Enantioselective C-C Bond Formation during the Oxidation of 5-Phenylpent-2-enyl Carboxylates with Hypervalent Iodine(III)

Article abstract of DOI:10.1021/acs.joc.7b01141

The oxidation of (5-acyloxypent-3-enyl)benzene with hypervalent iodine(III) afforded 2-oxy-1-(oxymethyl)tetrahydronaphthalene under metal-free conditions. The acyloxy group may nucleophilically participate in the oxidative cyclization. A lactate-based chi

Full text of DOI:10.1021/acs.joc.7b01141

Note
Enantioselective C-C Bond Formation during the Oxidation of
5-Phenylpent-2-enyl Carboxylates with Hypervalent Iodine(III)
Mio Shimogaki, Morifumi Fujita, and Takashi Sugimura
J. Org. Chem., Just Accepted Manuscript • Publication Date (Web): 29 May 2017
Downloaded from http://pubs.acs.org on May 30, 2017
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Enantioselective
C–C Bond Formation during the Oxidation of
5-Phenylpent-2-enyl Carboxylates with Hypervalent Iodine(III)
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Mio Shimogaki, Morifumi Fujita,* Takashi Sugimura
Graduate School of Material Science, University of Hyogo, Kohto, Kamigori, Hyogo
678-1297, Japan
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X
O
R
O
R
OCOR
OCOR
Ar
I
O
X
O
Participation of Acyloxy
C-C Bond Formation
cis-Selective
Abstract: The oxidation of (5ꢀacyloxypentꢀ3ꢀenyl)benzene with hypervalent iodine(III)
afforded 2ꢀoxyꢀ1ꢀ(oxymethyl)tetrahydronaphthalene under metalꢀfree conditions. The
acyloxy group may nucleophilically participate in the oxidative cyclization. A
lactateꢀbased chiral hypervalent iodine afforded an enantioselective variant of
oxyarylation with up to 89% ee.
Oxidative 1,2ꢀdifunctionalization of alkenes with hypervalent iodine reagents offers a
powerful strategy for constructing useful molecular complexity, because a wide range of
functional groups, such as halogen, oxygen, nitrogen, and sulfur nucleophiles, is
incorporated into the C=C of alkene substrates.1–4 In particular, highly enantioselective
oxidation was achieved in several types of vicinal difunctionalization reactions using
lactateꢀbased chiral hypervalent iodine reagents.4,5 There are few examples of the
addition of a carbon nucleophile compared to many examples of the addition of a
heteroatom nucleophile. Transitionꢀmetal catalysts facilitate carbonꢀcarbon bond
formation during the oxidation of alkenes with hypervalent iodine.6,7 However,
metalꢀfree reactions are limited to achiral or racemic transformation using electronꢀrich
arylꢀsubstituted substrates.8 Under these circumstances, we recently found that
enantioselective C–C bond formation was achieved by using 6ꢀarylꢀ1ꢀsilyloxyhexꢀ3ꢀene
substrates and lactateꢀbased chiral hypervalent iodine reagents.9
In this study, we employed neighboring group participation of an acyloxy group for
oxidative arylation. Reactions involving neighboring group participation are
advantageous in terms of powerful stereocontrol and unique stereoselectivity.10 This
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participation usually accelerates the formation of the product. Herein, we demonstrate
oxidative C–C formation promoted by neighboring group participation of an acyloxy
8
9
group.
This
reaction
stereoselectively
provides
the
tetrahydroꢀ2ꢀhydroxyꢀ1ꢀ(hydroxymethyl)naphthalene structure, which is found in
serrulatane diterpenes (Figure 1).11
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OH
OH
X
OH
X = H, OH
H
H
Figure 1. Serrulatane diterpenes.
Reactions of 5ꢀphenylpentꢀ2ꢀenyl carboxylate 1 with (diacetoxyiodo)benzene are
summarized in Table 1. Boron trifluoride diethyl etherate (BF3·OEt2) has been widely
used as an activator for oxidation with hypervalent iodine reagents.12 Thus, the reaction
of 5ꢀphenylpentꢀ2ꢀenyl acetate (1a) with (diacetoxyiodo)benzene was examined in the
presence of BF3·OEt2 at −80 °C for 10 h. However, the reaction did not proceed and
substrate 1a was recovered. In addition to BF3·OEt2, triflic acid or acetic acid was
employed, and the reaction temperature was elevated from −80 °C to 0 °C (entries 1 and
2). Pleasingly, the substrate was consumed under the reaction conditions and a
regioisomeric mixture of the acetoxyhydroxy products 2a and 2a' was obtained. The
structures of 2a and 2a' were confirmed by the fact that acetylation of the mixture led to
single diacetoxy compound 3a. The oxidation led to carbonꢀcarbon bond formation as a
result of oxidative arylation of the alkene. When HF·pyridine was used as a coactivator
together with BF3·OEt2, the oxidative arylation of 1a proceeded even at −80 °C within 1
h (entries 3 and 4). The lower yield of isolated 2a + 2a' (entry 3) compared to that of 3a
(entry 4) might be due to some loss of the hydroxy products, 2a and 2a', during
purification through column chromatography. The oxidation of benzoate substrate 1b at
−80 °C for 1 h followed by benzoylation also yielded oxidative arylation product 3b in
61% yield (entry 5). In the absence of HF·pyridine, the reaction of 1b required warming
to −40 °C and a longer reaction time (11 h), which resulted in a low 26% yield (entry 6).
The oxidative arylation of pivalate substrate 1c yielded a mixture of 2c and 2c' with a
9:1 ratio (entry 7). Another run of the oxidation of 1c followed by pivalation yielded 3c
in 59% yield.
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Table 1. Oxidative Arylation of 1 with (Diacetoxyiodo)benzenea
8
9
OH
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OCOR
O
R
OCOR
OCOR
(RCO)2O
or RCOCl
PhI(OAc)2
2
+
O
BF3—OEt2
HX
OCOR
OH
CH2Cl2
1
a: R = Me
b: R = Ph
3
80 ºC
c: R = t-Bu
2'
entry
1 (R)
HX
2 / 2'
yield (%)
1a (Me)
1a (Me)
1a (Me)
1a (Me)
1b (Ph)
1b (Ph)
1c (t-Bu)
TfOHb,c
AcOHc,e
HF—pyf
HF—pyf
HF—pyf
ꢀ g
1
2
3
4
5
6
7
7:3
6:4
7:3
nd
36 (3a)d
70 (3a)d
56 (2a+2a')
67 (3a)d
6:4
5:5
9:1
61 (3b)d
26 (3b)d
HF—pyf
78 (2c+2c')
a 1 (0.20 mmol), PhI(OAc)2 (0.24 mmol), and BF3·OEt2 (0.80 mmol) in CH2Cl2 (8 mL)
at −80 °C, unless otherwise noted. b TfOH (0.57 mmol) was added. c Reaction
temperature was elevated from −80 °C to 0 °C. d The crude reaction mixture was
acylated. e AcOH (1.75 mmol) was added. f HF·py (50 ꢁL) was added. g Reaction
temperature was elevated from −80 °C to −40 °C.
To determine the cis/trans configuration of 3, we initially focused on the coupling
1
constant between the 1ꢀH and 2ꢀH (J1,2) in the H NMR spectrum. A relatively small
coupling constant (J1,2 = 4.8 Hz) was observed for acetate 3a. In the cases of benzoate
3b and pivalate 3c, the coupling constant J1,2 was 5.5 Hz. Such moderate coupling
constant is compatible with cisꢀ and transꢀconfigurations. Even in the transꢀisomer, the
2ꢀsubstituent located in a pseudoaxial position would reduce the coupling constant. In
fact, 6 Hz for J1,2 was reported for a trans derivative,11a which was isolated as a
serrulatane diterpene.11 The trans configuration of the natural product was confirmed by
single crystal Xꢀray crystallography.11b Accordingly, we undertook stereochemical
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determination of 3 by Xꢀray crystallographic analysis. Fortunately, a single crystal of 3b
was obtained and successfully subjected to Xꢀray crystallographic analysis,13 which
disclosed the cisꢀconfiguration of 3b.
9
On the basis of the reaction conditions summarized in Table 1, an enantioselective
variant of the oxidative arylation of 1 was examined using lactateꢀbased chiral
hypervalent iodine reagents 4a and 4b (Table 2). Immediate progress at a low reaction
temperature (−80 °C) is one of the attractive aspects of this reaction, and thus
HF·pyridine was used as a coactivator together with the BF3·OEt2 activator (entries 1
and 2). Bulky mentyl reagent 4b led to a slight increase in enantioselectivity (74% ee;
entry 2) in comparison with simple reagent 4a (69% ee; entry 1). Aiming at a further
increase in the enantioselectivity, we found that trimethylsilyl triflate functioned as a
suitable coactivator leading to high enantioselectivity (85% ee; entry 3). The
enantioselectivity further increased in the oxidative arylation of pivalate substrate 1c
(89% ee; entry 4).
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Table 2. Enantioselectivity in Oxyarylation of 1a
O
R
Ar*I(OAc)2
4
OCOR
OCOR
HF—py or
TMSOTf
(RCO)2O
or RCOCl
BF3—OEt2
O
80 ºC
CH2Cl2
3
1
OMe
O
O
O
I(OAc)2
O
I(OAc)2
O
4a
4b
3
ee (%)
69
entry
yield (%)
59
1 (R)
4
1a (Me)
1
2
3b
4b
4a
1a (Me)
1a (Me)
1c (t-Bu)
4b
4b
4b
55
59
37
74
85
89
a 1 (0.20 mmol), 4 (0.40 mol), HF·py (50 ꢁL), and BF3·OEt2 (0.80 mmol) in CH2Cl2 (8
b
mL) at −80 °C for 3–6 h, then acylation. TMSOTf (0.80 mmol) was used instead of
HF·py.
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To obtain an insight into the mechanistic role of the acyloxy group of 1, reactions of
acyloxyꢀdeficient substrates were examined. At first, (E)ꢀ5ꢀphenylpentꢀ2ꢀenꢀ1ꢀol and
(E)ꢀ5ꢀphenylpentꢀ2ꢀenyl methyl ether were subjected to the oxidation under the same
conditions using (diacetoxyiodo)benzene in the presence of HF·pyridine and BF3·OEt2
at −80 °C. In these reactions, most of the substrate was recovered and the formation of
complex mixtures was observed. Therefore, the presence of carboxylate may be
important for the oxidative arylation. We then examined the use of a trifluoroacetate
substrate. The electronꢀdeficient acyloxy group resulted in recovery of the substrate.
These results indicate the importance of nucleophilic participation of the acyloxy group
with respect to the promotion of oxidative arylation.
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Scheme 1. Plausible Reaction Mechanism
O
R
Y
O
R
O
R
O
Ar
O
Ar
O
I
I
Ar
Ph
I
X
Ph
X
Ph
X
5
6
6'
X,Y = F, OTf, OAc
acid
1 + ArI(OAc)2
Y
O
R
O
R
O
O
H2O
OH
O
R
O
2 + 2'
A plausible reaction mechanism based on the above mentioned results is illustrated in
Scheme 1. The oxidative arylation may be initiated by electrophilic attack of the
activated hypervalent iodine reagent to the olefin substrate 1 to generate reactive species
5. The lactateꢀbased chiral hypervalent iodine reagent differentiates between the
enantiotopic faces of the olefin. The enantioselectivity in the oxidative arylation of 1 is
similar to that in the usual 1,2ꢀdifunctionalization of alkenes reported previously.4 This
is consistent with a reaction mechanism initiated by electrophilic attack of the iodine
reagent to the olefin. Nucleophilic participation of the acyloxy group may trap reactive
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species 5 to yield 1,3ꢀdioxanꢀ2ꢀyl cation intermediate 6, which may be reversibly
trapped at the 2ꢀposition by a nucleophile, such as fluoride, triflate, or acetate,
depending on the reaction conditions. The iodonio group of 6/6' may be
nucleophilically substituted by the phenyl group. The cisꢀconfiguration of oxidative
arylation product 3 is rationalized by syn addition of the acyloxy group and the aryl
group to the olefin as shown in the mechanism. Quenching the reaction with water
results in the formation of the hemiorthoester, which is finally converted to a mixture of
2 and 2'.
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In summary, we have developed the enantioselective oxidative arylation of alkenes
promoted by participation of the acyloxy group under metalꢀfree conditions. This
reaction
stereoselectively
provides
the
tetrahydroꢀ2ꢀhydroxyꢀ1ꢀ(hydroxymethyl)naphthalene structure, which is found in
serrulatane diterpenes.
Experimental Section
General. Proton and 13C{1H}NMR spectra were measured on a JEOL ECAꢀ600
spectrometer as solutions in CDCl3. Proton NMR spectra were recorded using the
13
residual CHCl3 as an internal reference (7.24 ppm) and C{1H}NMR using CDCl3 as
an internal reference (77.00 ppm). For mass spectra measurements was used JEOL
JMSꢀT100LC and ThermoFisher Exactive. Optical rotations were measured on a
PerkinꢀElmer 241 polarimeter. Gas chromatography was performed on Shimadzu
GCꢀ17A. Reaction temperature was controlled using EYELA, PSLꢀ1800 and PSLꢀ1810
low temperature baths with magnetic stirrer.
Material. Unless otherwise noted, the reagents were commercially available and were
used without further purification. Dichloromethane was purified by distillation over
calcium hydride. Boron trifluoride diethyl etherate was purified by distillation over
Ca(OH)2. Column chromatography was performed on silica gel 60 (0.063ꢀ0.200 mm)
from Merck. Hypervalent iodine reagents, 4a4a and 4b9 were prepared as reported
previously.
(E)ꢀ5ꢀPhenylpentꢀ2ꢀenyl acetate (1a).15 The substrates 1a-c were prepared from
3ꢀphenylpropionaldehyde. The aldehyde (4 mL, 30 mmol) was reacted with triethyl
phosphonoacetate in the presence of nꢀbutyl lithium to yield ethyl
5ꢀphenylpentꢀ2ꢀenoate (4.7 g, 23 mmol, 77% yield). Reduction of the 5ꢀphenylꢀ2ꢀenoate
(4.7 g, 23 mmol) with DIBALꢀH at 0 °C gave (E)ꢀphenylpentꢀ2ꢀenꢀ1ꢀol (3.51 g, 21.6
mmol, 94% yield). Acetylation of the alcohol (500 mg, 3.1 mmol) with acetic anhydride
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gave 1a (561 mg, 2.75 mmol, 89% yield); oil; 1H NMR (600 MHz, CDCl3) δ 7.26 (t, J =
7.6 Hz, 2H), 7.17 (t, J = 7.6 Hz, 1H), 7.15 (d, J = 7.6 Hz, 2H), 5.80 (dt, J = 15.8, 6.9 Hz,
1H), 5.58 (dt, J = 15.8, 6.9 Hz, 1H), 4.49 (d, J = 6.9 Hz, 2H), 2.69 (t, J = 6.9 Hz, 2H),
2.36 (q, J = 6.9 Hz, 2H), 2.04 (s, 3H); 13C{1H}NMR (150 MHz, CDCl3) δ 170.9, 141.5,
135.4, 128.4, 128.3, 125.9, 124.4, 65.1, 35.3, 34.0, 21.0; IR (neat) 2934, 1740, 1230
cm−1.
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(E)ꢀ5ꢀPhenylpentꢀ2ꢀenyl benzoate (1b). (E)ꢀPhenylpentꢀ2ꢀenꢀ1ꢀol was prepared by
reduction of (E)ꢀethylꢀ5ꢀphenylpentꢀ2ꢀenoate in the same way as 1a. Benzoylation of
the alcohol (500 mg, 3.1 mmol) with benzoyl chloride gave 1b (810 mg, 3.04 mmol,
98% yield); oil; 1H NMR (600 MHz, CDCl3) δ 8.03 (d, J = 7.6 Hz, 2H), 7.54 (t, J = 7.6
Hz, 1H), 7.42 (t, J = 7.6 Hz, 2H), 7.26 (t, J = 7.6 Hz, 2H), 7.17 (t, J = 7.6 Hz, 1H), 7.16
(d, J = 7.6 Hz, 2H), 5.88 (dt, J = 15.8, 6.9 Hz, 1H), 5.70 (dt, J = 15.8, 6.9 Hz, 1H), 4.74
13
(d, J = 6.9 Hz, 2H), 2.71 (t, J = 6.9 Hz, 2H), 2.39 (q, J = 6.9 Hz, 2H); C{1H}NMR
(150 MHz, CDCl3) δ 166.4, 141.5, 135.3, 132.8, 130.3, 129.6, 128.4, 128.3, 125.9,
124.5, 65.5, 35.3, 34.1; HRMS (ESIꢀTOF) m/z calcd for C18H18NaO2 (M + Na)+
289.1204, found 289.1200; IR (neat) 2932, 1717, 1269 cm−1.
(E)ꢀ5ꢀPhenylpentꢀ2ꢀenyl pivalate (1c). (E)ꢀPhenylpentꢀ2ꢀenꢀ1ꢀol was prepared by
reduction of (E)ꢀethylꢀ5ꢀphenylpentꢀ2ꢀenoate in the same way as 1a. Pivaloylation of
the alcohol (320 mg, 2 mmol) with pivaloyl chloride gave 1c (551 mg, 1.13 mmol, 57%
1
yield); oil; H NMR (600 MHz, CDCl3) δ 7.26 (t, J = 7.6 Hz, 2H), 7.18–7.14 (m, 3H),
5.76 (dt, J = 15.1, 6.9 Hz, 1H), 5.56 (dt, J = 15.1, 6.2 Hz, 1H), 4.47 (d, J = 6.2 Hz, 2H),
2.68 (t, J = 7.6 Hz, 2H), 2.36 (q, J = 7.6 Hz, 2H), 1.17 (s, 9H); 13C{1H}NMR (150 MHz,
CDCl3) δ 178.3, 141.5, 134.4, 128.4, 128.3, 125.8, 124.7, 64.8, 38.7, 35.3, 34.0, 27.2;
HRMS (ESIꢀOrbitrap) m/z calcd for C16H26NO2 (M + NH4)+ 264.1958, found 264.1957;
IR (neat) 2973, 1730, 1152 cm−1.
cisꢀ2ꢀAcetoxyꢀ1ꢀ(acetoxymethyl)ꢀ1,2,3,4ꢀtetrahydronaphthalene
(3a).
To
dichloromethane solution (8 mL) containing 1a (41 mg, 0.2 mmol),
(diacetoxyiodo)benzene (77 mg, 0.24 mmol), BF3·OEt2 (0.1 mL) and HF·pyridine (50
ꢁL) was added at –80 °C. After stirring at –80 °C for 1 h, the mixture was quenched by
water and extracted with dichloromethane. The organic phase was dried with Na2SO4,
and concentrated in vacuo. The crude mixture was treated with acetic anhydride and
pyridine, then purified by column chromatography (SiO2, eluent 20% ethyl acetate in
hexane) to give racemic 3a (34.9 mg, 0.13 mmol, 67% yield). The reaction of 1a (41 mg,
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0.2 mmol) with 4b (219 mg, 0.4 mmol) in the presence of BF3·OEt2 (0.1 mL) and
TMSOTf (0.14 mL) at –80 °C for 2.5 h. gave a mixture of 2a and 2a’. The crude
mixture was treated with acetic anhydride and pyridine, then purified by column
chromatography to give optically active 3a (30.1 mg, 0.11 mmol, 57% yield) with 85%
ee. 1H NMR (600 MHz, CDCl3) δ 7.24−7.21 (m, 1H), 7.18−7.13 (m, 2H), 7.12−7.08 (m,
1H), 5.31 (ddd, J = 8.2, 4.8, 3.4 Hz, 1H), 4.41 (dd, J = 11.0, 4.8 Hz, 1H), 4.36 (dd, J =
11.0, 6.9 Hz, 1H), 3.41 (dt, J = 6.9, 4.8 Hz, 1H), 2.94 (dt, J = 17.2, 6.9 Hz, 1H), 2.83 (dt,
J = 17.2, 6.9 Hz, 1H), 2.12 (ddt, J = 13.7, 8.2, 6.9 Hz, 1H), 2.05 (s, 3H), 2.04 (s, 3H),
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1.94 (dtd, J = 13.7, 6.9, 3.4 Hz, 1H); C{1H}NMR (150 MHz, CDCl3) δ 170.9, 170.5,
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135.8, 134.2, 128.8, 128.7, 126.8, 126.1, 70.1, 64.9, 40.5, 26.4, 25.0, 21.2, 21.0; HRMS
(ESIꢀTOF) m/z calcd for C15H18NaO4 (M + Na)+ 285.1103, found 285.1097; IR (neat)
1739, 1245 cm−1; [α]D20 = –34.1 (c = 0.60, CHCl3) for 85% ee; Enantiomeric ratio of 3a
was determined by gas chromatography equipped with a chiral column
(ChirasilꢀDEXꢀCB, 25 m × 0.25 mm × 0.25 ꢁm film thickness). Retention times of
(+)ꢀ3a and (−)ꢀ3a were 18.1 and 18.6 min, respectively, when the column temperature
was maintained at 170 °C.
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Proton NMR of 2a and 2a'. Selected data for 2a: H NMR (600 MHz, CDCl3) δ
7.23−7.11 (m, 4H), 5.43 (ddd, J = 8.9, 4.8, 3.4 Hz, 1H), 3.99 (dd, J = 11.0, 4.8 Hz, 1H),
3.87 (dd, J = 11.0, 7.6 Hz, 1H), 3.29−2.74 (m, 3H), 2.20−1.92 (m, 2H), 2.08 (s, 3H);
1
Selected data for 2a’: H NMR (600 MHz, CDCl3) δ 7.23−7.11 (m, 4H), 4.53 (dd, J =
11.0, 7.6 Hz, 1H), 4.48 (dd, J = 11.0, 5.5 Hz, 1H), 4.25 (dt, J = 8.9, 4.1 Hz, 1H),
3.29−2.74 (m, 3H), 2.20−1.92 (m, 2H), 2.08 (s, 3H).
cisꢀ2ꢀBenzoyloxyꢀ1ꢀ(benzoyloxymethyl)ꢀ1,2,3,4ꢀtetrahydronaphthalene (3b). To
dichloromethane solution (8 mL) containing 1b (53 mg, 0.2 mmol),
(diacetoxyiodo)benzene (77 mg, 0.24 mmol), BF3·OEt2 (0.1 mL) and HF·pyridine (50
ꢁL) was added at –80 °C. After stirring at –80 °C for 1 h, the mixture was quenched by
water and extracted with dichloromethane. The organic phase was dried with Na2SO4,
and concentrated in vacuo. The crude mixture was treated with benzoyl chloride and
triethylamine, then purified by column chromatography (SiO2, eluent 10% ethyl acetate
in hexane) to give racemic 3b (47.3 mg, 0.12 mmol, 61% yield); colorless needle; mp =
96.5−97.0 °C; 1H NMR (600 MHz, CDCl3) δ 7.98 (d, J = 7.6 Hz, 2H), 7.90 (d, J = 7.6
Hz, 2H), 7.54−7.45 (m, 2H), 7.41−7.37 (m, 1H), 7.34 (t, J = 7.6 Hz, 2H), 7.32 (t, J = 7.6
Hz, 2H), 7.23−7.12 (m, 3H), 5.67 (ddd, J = 9.6, 5.5, 2.7 Hz, 1H), 4.79 (dd, J = 11.0, 5.5
Hz, 1H), 4.69 (dd, J = 11.0, 7.6 Hz, 1H), 3.74 (dt, J = 7.6, 5.5 Hz, 1H), 3.07 (dt, J =
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17.2, 5.5 Hz, 1H), 2.95 (dt, J = 17.2, 6.8 Hz, 1H), 2.34 (dtd, J = 13.7, 9.6, 6.8 Hz, 1H),
2.14 (dtd, J = 13.7, 5.5, 2.7 Hz, 1H); C{1H}NMR (150 MHz, CDCl3) δ 166.4, 165.9,
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135.9, 134.3, 132.9, 132.8, 130.1, 129.9, 129.6, 129.5, 129.0, 128.9, 128.3, 128.2, 126.9,
126.3, 71.0, 65.7, 41.0, 26.7, 25.1; HRMS (ESIꢀTOF) m/z calcd for C25H22NaO4 (M +
Na)+ 409.1416, found 409.1410; IR (KBr) 1713, 1289 cm−1; The structure of 3b was
confirmed by Xꢀray crystallography.13
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Proton NMR of 2b and 2b'. Selected data for 2b: 1H NMR (600 MHz, CDCl3) δ 7.98
(d, J = 7.6 Hz, 2H), 7.54 (t, J = 7.6 Hz, 1H), 7.41 (t, J = 7.6 Hz, 2H), 7.23−7.12 (m, 4H),
5.72 (ddd, J = 8.2, 4.8, 2.7 Hz, 1H), 4.11 (dd, J = 11.0, 4.8 Hz, 1H), 3.91 (dd, J = 11.0,
8.2 Hz, 1H), 3.37 (dt, J = 8.2, 4.8 Hz, 1H), 3.11 (dt, J = 17.2, 6.9 Hz, 1H), 2.93 (dt, J =
17.2, 6.9 Hz, 1H), 2.31 (dq, J = 13.7, 6.9 Hz, 1H), 2.10 (dtd, J = 13.7, 6.9, 2.7 Hz, 1H);
Selected data for 2b’: 1H NMR (600 MHz, CDCl3) δ 8.02 (d, J = 7.6 Hz, 2H), 7.56 (t, J
= 7.6 Hz, 1H), 7.44 (t, J = 7.6 Hz, 2H), 7.23−7.12 (m, 4H), 4.80 (dd, J = 11.0, 8.2 Hz,
1H), 4.73 (dd, J = 11.0, 4.8 Hz, 1H), 4.32 (ddd, J = 8.2, 4.8, 2.7 Hz, 1H), 3.37 (dt, J =
8.2, 4.8 Hz, 1H), 3.05 (dt, J = 17.2, 6.9 Hz, 1H), 2.84 (dt, J = 17.2, 6.9 Hz, 1H), 2.06
(dq, J = 13.7, 6.9 Hz, 1H), 1.98 (dtd, J = 13.7, 6.9, 2.7 Hz, 1H).
cisꢀ1ꢀ(Hydroxymethyl)ꢀ2ꢀpivaloyloxyꢀ1,2,3,4ꢀtetrahydronaphthalene (2c). To
dichloromethane solution (8 mL) containing 1c (49 mg, 0.2 mmol),
(diacetoxyiodo)benzene (87 mg, 0.27 mmol), BF3·OEt2 (0.1 mL) and HF·pyridine (50
ꢁL) was added at –80 °C. After stirring at –80 °C for 5 h, the mixture was quenched by
water and extracted with dichloromethane. The organic phase was dried with Na2SO4,
and concentrated in vacuo. The crude mixture was purified by column chromatography
(SiO2, eluent 20% ethyl acetate in hexane) to give racemic 2c (40.7 mg, 0.16 mmol,
78% yield); oil; 1H NMR (600 MHz, CDCl3) δ 7.21−7.18 (m, 1H), 7.16−7.14 (m, 2H),
7.13−7.10 (m, 1H), 5.43 (ddd, J = 9.6, 4.8, 3.4 Hz, 1H), 4.01 (dd, J = 11.0, 4.8 Hz, 1H),
3.80 (dd, J = 11.0, 8.2 Hz, 1H), 3.24 (dt, J = 8.2, 4.8 Hz, 1H), 2.99 (dt, J = 17.2, 6.9 Hz,
1H), 2.85 (dt, J = 17.2, 6.9 Hz, 1H), 2.19−2.08 (m, 1H), 2.01−1.88 (m, 1H), 1.18 (s,
9H); HRMS (ESIꢀTOF) m/z calcd for C16H22NaO3 (M + Na)+ 285.1467, found
285.1466.
cisꢀ2ꢀPivaloyloxyꢀ1ꢀ(pivaloyloxymethyl)ꢀ1,2,3,4ꢀtetrahydronaphthalene (3c). To
dichloromethane solution (8 mL) containing 1c (48 mg, 0.2 mmol),
(diacetoxyiodo)benzene (77 mg, 0.24 mmol), BF3·OEt2 (0.1 mL) and HF·pyridine (50
ꢁL) was added at –80 °C. After stirring at –80 °C for 1 h, the mixture was quenched by
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water and extracted with dichloromethane. The organic phase was dried with Na2SO4,
and concentrated in vacuo. The crude mixture was pivaloylated, then purified by
column chromatography (SiO2, eluent 6% ethyl acetate in hexane) to give racemic 3c
(39.5 mg, 0.11 mmol, 59% yield). The reaction of 1c (49 mg, 0.20 mmol) with 4b (219
mg, 0.4 mmol) in the presence of BF3·OEt2 (0.10 mL) and TMSOTf (0.14 mL) at
–80 °C for 17 h gave a mixture of 2c and 2c’. The crude mixture was treated with
pivaloyl chloride and triethylamine, then purified by column chromatography to give
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optically active 3c (25.5 mg, 0.07mmol, 37% yield) with 89% ee. H NMR (600 MHz,
CDCl3) δ 7.23−7.08 (m, 4H), 5.34 (ddd, J = 7.6, 5.5, 3.4 Hz, 1H), 4.48 (dd, J = 11.0, 5.5
Hz, 1H), 4.29 (dd, J = 11.0, 7.6 Hz, 1H), 3.38 (dt, J = 7.6, 5.5 Hz, 1H), 2.92 (ddd, J =
17.2, 7.6, 6.2 Hz, 1H), 2.79 (dt, J = 17.2, 6.2 Hz, 1H), 2.17 (ddt, J = 13.7, 7.6, 6.2 Hz,
1H), 1.88 (dtd, J = 13.7, 6.2, 3.4 Hz, 1H), 1.16 (s, 9H), 1.15 (s, 9H); 13C{1H}NMR (150
MHz, CDCl3) δ 178.4, 177.7, 136.0, 134.2, 128.9, 128.1, 126.6, 126.0, 69.0, 64.4, 40.5,
39.0, 38.7, 27.1, 27.0, 25.7, 25.4; HRMS (ESIꢀTOF) m/z calcd for C21H30NaO4 (M +
20
Na)+ 369.2042, found 369.2035; IR (neat) 2972, 1728, 1154 cm−1; [α]D = –14.6 (c =
0.24, CHCl3) for 89% ee. Enantiomeric ratio of 3c was determined by gas
chromatography equipped with a chiral column (ChirasilꢀDEXꢀCB, 25 m × 0.25 mm ×
0.25 ꢁm film thickness). Retention times of (+)ꢀ3c and (−)ꢀ3c were 69.3 and 70.1 min,
respectively, when the column temperature was maintained at 160 °C.
Corresponding Author
* Tel.: +81 791580170. FAX: +81 791580115. Eꢀmail: fuji@sci.uꢀhyogo.ac.jp.
Acknowledgements
This research was partially supported by the Japan Society for the Promotion of Science
(JSPS) through GrantsꢀinꢀAid for Scientific Research (C) (26410057). We are very
grateful to Prof. Hiroki Akutsu, Osaka University for Xꢀray crystallographic analysis.
We thank Sayaka Kado at Center for Analytical Instrumentation, Chiba University for
ESIꢀMS measurements using Exactive (ThermoFisher Scientific). We also thank Issei
Nishimura, University of Hyogo for preparation of compounds.
Supporting Information
The Xꢀray crystallographic cif data of 3b, the copies of H NMR and 13C{1H}NMR
1
spectra for all new compounds, and the copies of GLC chart for determination of the
enantiomeric ratio of products. The Supporting Information is available free of charge
on the ACS Publications website.
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(13) Xꢀray crystallographic data for 3b has been deposited with the Cambridge
Crystallographic Data Centre database under code CCDC 1544511.
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(14) Arene attack followed by acyloxy participation cannot be rigorously excluded as an
alternative mechanism. However, the reactivity depending on nucleophilicity of the
internal acyloxy group strongly suggests the mechanism shown in Scheme 1, because
the arylation process may proceed via the usual irreversible electrophilic
addition/deprotonation sequence.
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(15) Hojo, M.; Sakuragi, R.; Okabe, S.; Hosomi, A. Chem. Commun. 2001, 357.
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