. The organic layer was
washed with satd aq NaCl, dried over anhydrous MgSO4,
and concentrated in vacuo. The residue was chromato-
graphed on silica gel with AcOEt–CH2Cl2 (1:30) to give
dihydrofuran 3d (1.03 g, 93.5%) as a colorless solid.
Compound 3d: yellow plates melted at 182.5–183.0 ꢁC
(from AcOEt–hexane); (55:45 mixture of diastereomers)
1H NMR (500 MHz, CDCl3): dH 1.04 (s, 9Hꢂ0.45), 1.07
(s, 9Hꢂ0.55), 1.35 (s, 3H), 6.38 (s, 3Hꢂ0.45), 1.40 (s,
3Hꢂ0.55), 1.43 (s, 3H), 1.51 (s, 3H), 4.00 (d, J¼8.2 Hz,
1Hꢂ0.45), 4.00 (d, J¼7.8 Hz, 1Hꢂ0.55), 4.05 (d,
J¼7.8 Hz, 1Hꢂ0.55), 4.06 (d, J¼8.2 Hz, 1Hꢂ0.45), 4.97
(br s, 1H), 3.74 (s, 3Hꢂ0.48), 3.75 (s, 3Hꢂ0.52), 3.95 (qAB
,
J¼8.0 Hz, 2Hꢂ0.48), 4.02 (qAB, J¼8.4 Hz, 2Hꢂ0.52),
4.86 (qAB, J¼13.3 Hz, 1Hꢂ0.52), 4.89 (qAB, J¼12.8 Hz,
1Hꢂ0.48), 5.70 (br s, 1Hꢂ0.48), 5.84 (br s, 1Hꢂ0.52),
6.95 (d, J¼8.2 Hz, 1Hꢂ0.48), 7.10 (d, J¼8.7 Hz, 1Hꢂ
0.52), 7.10–7.23 (m, 3H), 7.25–7.31 (m, 2H), 7.48 (d,
J¼9.2 Hz, 1Hꢂ0.48), 7.49 (d, J¼9.6 Hz, 1Hꢂ0.52), 7.77–
7.81 (m, 2H), 8.17 (d, J¼9.2 Hz, 1Hꢂ0.48), 8.18 (d,
J¼9.6 Hz, 1Hꢂ0.52) ppm. 13C NMR (125 MHz, CDCl3):
dC 27.3 and 27.3, 27.6 and 27.7, 32.0 and 32.1, 32.7, 47.4,
56.5 and 56.6, 62.9 and 63.1, 83.2 and 83.3, 114.1, 115.5
and 115.6, 115.8, 123.4 and 123.5, 124.5 and 124.9, 125.5
and 125.7, 126.2 and 126.3, 126.4, 126.4 and 126.5, 127.6,
127.9 and 128.1, 128.1 and 128.2, 128.2 and 128.3, 128.6
and 128.7, 128.8 and 128.9, 133.4 and 133.5, 133.8, 133.8,
134.0 and 134.1, 147.8 and 147.9, 149.9 and 150.0, 155.7
and 155.8 ppm. IR (KBr): ~n 3364, 2954, 2866, 1613, 1508,
1395, 1264, 1215, 1085, 1049 cmꢀ1. Mass (m/z, %): 482
(M+, 97), 481 (11), 480 (13), 468 (37), 467 (100), 466 (12),
465 (21), 452 (10), 449 (12), 434 (11), 403 (20), 394 (12),
393 (30), 374 (15), 370 (11), 279 (13), 239 (11), 57 (21).
HRMS (ESI): 505.2330, calcd for C32H34O4Na (M+Na+)
505.2355. Anal. Calcd for C32H34O4: C, 79.64; H, 7.10.
Found: C, 79.39; H, 7.07.
(s, 1H), 5.10 (qAB, J¼15.8 Hz, 2Hꢂ0.55), 5.10 (qAB
,
J¼15.1 Hz, 2Hꢂ0.45), 7.02–7.05 (m, 1H), 7.11–7.17 (m,
2H), 7.19–7.23 (m, 1H), 7.24 (d, J¼6.9 Hz, 1H), 7.30–7.32
(m, 1H), 7.34 (d, J¼9.2 Hz, 1H), 7.61 (s, 1H), 7.76 (d,
J¼8.2 Hz, 1Hꢂ0.45), 7.77 (d, J¼8.2 Hz, 1Hꢂ0.55), 8.01
(d, J¼9.2 Hz, 1H) ppm. 13C NMR (125 MHz, CDCl3): dC
24.1 and 24.3, 25.2 and 25.3, 27.3 and 27.4, 27.5 and 27.6,
31.9 and 32.0, 32.7, 47.3 and 47.3, 61.1 and 61.2, 83.2 and
83.3, 100.2 and 100.3, 114.3 and 114.4, 114.8 and 115.0,
117.8 and 117.8, 121.3 and 121.3, 124.2 and 124.3, 124.6
and 124.7, 124.8 and 124.8, 125.3 and 125.4, 125.5, 125.5
and 125.7, 126.7, 127.6 and 127.6, 127.7 and 127.7, 127.7,
127.9 and 127.9, 128.6, 133.1 and 133.2, 133.5, 133.8,
148.2 and 148.2, 148.7 and 148.8, 151.2 and 151.3 ppm.
IR (KBr): ~n 2955, 1614, 1371, 1275, 1051 cmꢀ1. Mass
(m/z, %): 508 (M+, 33), 451 (42), 450 (100), 436 (29), 435
(63), 420 (16), 403 (20), 379 (14). HRMS (ESI): 531.256,
calcd for C34H36O4Na (M+Na+) 531.2511. Anal. Calcd for
C34H36O4: C, 80.28; H, 7.13. Found: C, 79.94; H, 7.10.
4.1.10. Synthesis of 4-tert-butyl-5-[30-hydroxymethyl-
2-methoxy-20-(2-methoxyethoxy)-1,10-binaphthyl-5-
yl]-3,3-dimethyl-2,3-dihydrofuran (12). 2-Methoxyethyl
bromide (0.65 mL, 6.9 mmol) was added to a solution of
4-tert-butyl-5-(20-hydroxy-30-hydroxymethyl-2-methoxy-
1,10-binaphthyl-5-yl)-3,3-dimethyl-2,3-dihydrofuran (11)
(2.78 g, 5.76 mmol) and K2CO3 (1.30 g, 9.41 mmol) in
dry DMF (30 mL) under a nitrogen atmosphere at room
temperature and stirred for 12 h. The reaction mixture
was poured into satd aq NH4Cl and extracted with AcOEt.
The organic layer was washed with satd aq NaCl, dried
over anhydrous MgSO4, and concentrated in vacuo. The resi-
due was chromatographed on silica gel with AcOEt–hexane
(1:1) to give dihydrofuran 12 (2.87 g, 92.2%) as a colorless
solid. Compound 12: colorless granules melted at 150.5–
151.0 ꢁC (from AcOEt–hexane); (52:48 mixture of dia-
4.1.9. Synthesis of 4-tert-butyl-5-(20-hydroxy-30-hydroxy-
methyl-2-methoxy-1,10-binaphthyl-5-yl)-3,3-dimethyl-
2,3-dihydrofuran (11). MeI (0.60 mL, 9.6 mmol) was
added to a solution of 4-tert-butyl-5-[2-hydroxy-1-(2,2,-
dimethyl-1,3-dioxa-1,2,3,4-tetrahydroanthracen-9-yl)naph-
thalen-5-yl]-3,3-dimethyl-2,3-dihydrofuran (3d) (4.03 g,
7.92 mmol) and K2CO3 (1.64 g, 11.9 mmol) in dry DMF
(40 mL) under a nitrogen atmosphere at room temperature
and stirred for 9 h. The reaction mixture was poured into
satd aq NH4Cl and extracted with AcOEt. The organic layer
was washed with satd aq NaCl, dried over anhydrous
MgSO4, and concentrated in vacuo. The residue was chro-
matographed on silica gel with AcOEt–hexane (1:1) to
give 4.13 g of 4-tert-butyl-5-[2-methoxy-1-(2,2,-dimethyl-
1,3-dioxa-1,2,3,4-tetrahydroanthracen-9-yl)naphthalen-5-yl]-
3,3-dimethyl-2,3-dihydrofuran as a colorless solid. The
solid (4.13 g), ethylene glycol (5.0 mL, 90 mmol), and
TsOH$H2O (150 mg, 0.789 mmol) was dissolved in dry
1
stereomers) H NMR (500 MHz, CDCl3): dH 1.02 (s, 9Hꢂ
0.52), 1.06 (s, 9Hꢂ0.48), 1.44 (s, 3H), 1.51 (s, 3Hꢂ0.52),
1.52 (s, 3Hꢂ0.42), 3.12–3.30 (m, 2H), 3.23 (s, 3Hꢂ0.52),
3.27 (s, 3Hꢂ0.48), 3.34–3.43 (m, 1H), 3.48–3.56 (m, 1H),
3.75 (s, 3H), 4.03 (qAB, J¼8.0 Hz, 2Hꢂ0.52), 4.04 (qAB
,
J¼7.3 Hz, 2Hꢂ0.48), 4.36 (t, J¼7.1 Hz, 1Hꢂ0.48), 4.67
(t, J¼7.1 Hz, 1Hꢂ0.52), 4.81–4.90 (m, 2H), 7.04–7.22
(m, 4H), 7.27 (d, J¼6.4 Hz, 1H), 7.32–7.35 (m, 1H), 7.46
(d, J¼9.6 Hz, 1H), 7.82 (d, J¼8.2 Hz, 1H), 7.84 (s,
1Hꢂ0.48), 7.85 (s, 1Hꢂ0.52), 8.14 (d, J¼9.2 Hz,

12432
N. Hoshiya et al. / Tetrahedron 62 (2006) 12424–12437
1H) ppm. 13C NMR (125 MHz, CDCl3): dC 27.2, 27.6 and
27.7, 31.8 and 31.9, 32.6 and 32.6, 47.3, 56.4 and 56.5,
58.5 and 58.6, 62.6 and 62.7, 71.3, 71.7 and 71.9, 83.3 and
83.3, 113.7 and 113.9, 119.3 and 119.4, 123.1 and 123.4,
124.5 and 124.6, 124.9 and 125.2, 126.0, 126.0, 126.0,
126.1 and 126.1, 127.8, 127.8 and 127.9, 128.0 and 128.1,
128.1, 128.9 and 129.1, 133.4 and 133.4, 133.9, 133.9 and
133.9, 134.0 and 134.2, 148.0 and 148.0, 154.3 and 154.8,
154.9, 154.9 ppm. IR (KBr): ~n 3488, 2955, 2865, 1648,
1611, 1509, 1361, 1263, 1104, 1050 cmꢀ1. Mass (m/z, %):
540 (M+, 100), 526 (16), 525 (37), 492 (15), 462 (10), 403
(18), 59 (16), 57 (12). HRMS (ESI): 563.2753, calcd for
C35H40O5Na (M+Na+) 563.2773. Anal. Calcd for
C35H40O5: C, 77.75; H, 7.46. Found: C, 77.67; H, 7.38.
1 mg) in CH2Cl2 (3–10 mL) was irradiated externally with
940 W Na lamp under an oxygen atmosphere at 0 ꢁC for
1–4 h. The photolysate was concentrated in vacuo. The resi-
due was chromatographed on silica gel with CH2Cl2 to give
a stereoisomeric mixture of 1-(1,10-binaphthyl-5-yl)-5-tert-
butyl-4,4-dimethyl-2,6,7-trioxabicyclo[3.2.0]heptane cis-2
and trans-2 as a colorless solid (cis:trans¼64:36 for 2a,
42:58 for 2b, 48:52 for 2c, 43:57 for 2d, and 46:54 for 2e)
in 90–96% yields. The mixture was further separated into
pure cis-2 and pure trans-2 by means of column chromato-
graphy (SiO2).
4.2.1. 5-tert-Butyl-1-(2-hydroxy-1,10-binaphthyl-5-yl)-
4,4-dimethyl-2,6,7-trioxabicyclo[3.2.0]heptane (2a).
Compound cis-2a: colorless granules melted at 163.5–
164.0 ꢁC (from THF–AcOEt). 1H NMR (500 MHz,
CDCl3): dH 0.96 (s, 9H), 1.33 (s, 3H), 1.69 (s, 3H), 4.13
(d, J¼8.2 Hz, 1H), 4.73 (d, J¼8.2 Hz, 1H), 4.90 (s, 1H),
7.17 (d, J¼8.7 Hz, 1H), 7.23–7.33 (m, 3H), 7.35 (d,
J¼8.5 Hz, 1H), 7.51 (dd with fine coupling, J¼8.3 and
6.9 Hz, 1H), 7.57 (d, J¼6.9 Hz, 1H), 7.66 (dd, J¼8.3 and
6.9 Hz, 1H), 7.97 (d, J¼8.3 Hz, 1H), 8.03 (d, J¼8.3 Hz,
1H), 8.06–8.07 (m, 1H), 8.67 (br d, J¼8.5 Hz, 1H) ppm.
13C NMR (125 MHz, CDCl3): dC 20.1, 26.3, 26.8, 36.9,
45.7, 80.6, 106.0, 117.2, 117.7, 119.5, 125.2, 125.8, 125.9,
126.6, 127.0, 127.4, 128.0, 128.2, 128.4, 129.4, 129.6,
131.5, 131.5, 132.9, 134.2, 134.9, 150.5 ppm. IR (KBr): ~n
3512, 2978, 2893, 1613, 1473, 1385, 1264, 1203, 1038,
994 cmꢀ1. Mass (m/z, %): 454 (M+, 44), 398 (30), 314
(33), 298 (22), 297 (100), 269 (23), 268 (15), 252 (12),
251 (13). HRMS (ESI): 477.2032, calcd for C30H30O4Na
(M+Na+) 477.2042. Anal. Calcd for C30H30O4: C, 79.27;
H, 6.65. Found: C, 79.00; H, 6.66. Compound trans-2a: col-
orless granules melted at 163.0–164.0 ꢁC (from THF–
AcOEt). 1H NMR (500 MHz, CDCl3): dH 0.98 (s, 9H),
1.32 (s, 3H), 1.69 (s, 3H), 4.11 (d, J¼8.3 Hz, 1H), 4.73 (d,
J¼8.3 Hz, 1H), 4.87 (s, 1H), 7.18 (d, J¼8.3 Hz, 1H), 7.25
(dd, J¼8.3 and 7.3 Hz, 1H), 7.31–7.39 (m, 3H), 7.50 (d,
J¼6.7 Hz, 1H), 7.54 (dd, J¼7.8 and 7.3 Hz, 1H), 7.66
(dd, J¼8.3 and 6.7 Hz, 1H), 7.99 (d, J¼8.3 Hz, 1H), 8.04
(d, J¼7.8 Hz, 1H), 8.04–8.06 (m, 1H), 8.68–8.70 (m,
1H) ppm. 13C NMR (125 MHz, CDCl3): dC 20.1, 26.2,
26.8, 36.9, 45.7, 80.6, 106.0, 117.2, 118.7, 119.4, 125.2,
125.6, 126.1, 126.6, 126.7, 127.0, 127.4, 127.9, 128.2,
128.6, 129.4, 129.8, 131.5, 131.5, 132.8, 134.2, 135.0,
150.5 ppm. IR (KBr): ~n 3412, 2979, 2902, 1616, 1599,
1473, 1387, 1211, 1038 cmꢀ1. Mass (m/z, %): 454 (M+,
35), 398 (26), 314 (31), 298 (24), 297 (100), 269 (24), 268
(13), 251 (12), 250 (13), 239 (23), 57 (22). HRMS
(ESI): 509.2339, calcd for C31H34O5Na (M+Na++MeOH)
509.2304. Anal. Calcd for C30H30O4: C, 79.27; H, 6.65.
Found: C, 78.98; H, 6.60.
4.1.11. Synthesis of 4-tert-butyl-5-[2-hydroxy-30-hydroxy-
methyl-20-(2-methoxyethoxy)-1,10-binaphthyl-5-yl]-3,3-
dimethyl-2,3-dihydrofuran (3e). Sodium methanethiolate
(95%, 750 mg, 10.2 mmol) was added to a solution of
4-tert-butyl-5-[30-hydroxymethyl-2-methoxy-20-(2-methoxy-
ethoxy)-1,10-binaphthyl-5-yl]-3,3-dimethyl-2,3-dihydro-
furan (12) (2.87 g, 5.33 mmol) in dry DMF (30 mL) under
a nitrogen atmosphere at room temperature and stirred at
135 ꢁC for 1 h. The reaction mixture was poured into satd
aq NaHCO3 and extracted with AcOEt. The organic layer
was washed with satd aq NaCl, dried over anhydrous
MgSO4, and concentrated in vacuo. The residue was chroma-
tographed on silica gel with AcOEt–hexane (1:1) to give
dihydrofuran 3e (1.65 g, 58.8%) as a colorless solid.
Compound 3e: colorless granules melted at 178.0–179.0 ꢁC
(from MeOH–CH2Cl2); (50:50 mixture of diastereomers)
1H NMR (500 MHz, CDCl3): dH 1.00 (s, 9Hꢂ0.50), 1.05
(s, 9Hꢂ0.50), 1.43 (s, 3H), 1.51 (s, 3Hꢂ0.50), 1.52 (s,
3Hꢂ0.50), 3.11–3.15 (m, 1Hꢂ0.50), 3.20–3.27 (m,
1Hꢂ0.50), 3.21 (s, 3Hꢂ0.50), 3.24 (s, 3Hꢂ0.50), 3.29–
3.39 (m, 1H), 3.42–3.52 (m, 2H), 4.03 (qAB, J¼7.8 Hz,
2Hꢂ0.5), 4.04 (qAB
,
J¼7.8 Hz, 2Hꢂ0.50), 4.50 (t,
J¼7.1 Hz, 1Hꢂ0.50), 4.75 (t, J¼7.1 Hz, 1Hꢂ0.50), 4.78–
4.84 (m, 2H), 5.64 (s, 1Hꢂ0.50), 5.65 (s, 1Hꢂ0.50), 7.09–
7.28 (m, 5H), 7.34 (d, J¼9.2 Hz, 1H), 7.37–7.40 (m, 1H),
7.83 (d, J¼8.2 Hz, 1H), 7.86 (d, J¼2.7 Hz, 1H), 8.04 (d,
J¼9.2 Hz, 1H) ppm. 13C NMR (125 MHz, CDCl3): dC
27.3, 27.6 and 27.7, 31.8 and 31.9, 32.6 and 32.7, 47.3,
58.6 and 58.7, 62.3 and 62.4, 71.5 and 71.6, 71.7 and 71.8,
83.3 and 83.4, 115.0 and 115.2, 118.0 and 118.1, 121.0 and
120.3, 124.6 and 125.0, 125.2 and 125.3, 125.6, 125.8 and
125.9, 126.1 and 126.2, 126.8 and 126.9, 127.7 and 127.8,
128.0 and 128.2, 128.1, 128.3 and 128.4, 130.2 and 130.5,
130.7 and 130.8, 133.6, 133.7, 133.8, 134.3 and 134.5,
147.9 and 148.0, 151.5 and 151.6, 155.5 and 155.9 ppm.
IR (KBr): ~n 3379, 3284, 2955, 2865, 1647, 1617, 1468,
1396, 1300, 1237, 1129, 1105 cmꢀ1. Mass (m/z, %): 526
(M+, 100), 512 (26), 511 (66), 493 (10), 478 (17), 448 (10),
435 (11), 420 (16), 419 (12), 405 (14), 403 (19), 239 (10),
59 (36), 57 (17). HRMS (ESI): 549.2612, calcd for
C34H38O5Na (M+Na+) 549.2617. Anal. Calcd for
C34H38O5: C, 77.54; H, 7.27. Found: C, 77.83; H, 7.44.
4.2.2. 5-tert-Butyl-1-(2-hydroxy-20-methoxy-30-methoxy-
carbonyl-1,10-binaphthyl-5-yl)-4,4-dimethyl-2,6,7-trioxa-
bicyclo[3.2.0]heptane (2b). Compound cis-2b: colorless
1
plate melted at 170.0–171.0 ꢁC (from AcOEt–hexane). H
4.2. Synthesis of bicyclic dioxetanes 2: general
procedure
NMR (500 MHz, CDCl3): dH 0.91 (s, 9H), 1.32 (s, 3H),
1.68 (s, 3H), 3.42 (s, 3H), 3.96 (s, 3H), 4.14 (d, J¼8.2 Hz,
1H), 4.75 (d, J¼8.2 Hz, 1H), 5.14 (s, 1H), 7.13–7.17 (m,
2H), 7.25 (m, 1H), 7.36 (dd with fine coupling, J¼9.6 and
6.9 Hz, 1H), 7.38 (d, J¼9.6 Hz, 1H), 7.48 (dd with fine
A solution of 5-(1,10-binaphthyl-5-yl)-4-tert-butyl-3,3-di-
methyl-2,3-dihydrofuran 3 (50–200 mg) and TPP (ca.

N. Hoshiya et al. / Tetrahedron 62 (2006) 12424–12437
12433
coupling, J¼8.3 and 6.9 Hz, 1H), 7.97 (d, J¼8.3 Hz, 1H),
8.06–8.09 (m, 1H), 8.54 (s, 1H), 8.74–8.76 (m, 1H) ppm.
13C NMR (125 MHz, CDCl3): dC 20.0, 26.1, 26.7, 36.8,
45.7, 52.5, 61.7, 80.6, 106.0, 115.1, 117.7, 117.7, 124.1,
125.2, 125.4, 125.5, 126.2, 126.8, 127.6, 127.7, 128.6,
129.1, 129.2, 130.0, 131.5, 134.1, 134.8, 135.5, 151.0,
155.1, 166.6 ppm. IR (KBr): ~n 3406, 2960, 1704, 1620,
1269, 1224, 1003 cmꢀ1. Mass (m/z, %): 542 (M+, 56), 510
(M+ꢀ32, trace), 486 (12), 454 (13), 386 (28), 385 (100),
370 (23), 326 (19), 294 (15), 266 (24), 239 (13), 226 (12).
HRMS (ESI): 565.2182, calcd for C33H34O7Na (M+Na+)
565.2202. Anal. Calcd for C33H34O7: C, 73.04; H, 6.32.
Found: C, 72.76; H, 6.31. Compound trans-2b: colorless
granules melted at 163.5–164.0 ꢁC (from CH2Cl2). 1H
NMR (500 MHz, CDCl3): dH 0.97 (s, 9H), 1.33 (s, 3H),
1.69 (s, 3H), 3.43 (s, 3H), 3.98 (s, 3H), 4.13 (d, J¼8.7 Hz,
1H), 4.74 (d, J¼8.7 Hz, 1H), 5.10 (s, 1H), 7.12 (d,
J¼8.2 Hz, 1H), 7.16 (d, J¼8.5 Hz, 1H), 7.20 (dd, J¼8.5
and 7.0 Hz, 1H), 7.38 (d, J¼9.6 Hz, 1H), 7.39 (dd, J¼8.2
and 6.9 Hz, 1H), 7.50 (dd, J¼8.2 and 6.9 Hz, 1H), 7.99 (d,
J¼8.2 Hz, 1H), 8.05–8.08 (m, 1H), 8.55 (s, 1H), 8.71–8.75
(m, 1H) ppm. 13C NMR (125 MHz, CDCl3): dC 20.0, 26.2,
26.8, 36.9, 45.7, 52.5, 62.0, 80.6, 106.0, 115.1, 117.7,
124.0, 125.2, 125.4, 125.5, 126.1, 126.9, 127.6, 127.7,
128.7, 129.1, 129.3, 130.1, 131.6, 134.1, 134.8, 135.5,
151.0, 155.2, 166.6 ppm. IR (KBr): ~n 3406, 2960, 1704,
1621, 1224, 1003 cmꢀ1. Mass (m/z, %): 542 (M+, 45), 510
(M+ꢀ32, trace), 486 (13), 454 (14), 386 (26), 385 (100),
326 (21), 297 (13), 294 (14), 278 (13), 266 (29), 239 (18),
226 (17), 57 (66). HRMS (ESI): 565.2199, calcd for
C33H34O7Na (M+Na+) 565.2202. Anal. Calcd for
C33H34O7+CH2Cl2 (3.0% w/w): C, 71.26; H, 6.20. Found:
C, 70.97; H, 6.50.
and 6.7 Hz, 1H), 7.46 (d, J¼9.6 Hz, 1H), 7.52 (dd, J¼7.8
and 6.7 Hz, 1H), 7.98–8.01 (m, 1H), 8.12 (d, J¼7.8 Hz,
1H), 8.60 (s, 1H), 8.76–8.79 (m, 1H) ppm. 13C NMR
(125 MHz, acetone-d6): dC 20.2, 26.3, 27.1, 37.5, 46.4,
61.9, 81.1, 106.7, 116.4, 117.3, 119.0, 125.8, 125.9, 126.3,
126.5, 127.0, 127.3, 127.6, 128.4, 129.2, 129.4, 130.1,
131.0, 132.8, 133.9, 136.2, 136.8, 153.5, 155.8,
167.3 ppm. IR (KBr): ~n 3421, 3200, 2976, 2892, 1717,
1620, 1591, 1447, 1400, 1370, 1274, 1225, 1038 cmꢀ1
.
Mass (m/z, %): 528 (M+, 37), 500 (23), 472 (17), 444 (15),
386 (23), 385 (68), 372 (26), 371 (100), 370 (31), 356
(14), 343 (46), 327 (23), 326 (34), 294 (22), 267 (19), 266
(40), 255 (21), 239 (30), 226 (30), 57 (95). HRMS (ESI):
551.2039, calcd for C32H32O7Na (M+Na+) 551.2046.
Anal. Calcd for C32H32O7+H2O (1.7% w/w): C, 71.49; H,
6.19. Found: C, 71.17; H, 6.30.
4.2.4. 5-tert-Butyl-1-[2-hydroxy-1-(2,2-dimethyl-1,3-di-
oxa-1,2,3,4-tetrahydro-anthracen-9-yl)naphthalen-5-yl]-
4,4-dimethyl-2,6,7-trioxabicyclo[3.2.0]heptane (2d).
Compound cis-2d: colorless needles melted at 145.0–
146.0 ꢁC (from AcOEt–hexane). 1H NMR (400 MHz,
CDCl3): dH 0.91 (s, 9H), 1.32 (s, 3H), 1.35 (s, 3H), 1.38
(s, 3H), 1.67 (s, 3H). 4.13 (d, J¼8.5 Hz, 1H), 4.75 (d,
J¼8.5 Hz, 1H), 4.84 (s, 1H), 5.16 (qAB with fine coupling,
J¼15.1 Hz, 2H), 7.14–7.19 (m, 2H), 7.21–7.28 (m, 2H),
7.34 (d, J¼9.3 Hz, 1H), 7.36 (dd with fine coupling, J¼8.1
and 6.8 Hz, 1H), 7.69 (s, 1H), 7.82 (d, J¼8.1 Hz, 1H),
8.02–8.05 (m, 1H), 8.69–8.73 (m, 1H) ppm. 13C NMR
(125 MHz, CDCl3): dC 20.0, 24.3, 25.2, 26.1, 26.7, 36.8,
45.7, 61.2, 80.6, 100.2, 106.0, 114.9, 115.0, 117.3, 117.8,
121.3, 124.4, 124.6, 124.8, 124.9, 126.8, 127.0, 127.3,
127.8, 127.9, 127.9, 128.6, 131.1, 133.0, 134.8, 148.8,
150.8 ppm. IR (KBr): ~n 3500, 2993, 1617, 1371, 1135,
1039 cmꢀ1. Mass (m/z, %): 540 (M+, 10), 539 (27), 482
(35), 481 (100), 425 (17), 382 (13), 341 (19), 326 (23),
325 (91), 324 (31), 297 (11), 296 (11), 239 (11), 57 (22).
HRMS (ESI): 563.2413, calcd for C34H36O6Na (M+Na+)
563.2410. Anal. Calcd for C34H36O4+H2O (2.5% w/w): C,
73.62; H, 6.82. Found: C, 73.26; H, 6.91. Compound cis-
2d: colorless granules melted at 165.0–165.5 ꢁC (from
4.2.3. 5-tert-Butyl-1-(30-carboxy-2-hydroxy-20-methoxy-
1,10-binaphthyl-5-yl)-4,4-dimethyl-2,6,7-trioxabicy-
clo[3.2.0]heptane (2c). Compound cis-2c: colorless
granules melted at 179.5–180.5 ꢁC (from THF–hexane).
1H NMR (400 MHz, acetone-d6): dH 0.93 (s, 9H), 1.31 (s,
3H), 1.72 (s, 3H), 3.50 (s, 3H), 4.21 (d, J¼8.2 Hz, 1H),
4.65 (d, J¼8.2 Hz, 1H), 7.16–7.20 (m, 2H), 7.34 (dd,
J¼8.5 and 7.3 Hz, 1H), 7.42 (dd with fine coupling, J¼8.3
and 6.8 Hz, 1H), 7.46 (d, J¼9.3 Hz, 1H), 7.52 (dd with
fine coupling, J¼8.1 and 6.8 Hz, 1H), 7.99–8.02 (m, 1H),
8.12 (d, J¼8.1 Hz, 1H), 8.61 (s, 1H), 8.79 (br d, J¼9.3 Hz,
1H) ppm. 13C NMR (125 MHz, acetone-d6): dC 20.2, 26.2,
27.1, 37.5, 46.3, 61.7, 81.1, 106.6, 116.3, 118.4, 119.0,
125.8, 126.1, 126.2, 126.5, 126.9, 127.3, 127.6, 128.4,
129.2, 129.3, 130.0, 130.9, 132.6, 133.9, 136.2, 136.7,
153.5, 155.8, 167.3 ppm. IR (KBr): ~n 3412, 3126, 2976,
1
AcOEt–hexane). H NMR (400 MHz, CDCl3): dH 0.97 (s,
9H), 1.33 (s, 3H), 1.36 (s, 3H), 1.41 (s, 3H), 1.70 (s, 3H),
4.13 (d, J¼8.3 Hz, 1H), 4.74 (d, J¼8.3 Hz, 1H), 4.88 (s,
1H), 5.16 (qAB with fine coupling, J¼15.4 Hz, 2H), 7.09
(d, J¼8.3 Hz, 1H), 7.15 (d, J¼8.4 Hz, 1H), 7.24 (dd,
J¼8.3 and 7.3 Hz, 1H), 7.26 (dd with fine coupling, J¼8.4
and 7.3 Hz, 1H), 7.34 (d, J¼9.5 Hz, 1H), 7.36 (dd with
fine coupling, J¼8.1 and 6.8 Hz, 1H), 7.69 (s, 1H), 7.82
(d, J¼8.1 Hz, 1H), 8.00–8.04 (m, 1H), 8.66–8.68 (br d,
J¼9.5 Hz, 1H) ppm. 13C NMR (125 MHz, CDCl3): dC
20.1, 24.2, 25.3, 26.2, 26.8, 36.9, 45.7, 61.4, 80.6, 100.4,
105.9, 114.7, 115.1, 117.3, 117.8, 121.4, 124.3, 124.4,
124.9, 125.0, 126.8, 127.3, 127.8, 127.9, 128.0, 128.7,
131.3, 133.2, 134.8, 148.9, 150.8 ppm. IR (KBr): ~n 3416,
2979, 1617, 1371, 1268, 1133, 1046 cmꢀ1. Mass (m/z, %):
540 (M+, 9), 539 (24), 507 (10), 482 (34), 481 (95), 449
(35), 434 (23), 425 (17), 382 (14), 341 (20), 325 (27), 324
(100), 323 (35), 298 (10), 297 (15), 295 (11), 239 (12),
162 (12), 57 (33). HRMS (ESI): 595.2686, calcd for
C35H40O7Na (M+Na++MeOH) 595.2672. Anal. Calcd for
C34H36O4+AcOEt (2.0% w/w): C, 75.11; H, 6.76. Found:
C, 74.81; H, 6.75.
2911, 1735, 1619, 1590, 1446, 1355, 1224, 1038 cmꢀ1
.
Mass (m/z, %): 528 (M+, 25), 500 (14), 472 (14), 386 (15),
385 (42), 372 (28), 371 (100), 370 (19), 356 (15), 343
(26), 327 (18), 326 (28), 294 (17), 267 (20), 266 (27), 255
(16), 239 (26), 226 (23), 57 (55). HRMS (ESI): 551.2059,
calcd for C32H32O7Na (M+Na+) 551.2046. Anal. Calcd for
C32H32O7: C, 72.71; H, 6.10. Found: C, 72.32; H, 6.50.
Compound trans-2c: colorless granules melted at 175.0–
1
175.5 ꢁC (from AcOEt–hexane). H NMR (500 MHz, ace-
tone-d6): dH 0.96 (s, 9H), 1.31 (s, 3H), 1.73 (s, 3H), 3.54
(s, 3H), 4.18 (d, J¼8.2 Hz, 1H), 4.63 (d, J¼8.2 Hz, 1H),
7.15 (d, J¼8.7 Hz, 1H), 7.19 (d, J¼8.7 Hz, 1H), 7.33 (dd,
J¼8.7 and 7.3 Hz, 1H), 7.40 (dd with fine coupling, J¼8.7

12434
N. Hoshiya et al. / Tetrahedron 62 (2006) 12424–12437
4.2.5. 5-tert-Butyl-1-[2-hydroxy-30-hydroxymethyl-20-(2-
methoxyethoxy)-1,10-binaphthyl-5-yl]-4,4-dimethyl-
2,6,7-trioxabicyclo[3.2.0]heptane (2e). Compound cis-2e:
colorless granules melted at 165.5–166.0 ꢁC (from THF–
MeOH). 1H NMR (500 MHz, CDCl3): dH 0.89 (s, 9H),
1.32 (s, 3H), 1.67 (s, 3H), 3.20 (ddd, J¼10.8, 6.2, and
2.3 Hz, 1H), 3.05 (s, 3H), 3.30 (ddd, J¼10.8, 6.0, and
2.3 Hz, 1H), 3.37 (ddd, J¼10.8, 6.2, and 2.3 Hz, 1H), 3.45
(ddd, J¼10.8, 6.0, and 2.3 Hz, 1H), 4.15 (br d, J¼8.2 Hz,
1H), 4.48 (br s, 1H), 4.75 (d, J¼8.2 Hz, 1H), 4.87 (m, 2H),
5.11 (s, 1H), 7.17 (d, J¼8.2 Hz, 1H), 7.25 (dd, J¼8.2 and
6.9 Hz, 1H), 7.30 (dd, J¼8.2 and 6.9 Hz, 1H), 7.32 (d,
J¼8.2 Hz, 1H), 7.36 (d, J¼9.6 Hz, 1H), 7.44 (dd with fine
coupling, J¼8.2 and 6.9 Hz, 1H), 7.90 (d, J¼8.2 Hz, 1H),
7.95 (s, 1H), 8.08–8.10 (m, 1H), 8.75–8.78 (m, 1H) ppm.
13C NMR (125 MHz, CDCl3): dC 20.0, 26.1, 26.8, 36.8,
45.7, 58.8, 62.5, 71.6, 71.7, 80.7, 105.9, 115.8, 117.5,
120.0, 124.8, 125.6, 125.8, 126.8, 127.2, 127.7, 127.9,
128.3, 128.7, 128.8, 130.7, 130.8, 131.4, 133.5, 134.6,
134.7, 151.1, 155.7 ppm. IR (KBr): ~n 3307, 2961, 1618,
1516, 1400, 1335, 1234, 1104, 1040, 1020 cmꢀ1. Mass
(m/z, %): 558 (M+, 68), 540 (15), 402 (18), 401 (71), 339
(14), 372 (14), 342 (19), 325 (33), 324 (31), 297 (16), 296
(17), 269 (19), 239 (31), 59 (100), 57 (58). HRMS (ESI):
581.2503, calcd for C34H38O7Na (M+Na+) 581.2515.
Anal. Calcd for C34H38O7: C, 73.10; H, 6.86. Found: C,
72.91; H, 6.70. Compound trans-2e: colorless granules
(1.0ꢂ10ꢀ5 mol cmꢀ3, 1 mL) was added by means of a
syringe with immediate starting of measurement. The inten-
sity of the light emission time-course was recorded and
processed according to first-order kinetics. The total light
emission was estimated by comparing it with that of an ada-
mantylidene dioxetane, whose chemiluminescent efficiency
FCTICL has been reported to be 0.29 and was used here
as a standard.12
[K3(18C6)]+t-BuOꢀ in PhH–THF (1:1) (system B):
t-BuOK (1.0 mol cmꢀ3 in THF, 2 mL, 2 mmol) was added
to a solution of 18-crown-6 ether (555 mg, 2.10 mmol) in
dry benzene (10 mL) and dry THF (8 mL) at room tempera-
ture under a nitrogen atmosphere and stirred for 10 min.
Chemiluminescence measurement using the solution of
18-crown–ether complex of t-BuOK in PhH–THF was
carried out similarly to the case of system A.
4.4. Isolation of keto esters 14 from the spent reaction
mixture after chemiluminescent decomposition
of dioxetanes 2: general procedure
A solution of the dioxetane 2 (20–30 mg) in DMSO (3 mL)
was added to a solution of TBAF (1 M in THF, 0.1 mL) in
DMSO (0.9 mL) at room temperature under nitrogen atmo-
sphere. After stirring for 1 h, the reaction mixture was
poured into satd aq NH4Cl and extracted with AcOEt. The
organic layer was washed with satd aq NaCl, dried over
MgSO4, and concentrated in vacuo. 1H NMR spectral anal-
ysis showed that the residue was comprised of keto ester 14
without detectable amount of other products. The residue
was purified by column chromatography on silica gel with
AcOEt–hexane to give the corresponding keto ester 14.
1
melted at 165.0–166.0 ꢁC (from THF–MeOH). H NMR
(500 MHz, CDCl3): dH 0.96 (s, 9H), 1.33 (s, 3H), 1.69 (s,
3H), 3.25 (ddd, J¼10.8, 5.8, and 2.3 Hz, 1H), 3.31 (s, 3H),
3.34 (ddd, J¼10.8, 6.4, and 2.3 Hz, 1H), 3.27 (ddd,
J¼10.8, 6.4, and 2.3 Hz, 1H), 3.48 (ddd, J¼10.8, 5.8, and
2.3 Hz, 1H), 4.13 (d, J¼8.5 Hz, 1H), 4.69 (br s, 1H), 4.75
(d, J¼8.5 Hz, 1H), 4.86 (s, 2H), 5.11 (s, 1H), 7.90 (d,
J¼8.7 Hz, 1H), 7.25–7.32 (m, 3H), 7.36 (d, J¼9.6 Hz,
1H), 7.43 (dd with fine coupling, J¼7.8 and 7.3 Hz, 1H),
7.90 (d, J¼7.8 Hz, 1H), 7.95 (s, 1H), 8.07–8.10 (m, 1H),
8.73–8.75 (m, 1H) ppm. 13C NMR (125 MHz, CDCl3): dC
20.0, 26.1, 26.8, 36.9, 45.7, 58.8, 62.5, 71.7, 71.8, 80.6,
106.0, 115.8, 117.5, 117.7, 119.9, 124.6, 125.4, 125.7,
126.8, 127.1, 127.7, 128.0, 128.3, 128.7, 130.8, 130.9,
131.5, 133.6, 134.7, 134.7, 151.1, 155.9 ppm. IR (KBr): ~n
3421, 2976, 1618, 1474, 1400, 1370, 1234, 1106,
1038 cmꢀ1. Mass (m/z, %): 558 (M+, 50), 402 (18), 401
(56), 339 (17), 372 (13), 342 (18), 325 (28), 324 (26), 298
(13), 297 (20), 296 (12), 269 (19), 252 (12), 239 (31), 141
(13), 59 (100). HRMS (ESI): 581.2511, calcd for
C34H38O7Na (M+Na+) 581.2515. Anal. Calcd for
C34H38O7+CH3OH (2.1% w/w): C, 72.35; H, 6.98. Found:
C, 72.02; H, 7.07.
4.4.1. 2,2,4,4-Tetramethyl-3-oxopentyl 2-hydroxy-1,10-
binaphthyl-5-carboxylate (14a). Colorless granules melted
at 174.0–174.5 ꢁC (from AcOEt–hexane). 1H NMR
(500 MHz, CDCl3): dH 1.29 (s, 9H), 1.43 (s, 6H), 4.50 (s,
2H), 5.06 (br s, 1H), 7.19–7.22 (m, 1H), 7.25–7.35 (m,
3H), 7.43 (d, J¼9.6 Hz, 1H), 7.49–7.52 (m, 2H), 7.61–
7.65 (m, 1H), 7.89 (d with fine coupling, J¼6.9 Hz, 1H),
7.95 (d, J¼8.2 Hz, 1H), 8.01 (d, J¼8.2 Hz, 1H), 8.95 (d,
J¼9.6 Hz, 1H) ppm. 13C NMR (125 MHz, CDCl3): dC
23.7, 28.2, 45.9, 49.2, 72.3, 119.0, 119.1, 125.2, 125.6,
126.0, 126.6, 126.7, 126.9, 127.2, 127.3, 127.7, 128.5,
129.4, 129.6, 130.1, 131.2, 132.8, 134.1, 134.5, 151.1,
167.5, 216.1 ppm. IR (KBr): ~n 3411, 2974, 1719, 1685,
1668, 1512, 1366, 1262, 1136 cmꢀ1. Mass (m/z, %): 454
(M+, 56), 399 (10), 398 (33), 314 (39), 298 (33), 297
(100), 269 (27), 268 (16), 252 (13), 251 (14), 250 (18),
239 (29), 57 (39). HRMS (ESI): 509.2292, calcd for
C31H34O5Na (M+Na++MeOH) 509.2304. Anal. Calcd for
C30H30O4: C, 79.27; H, 6.65. Found: C, 78.86; H, 6.59.
4.3. Chemiluminescence measurement: general
procedure
Chemiluminescence were measured using a Hamamatsu
Photonics PMA-11 multi-channel detector and/or JASCO
FP-750 spectrometer.
4.4.2. 2,2,4,4-Tetramethyl-3-oxopentyl 2-hydroxy-20-
methoxy-30-methoxycarbonyl-1,10-binaphthyl-5-carbox-
ylate (14b). Colorless granules melted at 149.0–149.5 ꢁC
1
(from AcOEt–hexane). H NMR (500 MHz, CDCl3): dH
TBAF in DMSO (system A): freshly prepared solution
(2 mL) of TBAF (1.0ꢂ10ꢀ2 mol cmꢀ3) in DMSO was trans-
ferred to a quartz cell (10ꢂ10ꢂ50 mm) and the latter placed
in the spectrometer, which was thermostated with stirring at
25 ꢁC. After 3–5 min, a solution of the dioxetane in DMSO
1.30 (s, 9H), 1.44 (s, 6H), 3.46 (s, 3H), 3.96 (s, 3H), 4.50
(qAB, J¼11.0 Hz, 2H), 5.31 (br s, 1H), 7.15 (d, J¼8.7 Hz,
1H), 7.21–7.26 (m, 2H), 7.36 (dd with fine coupling,
J¼7.8 and 7.7 Hz, 1H), 7.47 (d, J¼9.2 Hz, 1H), 7.48 (dd,
J¼7.7 and 6.9 Hz, 1H), 7.90 (d with fine coupling,

N. Hoshiya et al. / Tetrahedron 62 (2006) 12424–12437
12435
J¼6.9 Hz, 1H), 7.97 (d, J¼7.8 Hz, 1H), 8.55 (s, 1H), 8.78 (d,
J¼9.2 Hz, 1H) ppm. 13C NMR (125 MHz, CDCl3): dC 23.7,
23.8, 28.2, 45.9, 49.2, 52.5, 62.0, 72.3, 114.9, 119.5, 123.8,
125.2, 125.2, 125.5, 126.2, 126.9, 127.5, 127.5, 128.2, 129.1,
129.3, 129.8, 130.0, 134.2, 134.3, 135.5, 151.6, 155.2, 166.6,
167.4, 216.1 ppm. IR (KBr): ~n 3431, 2955, 1716, 1687,
1620, 1446, 1365, 1308, 1251, 1136, 1061 cmꢀ1. Mass
(m/z, %): 542 (M+, 63), 486 (11), 454 (10), 386 (28), 385
(100), 370 (19), 326 (16), 294 (12), 266 (16), 57 (31).
HRMS (ESI): 565.2186, calcd for C33H34O7Na (M+Na+)
565.2202. Anal. Calcd for C33H34O7: C, 73.04; H, 6.32.
Found: C, 72.97; H, 6.30.
(500 MHz, CDCl3): dH 1.30 (s, 9H), 1.44 (s, 3H), 1.45 (s,
3H), 3.23–3.28 (m, 1H), 3.25–3.26 (m, 3H), 3.33 (ddd,
J¼11.0, 6.0, and 2.3 Hz, 1H), 4.43 (ddd, J¼11.0, 6.0, and
1.8 Hz, 1H), 3.51 (ddd, J¼11.0, 6.4, and 2.3 Hz, 1H), 4.50
(s, 2H), 4.64 (dd, J¼7.3 and 6.9 Hz, 1H), 4.79 (dd with
fine coupling, J¼12.4 and 7.3 Hz, 1H), 4.84 (dd, J¼12.4
and 6.9 Hz, 1H), 5.7 (br s, 1H), 7.11 (d, J¼8.2 Hz, 1H),
7.22–7.27 (m, 2H), 7.32 (d, J¼8.7 Hz, 1H), 7.39–7.46 (m,
1H), 7.45 (d, J¼9.6 Hz, 1H), 7.89 (d, J¼8.2 Hz, 1H),
7.89–7.90 (m, 1H), 7.91 (s, 1H), 8.97 (d, J¼9.6 Hz,
1H) ppm. 13C NMR (125 MHz, CDCl3): dC 23.7, 23.8,
28.2, 45.9, 49.2, 58.7, 62.4, 71.8, 71.8, 72.3, 115.5, 119.4,
119.9, 124.7, 125.4, 125.6, 126.9, 127.1, 127.4, 127.5,
128.2, 128.3, 130.1, 130.7, 130.8, 133.6, 134.3, 134.5,
151.8, 155.9, 167.5, 216.1 ppm. IR (KBr): ~n 3422, 2958,
2874, 1716, 1685, 1514, 1475, 1254, 1198, 1254, 1143,
1107, 1047 cmꢀ1. Mass (m/z, %): 558 (M+, 61), 540
(12), 402 (19), 401 (61), 372 (12), 343 (10), 342 (15), 326
(13), 325 (29), 324 (27), 297 (10), 296 (11), 269 (11),
268 (11), 239 (18), 59 (100), 57 (45). HRMS (ESI):
581.2480, calcd for C34H38O7Na (M+Na+) 581.2515.
Anal. Calcd for C34H38O7: C, 73.10; H, 6.86. Found: C,
73.17; H, 6.63.
4.4.3. 2,2,4,4-Tetramethyl-3-oxopentyl 30-carboxy-2-hy-
droxy-20-methoxy-1,10-binaphthyl-5-carboxylate (14c).
Colorless amorphous solid. H NMR (400 MHz, CDCl3):
1
dH 1.30 (s, 9H), 1.45 (s, 6H), 3.50 (s, 3H), 4.51 (s, 2H),
5.32 (br s, 1H), 7.22 (d, J¼8.5 Hz, 1H), 7.25–7.31 (m,
2H), 7.45 (dd, J¼8.1 and 6.8 Hz, 1H), 7.47 (d, J¼9.5 Hz,
1H), 7.56 (dd, J¼8.1 and 6.8 Hz, 1H), 7.93 (d with fine cou-
pling, J¼6.8 Hz, 1H), 8.05 (d, J¼8.1 Hz, 1H), 8.93 (s, 1H),
9.04 (d, J¼9.5 Hz, 1H), 11.2 (br s, 1H) ppm. 13C NMR
(100 MHz, CDCl3): dC 23.7, 23.7, 28.2, 45.9, 49.2, 62.5,
72.5, 113.8, 119.5, 121.0, 122.8, 125.2, 126.0, 126.9,
127.0, 127.7, 127.8, 129.0, 129.4, 130.1, 130.2, 130.5,
134.0, 136.2, 136.7, 151.7, 154.2, 165.6, 167.3,
216.1 ppm. IR (KBr): ~n 3422, 3293, 2983, 1711, 1686,
1624, 1516, 1458, 1366, 1259, 1219, 1105 cmꢀ1. Mass
(m/z, %): 528 (M+, 39), 500 (25), 472 (17), 444 (14), 385
(79), 372 (25), 371 (100), 370 (25), 360 (17), 356 (14),
344 (23), 343 (47), 327 (29), 326 (32), 294 (20), 267 (20),
266 (34), 255 (26), 239 (22), 226 (34), 57 (82). HRMS
(ESI): 551.2037, calcd for C32H32O7Na (M+Na+)
551.2046. Anal. Calcd for C32H32O7: C, 72.71; H, 6.10.
Found: C, 72.39; H, 6.29.
4.5. Fluorescence measurement: general procedure
Freshly prepared solution of 2.05–2.10ꢂ10ꢀ5 mol dmꢀ3 of
14a–14e and of 1.0ꢂ10ꢀ2 mol dmꢀ3 of TBAF in DMSO
was transferred to a quartz cell (10ꢂ10ꢂ50 mm) and the lat-
ter placed in the spectrometer, which was thermostated with
stirring at 25 ꢁC. Thus, the fluorescence spectra of 14a–14e
were measured by means of JASCO FP-750. The fluores-
cence of 14a–14e in 18-crown- ether complex of t-BuOK
in PhH–THF system was measured similarly to the case of
TBAF in DMSO.
4.4.4. 2,2,4,4-Tetramethyl-3-oxopentyl 6-hydroxy-5-(2,2-
dimethyl-1,3-dioxa-1,2,3,4-tetrahydroanthracen-9-yl)-
naphthalene-1-carboxylate (14d). Pale yellow amorphous
4.6. X-ray single crystallographic analysis of dioxetanes
X-ray diffraction data were collected on a Rigaku Mercury
CCD diffractometer with graphite monochromated Mo Ka
1
solid. H NMR (500 MHz, CDCl3): dH 1.30 (s, 9H), 1.37
˚
(s, 3H), 1.42 (s, 3H), 1.44 (s, 6H), 4.50 (qAB, J¼10.5 Hz,
2H), 5.05–5.06 (m, 1H), 5.12 (qAB, J¼15.3 Hz, 2H), 7.09
(d, J¼8.5 Hz, 1H), 7.19 (dd, J¼8.5 and 7.0 Hz, 1H), 7.21
(d with fine coupling, J¼7.9 Hz, 1H), 7.26 (dd, J¼8.2 and
7.0 Hz, 1H), 7.33 (dd, J¼7.9 and 7.1 Hz, 1H), 7.44 (d,
J¼9.4 Hz, 1H), 7.65 (s, 1H), 7.79 (d, J¼8.2 Hz, 1H), 7.88
(d with fine coupling, J¼7.1 Hz, 1H), 8.94 (d, J¼9.4 Hz,
1H) ppm. 13C NMR (125 MHz, CDCl3): dC 23.7, 23.7,
24.4, 25.1, 28.2, 45.9, 49.2, 61.1, 72.2, 100.4, 114.4,
114.7, 119.1, 121.3, 124.4, 124.5, 124.9, 125.0, 126.8,
127.0, 127.2, 127.3, 127.5, 127.8, 128.6, 130.0, 133.2,
134.4, 148.8, 151.5, 167.6, 216.0 ppm. IR (KBr): ~n 3448,
2983, 2865, 1715, 1685, 1612, 1438, 1259, 1178, 1138,
1115 cmꢀ1. Mass (m/z, %): 540 (M+, 20), 483 (34), 482
(88), 426 (21), 383 (12), 343 (20), 326 (26), 325 (100),
324 (33), 297 (14), 269 (12), 239 (13), 57 (15). HRMS
(ESI): 563.2379, calcd for C34H36O6Na (M+Na+)
563.2409. Anal. Calcd for C34H36O6: C, 75.53; H, 6.71.
Found: C, 75.21; H, 6.64.
(l¼0.71070 A) radiation. Data were processed using
CrystalClear.y The structure was solved by direct method
(SHELX97)z and expanded using Fourier techniques. The
non-hydrogen atoms were refined anisotropically. Hydrogen
atoms were refined using the riding model. The final cycle of
full-matrix least-squares refinement on F2 was based on 6532
observed reflections and 390 variable parameters (for 2a),
on 6312 observed reflections and 395 variable parameters
(for 2b), on 7001 observed reflections and 446 variable
parameters (for 2c), on 13,200 observed reflections and
846 variable parameters (for 2d), and on 7345 observed
reflections and 461 variable parameters (for 2e). All calcula-
tions were performed using the CrystalStructure crystallo-
graphic software package.x,{
y
z
x
Rigaku Corporation, 1999.
Sheldrick, G. M. University of Gottingen, Gottingen, Germany, 1997.
CrystalStructure 3.6.0: Crystal Structure Analysis Package, Rigaku and
Rigaku/MSC(2000–2003). 9009 New Trails Dr. The Woodlands, TX
77381, USA.
CRYSTALS Issue 10: Watkin, D. J.; Prout, C. K.; Carruthers, J. R.; Bet-
4.4.5. 2,2,4,4-Tetramethyl-3-oxopentyl 2-hydroxy-30-hy-
droxymethyl-20-(2-methoxyethoxy)-1,10-binaphthyl-5-
carboxylate (14e). Colorless amorphous solid. H NMR
{
1
teridge, P. W. Chemical Crystallography Laboratory, Oxford, UK, 1996.

12436
N. Hoshiya et al. / Tetrahedron 62 (2006) 12424–12437
Crystal data for compound cis-2a: C30H30O4$C4H8O
(Mr¼526.67), colorless platelet (recrystallized from THF),
0.30ꢂ0.20ꢂ0.08 mm, orthorhombic, space group Pccn
F(000)¼676.00, reflections collected/unique 17,692/7345
(Rint¼0.038), m(Mo Ka)¼0.86 cmꢀ1. An empirical absorp-
tion correction was applied, which resulted in trans-
mission factors ranging from 0.8324 to 1.0000. The data
were corrected for Lorentz and polarization effects. Final
R indices R1¼0.067 [I>2s(I)], wR2¼0.173 (all data),
GOF on F2¼1.013, and residual electron density 0.51/
˚
˚
˚
(#56), a¼23.64(3) A, b¼22.72(1) A, c¼10.635(8) A,
3
V¼5712.5(89) A , Z¼8, rcalcd¼1.225 g cmꢀ3, T¼150 K,
˚
2qmax¼55.0ꢁ, F(000)¼2256.00, reflections collected/unique
58,346/6532 (Rint¼0.083), m(Mo Ka)¼0.81 cmꢀ1. An em-
pirical absorption correction was applied, which resulted
in transmission factors ranging from 0.8818 to 1.0000. The
data were corrected for Lorentz and polarization effects. Fi-
nal R indices R1¼0.093 [I>2s(I)], wR2¼0.208 (all data),
GOF on F2¼0.768, and residual electron density 0.35/
ꢀ3
˚
ꢀ0.46 eA
.
Crystallographic data for the structural analysis of com-
pounds cis-2a, cis-2b, cis-2c, trans-2d, and cis-2e have
been deposited at the Cambridge Crystallographic Data
Center, CCDC-617817 (for cis-2a), ꢀ617818 (for cis-2b),
ꢀ620734 (for cis-2c), ꢀ617819 (for trans-2d), and
ꢀ617820 (for cis-2e). These data can be obtained free of
charge via www.ccdc.cam.ac.uk/conts/retrieving.html (or
from the Cambridge Crystallographic Data Center, 12 Union
Road, Cambridge CB21EZ, UK; fax: +44 1223 336 033 or
deposit@ccdc.cam.au.uk).
ꢀ3
˚
ꢀ0.32 eA
.
Crystal data for compound cis-2b: C33H34O7 (Mr¼542.63),
colorless platelet (recrystallized from dioxane), 0.30ꢂ
0.20ꢂ0.15 mm, monoclinic, space group C2/c (#15), a¼
ꢁ
˚
˚
˚
29.96(2) A, b¼12.904(6) A, c¼14.57(2) A, b¼96.138(8) ,
V¼5601.5(76) A , Z¼8, rcalcd¼1.287 g cmꢀ3, T¼150 K,
3
˚
2qmax¼55.0ꢁ, F(000)¼2304.00, reflections collected/unique
29,440/6312 (Rint¼0.038), m(Mo Ka)¼0.90 cmꢀ1. An
empirical absorption correction was applied, which resulted
in transmission factors ranging from 0.8452 to 1.0000. The
data were corrected for Lorentz and polarization effects.
Final R indices R1¼0.063 [I>2s(I)], wR2¼0.196 (all
data), GOF on F2¼1.002, and residual electron density
Acknowledgements
The authors gratefully acknowledge financial assistance
provided by a Grant-in aid (No. 13640546 and No.
14540506) for Scientific Research by the Ministry of Educa-
tion, Culture, Sports, Science, and Technology, Japan.
ꢀ3
˚
0.40/ꢀ0.39 eA
.
Crystal data for compound cis-2c: C32H32O7$C4H8O2
(Mr¼616.71), colorless prism (recrystallized from dioxane),
0.20ꢂ0.10ꢂ0.10 mm, triclinic, space group P-1 (#2),
References and notes
ꢁ
˚
˚
˚
a¼8.12(2) A, b¼13.40(2) A, c¼15.06(2) A, a¼89.43(9) ,
1. Canonica, S.; Wild, U. P. J. Phys. Chem. 1991, 95, 6535–6540
and references therein.
3
ꢁ
ꢁ
˚
b¼77.95(8) , g¼82.12(8) , V¼1587.1(46) A , Z¼2, rcalcd
¼
1.290 g cmꢀ3, T¼120 K, 2qmax¼55.0ꢁ, F(000)¼656.00,
reflections collected/unique 16,809/7001 (Rint¼0.046),
m(Mo Ka)¼0.92 cmꢀ1. An empirical absorption correction
was applied, which resulted in transmission factors ranging
from 0.8462 to 1.0000. The data were corrected for Lorentz
and polarization effects. Final R indices R1¼0.059
2. Beck, S.; Koster, H. Anal. Chem. 1990, 62, 2258–2270.
€
€
3. Adam, W.; Reihardt, D.; Saha-Moller, C. R. Analyst 1996, 121,
1527–1531.
4. Matsumoto, M. J. Photochem. Photobiol. C: Photochem. Rev.
2004, 5, 27–53.
5. Matsumoto, M.; Watanabe, N. Bull. Chem. Soc. Jpn. 2005, 78,
1899–1920.
6. CTICL of optically active dioxetanes bearing a 1-(1,3-dioxa-
1,2,3,4-tetrahydroanthracen-9-yl)-2-hydroxynaphthalen-5-yl
moiety has very recently reported by us as a preliminary com-
munication.7
7. Matsumoto, M.; Hamaoka, K.; Takashima, Y.; Yokokawa, M.;
Yamada, K.; Watanabe, N.; Ijuin, H. K. Chem. Commun. 2005,
808–810.
8. Hoshiya, N.; Fukuda, N.; Watanabe, N.; Matsumoto, M.
Tetrahedron 2006, 62, 5808–5820.
9. Hoshiya, N.; Fukuda, N.; Watanabe, N.; Matsumoto, M. ITE
Lett. 2006, 7, 50–53.
10. Encyclopedia of Reagents for Organic Synthesis; Paquette,
L. A., Ed.; Wiley: New York, NY, 1995; Vol. 7, pp 4788–4796.
11. Dihydrofuran 3e could be prepared also by the use of dihydro-
furan 8, not through dihydrofuran 11, though 11 was a key
intermediate for new CTICL-active dioxetanes, which will be
reported elsewhere in near future.
[I>2s(I)], wR2¼0.151 (all data), GOFꢀo3n F2¼1.003, and
˚
residual electron density 0.62/ꢀ0.70 eA
.
Crystal data for compound trans-2d: C34H36O6$0.5(C4H8O)
(Mr¼576.71), colorless prism (recrystallized from THF),
0.30ꢂ0.25ꢂ0.10 mm, triclinic, space group P-1 (#2), a¼
ꢁ
˚
˚
˚
10.930(11) A, b¼16.31(2) A, c¼18.60(3) A, a¼107.22(3) ,
3
b¼98.74(3)ꢁ, g¼102.62(3)ꢁ, V¼3004.5(66) A , Z¼4,
˚
rcalcd¼1.275 g cmꢀ3, T¼150 K, 2qmax¼55.0ꢁ, F(000)¼
1232.00, reflections collected/unique 31,765/13,200
(Rint¼0.039), m(Mo Ka)¼0.86 cmꢀ1. An empirical absorp-
tion correction was applied, which resulted in transmission
factors ranging from 0.8740 to 1.0000. The data were
corrected for Lorentz and polarization effects. Final R
indices R1¼0.065 [I>2s(I)], wR2¼0.162 (all data), GOF
on F2¼1.017, and residual electron density 0.38/
ꢀ3
˚
ꢀ0.30 eA
.
Crystal data for compound cis-2e: C34H38O7$C4H8O
(Mr¼630.78), colorless prism (recrystallized from THF),
0.20ꢂ0.10ꢂ0.10 mm, triclinic, space group P-1 (#2),
12. Trofimov, A. V.; Mielke, K.; Vasl’ev, R. F.; Adam, W.
Photochem. Photobiol. 1996, 63, 463–467.
13. According to several reports of X-ray single crystallographic
analysis of [K3(crown ether)]+ArOꢀ, ArOꢀ coordinates
with distance of ca. 270 pm between the oxido anion and
central potassium ion. Therefore, upper-Nap could lie in
˚
˚
˚
a¼10.193(5) A, b¼11.647(12) A, c¼14.59(2) A, a¼
3
ꢁ
ꢁ
ꢁ
˚
88.59(8) , b¼77.07(7) , g¼85.02(8) , V¼1681.9(31) A ,
Z¼2, rcalcd¼1.245 g cmꢀ3
,
T¼150 K, 2qmax¼55.0ꢁ,

N. Hoshiya et al. / Tetrahedron 62 (2006) 12424–12437
12437
a conformation where it collides with the face of crown ether
complex.14–16
14. Caswell, L. R.; Hardcastle, J. E.; Jorda, T. A.; Alam, I.;
McDowell, K. A.; Mahan, F.; Fronczek, R.; Gandour, R. D.
J. Inclusion Phenom. Macrocyclic Chem. 1992, 13, 37–45.
15. Fronczek, F. R.; Gandour, R. D.; Gehrig, L. B.; Caswell, L. R.;
McDowell, K. A. J. Inclusion Phenom. Macrocyclic Chem.
1987, 5, 379–383.
16. Barnes, J. C.; Collard, J. Acta Crystallogr., Sect. C: Cryst.
Struct. Commun. 1988, 44, 565–566.