Gold-catalyzed chemoselective formal (3+2)-Annulation reaction between β-naphthols and methyl aryldiazoacetate

Article abstract of DOI:10.1016/j.tet.2019.05.040

A chemoselective domino annulation reaction of β-naphthols with methyl aryldiazoacetate is described. The gold catalyst promoted C–H functionalization of β-naphthols, whereas a rhodium or copper complex led to O–H insertion reactions. Consecutive intramol

Full text of DOI:10.1016/j.tet.2019.05.040

Tetrahedron xxx (xxxx) xxx
Contents lists available at ScienceDirect
Tetrahedron
journal homepage: www.elsevier.com/locate/tet
Gold-catalyzed chemoselective formal (3þ2)-Annulation reaction
between
b-naphthols and methyl aryldiazoacetate
,
, b, *
Shingo Harada a **, Chigaya Sakai a, Koki Tanikawa a, Tetsuhiro Nemoto a
a Graduate School of Pharmaceutical Sciences, Chiba University, 1-8-1, Inohana, Chuo-ku, Chiba 260-8675, Japan
b Molecular Chirality Research Center, Chiba University, 1-33, Yayoi-cho, Inage-ku, Chiba 263-8522, Japan
a r t i c l e i n f o
a b s t r a c t
Article history:
A chemoselective domino annulation reaction of
The gold catalyst promoted CeH functionalization of
b
-naphthols with methyl aryldiazoacetate is described.
-naphthols, whereas a rhodium or copper complex
led to OeH insertion reactions. Consecutive intramolecular lactonization occurred after site-selective
alkylation at the 1-position of -naphthol, providing functionalized naphthofuranone derivatives. The
Received 19 March 2019
Received in revised form
15 May 2019
Accepted 21 May 2019
Available online xxx
b
b
product was transformed into a chiral molecule bearing an all-carbon quaternary stereogenic center with
high enantioselectivity.
© 2019 Elsevier Ltd. All rights reserved.
Keywords:
Naphthols
Heterocycle
Diazo compounds
Carbene
Gold
1. Introduction
2014, Liu, Zhang and Lan, Shi independently reported chemo- and
site-selective C(sp2)ꢀH functionalization of unprotected phenols
Metal catalyst-mediated direct carbon-hydrogen (CeH) func-
tionalization has emerged as a powerful and versatile synthetic
strategy for forming carbonecarbon bonds [1]. One of the most
reliable methods for the functionalization of aromatic C(sp2)eH is a
carbene transfer reaction, typically using diazo compounds, in the
presence of a transition-metal catalyst [2]. Yu [3], Davies [4], Liu [5],
using a Au catalyst with a phosphite ligand and donor/acceptor-
substituted diazo compounds (Scheme 1 (a)) [12,13], while a Rh,
Cu, Ru, In, or Pd catalyst caused OeH insertion [9]. Although lac-
tonization of the products obtained by the Au-catalyzed ortho-
functionalization of p-cresol was also reported, the two step pro-
cedure involving harsh conditions (a stoichiometric amount of TFA
at high temperature) was required.
ꢀ
Zhang [6] Rovis [7], and Perez [8] have greatly contributed to the
research field of direct C(sp2)ꢀH functionalization of aromatic
molecules using metal-carbene species. The CeH functionalization
of unprotected phenols and their derivatives, however, has
remained a challenge as the potentially reactive phenolic hydroxy
group leads to competitive OeH insertion reactions with the metal-
carbene complex [9].
(1)
Homogeneous gold catalysis was recently recognized as a
valuable method for rapidly synthesizing a complex carbon skel-
eton due to its unique catalytic activities [10]. Gold-carbene is often
proposed as the key chemical species in these reactions [11]. In
Our laboratory has also endeavored to develop novel metal-
carbene reactions [14] and, in 2017, reported an intramolecular
asymmetric dearomatization of phenols using Ag-carbene gener-
ated from a-diazoacetamides, whereas a Rh or Cu catalyst caused
mainly a CeH insertion reaction and Büchner reaction [15]. To
further develop the reaction, we focused on designing an inter-
molecular reaction taking advantage of the metal-dependent
reactivity of the carbene species [16]. During our research, we
found that a reaction of metal-stabilized donor/acceptor carbene
with 2-naphthol chemoselectively produced a naphthofuranone
* Corresponding author. Graduate School of Pharmaceutical Sciences, Chiba
University, 1-8-1, Inohana, Chuo-ku, Chiba 260-8675, Japan.
** Corresponding author.
E-mail addresses: Sharada@chiba-u.jp (S. Harada), tnemoto@faculty.chiba-u.jp
(T. Nemoto).
https://doi.org/10.1016/j.tet.2019.05.040
0040-4020/© 2019 Elsevier Ltd. All rights reserved.
Please cite this article as: S. Harada et al., Gold-catalyzed chemoselective formal (3þ2)-Annulation reaction between
b-naphthols and methyl
aryldiazoacetate, Tetrahedron, https://doi.org/10.1016/j.tet.2019.05.040

2
S. Harada et al. / Tetrahedron xxx (xxxx) xxx
Table 1
derivative over the OeH insertion reaction (Scheme 1 (b)). In this
formal (3 þ 2) reaction, a donor/acceptor-substituted diazo ester
functioned as a vicinal dielectrophile in one-pot (eq (1)). Naph-
thofuranone skeletons are often observed in the core structure of
natural products and biologically related molecules [17]; therefore,
an effective strategy for constructing the molecular architecture is
desirable [18]. Herein, we describe the development of a CeH
functionalization/lactonization domino annulation of naphthols
with donor/acceptor-substituted diazo compounds, affording
functionalized naphthofuranones.
Optimization of the reaction conditions.
entry
catalyst(s)
solvent
Yield (%)a
ratio
3a: 4a
1
2
3
4
5
6
7
8
Rh2(OAc)4
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CDCl3
PhCl
PhCl
PhCl
PhCl
PhCl
PhCl
PhCl
PhCl
PhCl
PhCl
PhCl
13
53
19
0
<5:>95
<5:>95
<5:>95
e
Cu(NCMe)4PF6
2. Results and discussion
[(h
3-C3H5)PdCl]2
Fe(OAc)2
AgNTf2
We commenced our study using 2-naphthol (1a) and methyl 2-
diazo-2-phenylacetate (2a) as a donor/acceptor carbene precursor
in the presence of a metal catalyst (Table 1). The reaction with a
commonly used rhodium(II) acetate dimer (5 mol %) in dichloro-
methane solvent at room temperature gave OeH insertion product
4a in 13% yield (entry 1). Similar results were obtained in the re-
action using Cu or Pd catalysts (entries 2 and 3). Reversed che-
45
76
80
85
68
71
22
33
41
0
92 : 8
>95: <5
>95: <5
>95: <5
>95: <5
>95: <5
82 : 18
51:49
70 : 30
e
Ph3PAuCl/AgSbF6
Ph3PAuCl/AgSbF6
Ph3PAuCl/AgSbF6
(ArO)3PAuCl/AgSbF6
IPrAuCl/AgSbF6
Ph3PAuCl/AgBF4
Ph3PAuCl/AgO2CCF3
Ph3PAuCl/AgPF6
Ph3PAuCl
AgSbF6
Ph3PAuNTf2
Ph3PAgSbF6
none
9
10
11
12
13
14
15
16
17
18
moselectivity
was
observed
when
using
silver
bis(trifluoromethanesulfonyl)imide (AgNTf2), affording the desired
CeH functionalized product 3a (3a: 4a ¼ 92 : 8, entry 5). The use of
a Au catalyst possessing triphenylphosphine provided 3a in 76%
yield without detectable production of 4a (entry 6). A solvent
survey revealed that chlorobenzene was suitable for the trans-
formation (entries 7 and 8). Further examination of the Au catalysts
and Ag salts did not improve the yield of 3 or the chemoselectivity
(entries 9e18) [19], and therefore the reaction conditions of entry
[8] were considered optimal.
The substrate generality was evaluated, and the results are
summarized in Table 2. Naphthofuranones having aryl groups with
electron-withdrawing and -releasing substituents were obtained in
good to excellent yield with complete chemoselectivity (60%e98%
yield, 3 ab-ae). Electron-abundant and deficient naphthols were
also provided by the formal (3 þ 2) annulation reaction, furnishing
3ba, 3ca, and 3da in 52%, 83%, and 72% yield, respectively. When
2
29
0
40 : 60
>95: <5
e
0
e
a
The sum of the yields of 3a and 4a. Ar is 2,4-t-Bu2-C6H3. IPr is 1,3-bis(2,6-
diisopropylphenyl)imidazol-2-ylidene.
phenylacetate (2i), providing 3aa in 86% yield. The lactonization of
indolinone 2j with diazo functionality did not proceed under gold
catalysis.
Application of O-protected 2-naphthol 5 under the optimized
conditions led to the isolation of methyl ester 6 (eq (3)). Removal of
the TBS group by treatment with HF-pyridine led to lactonization
[20]. Based on these results, a plausible reaction pathway is
depicted in Scheme 3. Electrophilic addition of Au-carbene 7,
generated from the catalysts and diazo compound 1, to the 1-
position of the naphthol would create a CeC bond, providing the
intermediate 8. Subsequent rearomatization to naphthol and pro-
todeauration occurred concomitantly with regeneration of the Au
catalyst, providing CeH-functionalized product 9. The final intra-
molecular cyclization seemed to proceed rapidly, but it is yet un-
clear whether the Au complex as a Lewis acid is involved in the
lactonization.
phenanthren-9-ol (1e) was used as
a
nucleophile, 3-
phenylphenanthrofuranones 3ea, 3ef, 3ee, 3eg, and 3eh were ob-
tained in good yield without the production of 4 or any regioisomer.
Additional scope and limitations were studied (Scheme 2). The
reaction of a-naphthol (1f) with 2a afforded OeH insertion product
4fa. Similar reactivity was observed when using benzyl 2-diazo-2-
(3)
First, we considered applying the reaction to an asymmetric
synthesis, but the synthesized 1-arylnaphthofuranone 10 sponta-
neously racemized, even without treatment with acid or base (eq
(4)). The racemization process is likely through aromatization-
dearomatization of the furanone unit via a naphthofuran-2-ol 11,
which is a potentially useful intermediate for the dynamic kinetic
resolution (DKR) method [21]. Toward the asymmetric synthesis, a
Tsuji-Trost reaction was performed using 3a as the substrate under
palladium catalysis, producing functionalized naphthofuranone
possessing an all-carbon quaternary stereogenic center in excellent
yield with high enantioselectivity [22] (Scheme 4).
Scheme 1. Reactions of metal-carbenes with phenols and naphthols.
Please cite this article as: S. Harada et al., Gold-catalyzed chemoselective formal (3þ2)-Annulation reaction between
b-naphthols and methyl
aryldiazoacetate, Tetrahedron, https://doi.org/10.1016/j.tet.2019.05.040

S. Harada et al. / Tetrahedron xxx (xxxx) xxx
3
(4)
3. Conclusion
In summary, we established a gold-catalyzed CeH functionali-
zation of 2-naphthols and phenanthren-9-ols followed by a lacto-
nization in moderate to excellent yields. High chemoselectivity was
achieved by taking advantage of the unique characteristics of the
gold-carbene species. The synthesized arylnaphthofuranone was
converted to a functionalized molecule in an optically enriched
form through palladium-catalyzed enantioselective alkenylation.
Further development of the reaction with metal-carbenes will be
reported in due course.
Scheme 2. Substrate scope and limitations.
and 100 MHz, respectively. Chemical shifts are reported in ppm
using tetramethylsilane as the internal standard in CDCl3 or DMF-
d7 solvent. ESI mass spectra were measured on JEOL AccuTOF LC-
plus JMS-T100LP. Optical rotation was measured on a JASCO P-
1020 polarimeter. The enantiomeric excess (ee) was determined by
HPLC analysis. HPLC was performed on JASCO HPLC systems con-
sisting of the following: pump, PU-980; detector, UV-970; column
DAICEL CHIRALCEL OD-H; mobile phase, n-hexane/i-PrOH. Melting
4. Experimental section
4.1. General information
IR spectra were recorded on a JASCO FT/IR 230 Fourier transform
infrared spectrophotometer, equipped with ATR (Smiths Detection,
DuraSample IR II). 1H and 13C NMR spectra were recorded at 400
Table 2
Substrate scope.
Please cite this article as: S. Harada et al., Gold-catalyzed chemoselective formal (3þ2)-Annulation reaction between
b-naphthols and methyl
aryldiazoacetate, Tetrahedron, https://doi.org/10.1016/j.tet.2019.05.040

4
S. Harada et al. / Tetrahedron xxx (xxxx) xxx
C
18H11Oꢀ2 m/z 259.0765, found 259.0759.
1-(4-bromophenyl)naphtho[2,1-b]furan-2(1H)-one (3 ab). Pre-
pared according to the general procedure A and isolated as yellow
solid (57.3 mg, 84% yield): mp 91e93 ꢁC; Rf ¼ 0.6 (n-hexane/EtOAc,
2/1); 1H NMR (400 MHz, CDCl3)
d
5.16 (s,1H), 7.12 (d, J ¼ 8.4 Hz, 2H),
7.29e7.33 (m, 1H), 7.38e7.50 (m, 5H), 7.89e7.93 (m, 1H), 7.95 (d,
J ¼ 8.8 Hz, 1H); 13C NMR (100 MHz, CDCl3)
d 49.2, 111.5, 118.6, 122.5,
123.1, 125.0, 127.8, 129.2, 129.4, 123.0 (2C), 131.0, 131.1, 132.4 (2C),
133.7, 152.0, 175.0; IR (ATR)
n 2952, 1804, 1632, 1579, 1522,
1487 cmꢀ1; HRMS (ESI-TOF) [M ꢀ H]ꢀ calcd for C18H10BrOꢀ2 m/z
336.9870, found 336.9875.
1-(3-chlorophenyl)naphtho[2,1-b]furan-2(1H)-one (3ac). Pre-
pared according to the general procedure A and isolated as yellow
solid (35.4 mg, 60% yield): mp 110e112 ꢁC; Rf ¼ 0.6 (n-hexane/
Scheme 3. Proposed reaction pathway.
EtOAc, 2/1); 1H NMR (400 MHz, CDCl3)
d 5.15 (s, 1H), 7.12 (d,
J ¼ 7.2 Hz, 1H), 7.21e7.35 (m, 4H), 7.37e7.47 (m, 3H), 7.89e7.94 (m,
1H), 7.96 (d, J ¼ 8.8 Hz, 1H); 13C NMR (100 MHz, CDCl3)
d 49.3, 111.5,
118.5, 123.1, 125.0, 126.5, 127.9, 128.5, 128.6, 129.2, 129.4, 130.4,
131.0, 131.1, 135.1, 136.6, 152.0, 174.9; IR (ATR)
n 2925, 1808, 1633,
1581, 1523, 1474 cmꢀ1
;
HRMS (ESI-TOF) [M ꢀ H]ꢀ calcd for
C
18H10ClOꢀ2 m/z 293.0375, found 293.0372.
1-(3-methoxyphenyl)naphtho[2,1-b]furan-2(1H)-one (3ad). Pre-
Scheme 4. An enantioselective DKR of 3a.
pared according to the general procedure A and isolated as yellow
solid (41.4 mg, 71% yield): mp 82e84 ꢁC; Rf ¼ 0.5 (n-hexane/EtOAc,
2/1); 1H NMR (400 MHz, CDCl3)
d 3.74 (s, 3H), 5.13 (s, 1H), 6.78 (d,
J ¼ 2.0 Hz, 1H), 6.80 (d, J ¼ 7.6 Hz, 1H), 6.86 (dd, J ¼ 8.0, 2.4 Hz, 1H),
points were measured with a SIBATA NEL-270 melting point
apparatus. Analytical thin layer chromatography was performed on
Kieselgel 60F254, 0.25 mm thickness plates. Column chromatog-
raphy was performed with silica gel 60 N (spherical, neutral
63e210 mesh). All commercially available reagents were used
directly without purification unless otherwise stated. All solvents
were purified following standard procedures. Reactions were con-
ducted in dry solvent. Other reagents were purified by the usual
methods.
7.25 (t, J ¼ 7.6 Hz, 1H), 7.36e7.46 (m, 4H), 7.87e7.91 (m, 1H), 7.92 (d,
J ¼ 8.8 Hz, 1H); 13C NMR (100 MHz, CDCl3)
d 49.7, 55.2, 111.4, 113.5,
114.3, 119.3, 120.6, 123.2, 124.9, 127.6, 129.2, 129.3, 130.2, 130.7,
131.0, 136.2, 151.9, 160.1, 175.4; IR (ATR)
n 2925, 2837, 1807, 1633,
1599, 1584, cmꢀ1; HRMS (ESI-TOF) [M ꢀ H]ꢀ calcd for C19H13Oꢀ3 m/z
289.0870, found 289.0874.
1-(4-(tert-butyl)phenyl)naphtho[2,1-b]furan-2(1H)-one
(3ae).
Prepared according to the general procedure A and isolated as
white solid (62.1 mg, 98% yield): mp 97e98 ꢁC; Rf ¼ 0.7 (n-hexane/
EtOAc, 2/1); 1H NMR (400 MHz, CDCl3)
d 1.29 (s, 9H), 5.16 (s, 1H),
4.2. Compounds 1, 2, 5, 13
7.15 (d, J ¼ 8 Hz, 2H), 7.34 (d, J ¼ 8.4 Hz, 2H), 7.38e7.45 (m, 4H),
7.87e7.94 (m, 2H); 13C NMR (100 MHz, CDCl3)
31.2 (3C), 34.5, 49.3,
111.5, 119.6, 123.4, 124.8, 126.1 (2C), 127.6, 127.9 (2C), 129.2, 129.4,
d
Substrates 1d [23], 2a-c [24], 2d [25], 2e [26], 2f-h [24], 5 [27],
and 13 [28] were synthesized in our lab by the reported procedures.
130.6, 131.0, 131.6, 151.2, 151.9, 175.9; IR (ATR)
n 2962, 1808, 1633,
1582, 1522, 1461 cmꢀ1; HRMS (ESI-TOF) [M þ Na]þ calcd for
22H20NaOþ2 m/z 339.1356, found 339.1352.
4.3. General procedure (Table 2)
C
8-methoxy-1-phenylnaphtho[2,1-b]furan-2(1H)-one (3ba). Pre-
General Procedure A for the Synthesis of CeH Functionalized
Product 3. In a dried glass tube, a solution of compound 1 (0.3 mmol,
1.5 eq), Ph3PAuCl (5 mol %, 4.94 mg), and AgSbF6 (5 mol %, 3.44 mg)
in chlorobenzene (2 mL) was stirred at room temperature for
20 min. Then a solution of diazocompound 2 (0.2 mmol, 1 eq) in
chlorobenzene (2 mL) was added to the reaction mixture by a sy-
ringe in 1 min, and the resulting mixture was continually stirred at
room temperature for 1 h. The reaction mixture was concentrated
under reduced pressure and purified by flash chromatography on
silica gel (column condition; gradient elution: n-hexane/EtOAc, 15/
1) to afford the desired product 3.
pared according to the general procedure A and isolated as white
solid (30.2 mg, 52% yield): mp 132e134 ꢁC; Rf ¼ 0.6 (n-hexane/
EtOAc, 2/1); 1H NMR (400 MHz, CDCl3)
d 3.94 (s, 3H), 5.02 (s, 1H),
7.10 (dd, J ¼ 9.2, 2.8 Hz, 1H), 7.16 (d, J ¼ 2.8 Hz, 1H), 7.27e7.30 (m,
2H), 7.34e7.41 (m, 3H), 7.45 (s, 1H), 7.59 (s, 1H), 7.67 (d, J ¼ 9.2 Hz,
1H); 13C NMR (100 MHz, CDCl3)
d 49.8, 55.1, 101.7, 108.8, 117.5, 118.3,
126.4, 128.27, 128.32 (2C), 128.4, 129.2 (2C), 130.3, 130.8, 134.6,
152.4, 158.8, 175.7; IR (ATR)
n 2962, 1807, 1646, 1413, 1259,
1212 cmꢀ1; HRMS (ESI-TOF) [M ꢀ H]ꢀ calcd for C19H13Oꢀ3 m/z
289.0870, found 289.0877.
7-bromo-1-phenylnaphtho[2,1-b]furan-2(1H)-one (3ca). Pre-
pared according to the general procedure A and isolated as white
solid (50.1 mg, 74% yield): mp 159e160 ꢁC; Rf ¼ 0.7 (n-hexane/
4.4. Characterization of 3
EtOAc, 2/1); 1H NMR (400 MHz, CDCl3)
d 5.19 (s, 1H), 7.18e7.24 (m,
1-phenylnaphtho[2,1-b]furan-2(1H)-one (3aa). Prepared accord-
ing to the general procedure A and isolated as white solid (44.4 mg,
85% yield): mp 171e172 ꢁC; Rf ¼ 0.5 (n-hexane/EtOAc, 5/1); 1H NMR
3H), 7.32e7.38 (m, 3H), 7.44e7.49 (m, 2H), 7.85 (d, J ¼ 8.8 Hz, 1H),
8.07 (d, J ¼ 1.6 Hz, 1H); 13C NMR (100 MHz, CDCl3)
d 49.6, 112.6,
118.8, 119.7, 124.9, 127.8, 128.3 (2C), 128.5, 129.3 (2C), 129.8, 131.0,
(400 MHz, CDCl3)
d
5.15 (s, 1H), 7.18e7.27 (m, 2H), 7.28e7.48 (m,
131.2, 132.1, 134.4, 152.2, 175.1; IR (ATR) n 3063, 3031, 1806, 1631,
7H), 7.86e7.96 (m, 2H); 13C NMR (100 MHz, CDCl3)
119.3, 123.2, 124.9, 127.6, 128.29, 128.31 (2C), 129.19 (2C), 129.24,
d
49.8, 111.4,
1577,1509 cmꢀ1; HRMS (ESI-TOF) [M ꢀ H]ꢀ calcd for C18H10BrOꢀ2 m/
z 336.9870, found 336.9871.
129.3, 130.7, 131.0, 134.8, 151.9, 175.6; IR (ATR)
n
2931, 1808, 1633,
methyl
2-oxo-1-phenyl-1,2-dihydronaphtho[2,1-b]furan-6-
1585, 1522, 1496 cmꢀ1
;
HRMS (ESI-TOF) [M ꢀ H]ꢀ calcd for
carboxylate (3da). Prepared according to the general procedure A
Please cite this article as: S. Harada et al., Gold-catalyzed chemoselective formal (3þ2)-Annulation reaction between
b-naphthols and methyl
aryldiazoacetate, Tetrahedron, https://doi.org/10.1016/j.tet.2019.05.040

S. Harada et al. / Tetrahedron xxx (xxxx) xxx
5
and isolated as yellow solid (45.9 mg, 72% yield): mp 130e132 ꢁC;
4.5. Synthesis and characterization of 4aa and 4fa
Rf ¼ 0.3 (n-hexane/EtOAc, 5/1); 1H NMR (400 MHz, CDCl3)
d 4.02 (s,
3H), 5.21 (s, 1H), 7.19e7.23 (m, 2H), 7.34 (d, J ¼ 2.4 Hz, 2H), 7.35 (d,
J ¼ 2 Hz, 1H), 7.37e7.43 (m, 1H), 7.50e7.58 (m, 2H), 8.09 (d,
J ¼ 1.2 Hz, 1H), 9.05 (d, J ¼ 9.2 Hz, 1H); 13C NMR (100 MHz, CDCl3)
methyl 2-(naphthalen-2-yloxy)-2-phenylacetate (4aa). To a stir-
red solution of 2-naphthol (1a) (0.3 mmol, 1.5 eq), Rh2(OAc)4 (5 mol
%) in dichloromethane (0.05 M) in a test tube, were added methyl 2-
diazo-2-phenylacetate (2a) (0.2 mmol, 1 eq), and the reaction
mixture was stirred at room temperature until the substrate dis-
appeared. The reaction mixture was concentrated under reduced
pressure and purified by flash chromatography on silica gel (col-
umn condition; gradient elution: n-hexane/EtOAc, 20/1) to afford
the product 4aa. Spectroscopic data are in agreement with litera-
ture[29].
d
49.8, 52.4, 112.9, 119.8, 126.4, 128.2, 128.3 (2C), 128.4, 128.5, 128.7,
128.87, 128.89, 129.3, 129.9 (2C), 134.7, 152.2, 167.7, 175.2; IR (ATR)
n
2951, 1812, 1716, 1629, 1526, 1496 cmꢀ1; HRMS (ESI-TOF) [M ꢀ H]ꢀ
calcd for C20H13Oꢀ4 m/z 317.0819, found 317.0812.
3-phenylphenanthro[9,10-b]furan-2(3H)-one (3ea). Prepared ac-
cording to the general procedure A and isolated as white solid
(51.8 mg, 84% yield): mp 197e198 ꢁC; Rf ¼ 0.5 (n-hexane/EtOAc, 5/
1); 1H NMR (400 MHz, CDCl3)
d
5.26 (s, 1H), 7.19e7.37 (m, 5H),
methyl 2-(naphthalen-1-yloxy)-2-phenylacetate (4fa). Prepared
according to the general procedure A and isolated as red liquid
(38.8 mg, 66% yield): Rf ¼ 0.3 (n-hexane/EtOAc, 3/1); 1H NMR
7.38e7.50 (m, 2H), 7.58 (t, J ¼ 7.6 Hz, 1H), 7.67e7.83 (m, 2H), 8.20 (d,
J ¼ 8.0 Hz, 1H), 8.75 (dd, J ¼ 17.6, 8.0 Hz, 2H); 13C NMR (100 MHz,
DMF-d7)
d
51.0, 118.0, 120.8, 122.3, 124.6, 124.7, 124.8, 126.4, 128.2,
(400 MHz, CDCl3)
d
3.76 (s, 3H), 5.71 (s, 1H), 6.51 (d, J ¼ 8.0 Hz, 1H),
128.3, 128.4, 128.8, 128.9, 129.0, 129.3 (2C), 129.9 (2C), 132.1, 136.8,
7.01 (d, J ¼ 7.6 Hz, 1H), 7.23e7.34 (m, 6H), 7.45 (dtd, J ¼ 20.0, 6.4,
148.9, 176.5; IR (ATR)
n ;
3056, 1803, 1601, 1509, 1449, 1410 cmꢀ1
1.2 Hz, 2H), 7.89 (d, J ¼ 7.6 Hz, 1H), 8.21 (d, J ¼ 8.8 Hz, 1H); 13C NMR
HRMS (ESI-TOF) [M ꢀ H]ꢀ calcd for C22H13Oꢀ2 m/z 309.0921, found
(100 MHz, CDCl3) d 52.6, 53.1, 107.9, 122.7, 122.8, 124.87, 124.92,
309.0921.
126.2, 126.6, 127.0, 127.3, 128.6 (2C), 128.9 (2C), 132.5, 137.9, 151.5,
3-(p-tolyl)phenanthro[9,10-b]furan-2(3H)-one (3ef). Prepared
according to the general procedure A and isolated as white solid
(62.5 mg, 90% yield): mp 172e173 ꢁC; Rf ¼ 0.6 (n-hexane/EtOAc, 4/
174.3; IR (ATR)
n
3408, 2950, 1715, 1628, 1588, 1518 cmꢀ1
.
4.6. Synthesis and characterization of 6
1); 1H NMR (400 MHz, CDCl3)
d 2.32 (s, 3H), 5.15 (s, 1H), 7.14 (s, 4H),
7.35e7.48 (m, 2H), 7.56 (td, J ¼ 8.4, 1.6 Hz, 1H), 7.68e7.83 (m, 2H),
methyl 2-(6-bromo-2-((tert-butyldimethylsilyl)oxy)naphthalen-1-
yl)-2-phenylacetate (6). To a stirred solution of Ph3PAuCl (5 mol%),
and AgSbF6 (5 mol%) in chlorobenzene (3 mL) in a flask, were added
8.16 (d, J ¼ 8.0 Hz, 1H), 8.71 (dd, J ¼ 16.8, 8.4 Hz, 2H); 13C NMR
(100 MHz, CDCl3)
d 21.1, 50.2, 116.1, 120.2, 122.2, 123.2, 123.6, 124.1,
125.5, 127.3, 127.5, 127.6, 127.9, 128.2 (2C), 128.3, 129.9 (2C), 131.5,
((6-bromonaphthalen-2-yl)oxy)(tert-butyl)dimethylsilane
(5)
131.7, 138.2, 148.6, 175.9; IR (ATR)
n
3056, 2918, 1808, 1611, 1511,
(0.45 mmol, 1.5 eq) after 30 min. Methyl 2-diazo-2-phenylacetate
(2a) (0.3 mmol, 1 eq) dissolved in chlorobenzene (3 mL) were
added over 2 h using a syringe pump and the reaction mixture was
stirred at room temperature for 1 h. The reaction mixture was
concentrated under reduced pressure and purified by flash chro-
matography on silica gel (column condition; gradient elution: n-
hexane/EtOAc, 30/1) to afford the desired product 6 as a white solid
(38.7 mg, 27% yield): mp 112e113 ꢁC; Rf ¼ 0.7 (n-hexane/EtOAc, 5/
1449 cmꢀ1; HRMS (ESI-TOF) [M þ Na]þ calcd for C23H16NaOþ2 m/z
347.1048, found 347.0918.
3-(4-(tert-butyl)phenyl)phenanthro[9,10-b]furan-2(3H)-one
(3ee). Prepared according to the general procedure A and isolated
as white solid (74.7 mg, 96% yield): mp 160e162 ꢁC; Rf ¼ 0.7 (n-
hexane/EtOAc, 4/1); 1H NMR (400 MHz, CDCl3)
d 1.29 (s, 9H), 5.23
(s, 1H), 7.20 (d, J ¼ 8.8 Hz, 2H), 7.35 (d, J ¼ 8.8 Hz, 2H), 7.42e7.52 (m,
2H), 7.58 (t, J ¼ 6.8, 1.2 Hz, 1H), 7.70e7.84 (m, 2H), 8.19 (d, J ¼ 7.6 Hz,
1); 1H NMR (400 MHz, CDCl3)
d 0.12 (s, 3H), 0.22 (s, 3H), 0.95 (s, 9H),
1H), 8.74 (dd, J ¼ 18, 8.4 Hz, 2H); 13C NMR (100 MHz, CDCl3)
d
31.2
3.65 (s, 3H), 6.05 (s, 1H), 7.14 (d, J ¼ 7.6 Hz, 2H), 7.17e7.27 (m, 4H),
7.36 (dd, J ¼ 9.2, 2.4 Hz, 1H), 7.60 (d, J ¼ 8.8 Hz, 1H), 7.65 (d,
J ¼ 9.2 Hz, 1H), 7.93 (d, J ¼ 2.4 Hz, 1H); 13C NMR (100 MHz, CDCl3)
(3C), 34.5, 50.1, 116.1, 120.3, 122.2, 123.3, 123.5, 124.3, 125.5, 126.2
(2C), 127.3, 127.5, 127.6, 127.875, 127.884 (2C), 128.3, 131.46, 131.50,
148.6, 151.2, 175.9; IR (ATR)
n
3060, 2954, 1803, 1506, 1348,
d
ꢀ4.04, ꢀ4.01, 18.3, 25.7 (3C), 47.1, 52.2, 117.3, 121.3, 121.8, 126.6,
1330 cmꢀ1; HRMS (ESI-TOF) [M þ Na]þ calcd for C26H22NaOþ2 m/z
126.7, 128.0 (2C), 128.4, 128.9 (2C), 129.6, 130.3, 130.9, 131.9, 137.0,
389.1518, found 389.1511.
151.9, 173.6; IR (ATR)
n 3061, 3029, 2952, 2929, 2885, 2857, 1737,
3-(4-methoxyphenyl)phenanthro[9,10-b]furan-2(3H)-one (3eg).
Prepared according to the general procedure A and isolated as
white solid (66.1 mg, 91% yield): mp 183e185 ꢁC; Rf ¼ 0.5 (n-hex-
1616, 1588, 1495 cmꢀ1; HRMS (ESI-TOF) [M þ Na]þ calcd for
C25H29BrNaO3Siþ m/z 507.0967, found 507.0931.
ane/EtOAc, 4/1); 1H NMR (400 MHz, CDCl3)
d
3.78 (s, 3H), 5.19 (s,
4.7. Synthesis and characterization of 14
1H), 6.87 (d, J ¼ 8.8 Hz, 2H), 7.19 (d, J ¼ 8.8 Hz, 2H), 7.39e7.51 (m,
2H), 7.58 (t, J ¼ 6.8, 1.6 Hz, 1H), 7.70e7.83 (m, 2H), 8.19 (d, J ¼ 7.6 Hz,
(S)-1-cinnamyl-1-phenylnaphtho[2,1-b]furan-2(1H)-one (14). To
a stirred mixture of cinnamyl acetate (13) (0.09 mmol, 1.8 eq), 1-
phenylnaphtho[2,1-b]furan-2(1H)-one (3aa) (0.05 mmol, 1 eq),
allylpalladium(II) chloride dimer (5 mol%), (R,R)-DACH-phenyl
Trost ligand (12 mol%) in THF (0.05 M) was added Cs2CO3
(0.075 mmol, 1.5 eq) at room temperature. After being stirred for
4 h, the reaction mixture was concentrated under reduced pressure,
and the obtained residue was purified by flash column chroma-
tography on silica gel (column condition; gradient elution: n-hex-
ane/EtOAc 20/1 to 15/1) to give 14 as colorless oil (17.9 mg, 95%
yield): Rf ¼ 0.4 (n-hexane/EtOAc, 5/1); 1H NMR (400 MHz, CDCl3)
1H), 8.74 (dd, J ¼ 16.4, 7.6 Hz, 2H); 13C NMR (100 MHz, CDCl3)
d 49.8,
55.3, 114.7 (2C), 116.1, 120.3, 122.2, 123.2, 123.6, 124.2, 125.5, 126.6,
127.4, 127.5, 127.6, 127.9, 128.3, 129.4 (2C), 131.5, 148.6, 159.6, 176.0;
IR (ATR) n
2939, 2357, 2304, 1800,1506,1348 cmꢀ1; HRMS (ESI-TOF)
[M þ Na]þ calcd for C23H16NaOþ2 m/z 363.0997, found 363.0996.
3-(4-chlorophenyl)phenanthro[9,10-b]furan-2(3H)-one
(3eh).
Prepared according to the general procedure A and isolated as
white solid (59.4 mg, 86% yield): mp 175e177 ꢁC; Rf ¼ 0.6 (n-hex-
ane/EtOAc, 4/1); 1H NMR (400 MHz, CDCl3)
d 5.21 (s, 1H), 7.18e7.29
(m, 2H), 7.30e7.40 (m, 3H), 7.48 (td, J ¼ 8.4, 1.6 Hz, 1H), 7.60 (td,
J ¼ 8.8, 1.2 Hz, 1H), 7.71e7.86 (m, 2H), 8.18 (d, J ¼ 8.0 Hz, 1H), 8.74
d
3.53 (ddd, J ¼ 13.2, 6.4, 0.8 Hz, 1H), 3.64 (ddd, J ¼ 13.2, 8.0, 0.8 Hz,
(dd, J ¼ 14.8, 8.8 Hz, 2H); 13C NMR (100 MHz, CDCl3)
d
49.6, 115.3,
1H), 5.55 (ddd, J ¼ 15.2, 8.4, 6.8 Hz, 1H), 6.36 (d, J ¼ 15.6 Hz, 1H),
6.98 (dd, J ¼ 7.6, 1.6 Hz, 2H), 7.10e7.18 (m, 3H), 7.29e7.41 (m, 6H),
7.42e7.47 (m, 2H), 7.48e7.55 (m, 1H), 7.90e7.97 (m, 2H); 13C NMR
120.1, 122.2, 123.3, 123.7, 124.0,125.7, 127.3, 127.5, 127.7, 128.1, 128.4,
129.5 (2C), 129.7 (2C), 131.6, 133.1, 134.4, 148.9, 175.2; IR (ATR)
n
3057, 2123, 1800, 1610, 1508, 1491 cmꢀ1; HRMS (ESI-TOF) [M þ H]þ
(100 MHz, CDCl3)
d 40.0, 57.6, 111.6, 121.6, 122.4, 123.0, 124.8, 126.2
calcd for C22H14Oþ2 m/z 345.0682, found 345.0675.
(2C), 127.1 (2C), 127.4, 127.6, 128.2, 128.3 (2C), 129.0 (2C), 129.3,
Please cite this article as: S. Harada et al., Gold-catalyzed chemoselective formal (3þ2)-Annulation reaction between
b-naphthols and methyl
aryldiazoacetate, Tetrahedron, https://doi.org/10.1016/j.tet.2019.05.040

6
S. Harada et al. / Tetrahedron xxx (xxxx) xxx
compounds: selectivity and diversity, Chem. Soc. Rev. 45 (2016) 506e516.
[7] T.K. 7Hyster, K.E. Ruhl, T. Rovis, A coupling of benzamides and donor/acceptor
129.7, 130.8, 131.2, 135.0, 136.6, 137.9, 151.1, 178.3; IR (ATR)
n 3059,
3029, 2923, 2853, 1799, 1722, 1631, 1581, 1522, 1496 cmꢀ1; HRMS
diazo compounds to form
g-lactams via Rh(III)-Catalyzed CeH activation,
(ESI-TOF) [M þ Na]þ calcd for C27H20NaOþ2 m/z 399.1361, found
J. Am. Chem. Soc. 135 (2013) 5364e5367.
399.1372; [a]
20 ꢀ36.7ꢁ (c 0.23, CHCl3); The enantiomeric ratio was
ꢀ
[8] (a) M.R. Fructos, T.R. Belderrain, P. de Fremont, N.M. Scott, S.P. Nolan,
D
ꢀ
M.M. Díaz-Requejo, P.J. Perez, A gold catalyst for carbene-transfer reactions
determined to be 93 : 7 by analytical chiral HPLC. Retention time:
8.16 min, 10.34 min (OD-H column, 90/10 n-hexane/i-PrOH, 1 mL/
min, 254 nm).
from ethyl diazoacetate, Angew. Chem. Int. Ed. 44 (2005) 5284e5288;
ꢀ
ꢀ
(b) I. Rivilla, B.P. Gomez-Emeterio, M.R. Fructos, M.M. Díaz-Requejo, P.J. Perez,
Exclusive aromatic vs aliphatic CꢀH bond functionalization by carbene
insertion with gold-based catalysts, Organometallics 30 (2011) 2855e2860;
ꢀ
(c) M.R. Fructos, M.M. Díaz-Requejo, P.J. Perez, Gold and diazo reagents: a
Acknowledgement
fruitful tool for developing molecular complexity, Chem. Commun. 52 (2016)
7326e7335.
[9] For reviews, see: (a) D. Gillingham, N. Fei, Catalytic XeH insertion reactions
based on carbenoids, Chem. Soc. Rev. 42 (2013) 4918e4931;
(b) X. Guo, W. Hu, Novel multicomponent reactions via trapping of protic
onium ylides with electrophiles, Acc. Chem. Res. 46 (2013) 2427e2440;
(c) S.-F. Zhu, Q.-L. Zhou, Transition-metal-catalyzed enantioselective
HeteroatomꢀHydrogen bond insertion reactions, Acc. Chem. Res. 45 (2012)
1365e1377;
This work was supported by Futaba Electronics Memorial
Foundation, JSPS KAKENHI Grant Numbers JP18K05098 and
18H02550.
Appendix A. Supplementary data
(d) D.J. Miller, C.J. Moody, Synthetic applications of the O-H insertion reactions
of carbenes and carbenoids derived from diazocarbonyl and related diazo
compounds, Tetrahedron 51 (1995) 10811e10843. For selected examples,
see:;
(e) P. Yates, The copper-catalyzed decomposition of diazoketones, J. Am.
Chem. Soc. 74 (1952) 5376e5381;
(f) Z. Zhu, J.H. Espenson, Organic reactions catalyzed by methylrhenium
Trioxide: reactions of ethyl diazoacetate and organic azides, J. Am. Chem. Soc.
118 (1996) 9901e9907;
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.tet.2019.05.040.
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b-naphthols and methyl
aryldiazoacetate, Tetrahedron, https://doi.org/10.1016/j.tet.2019.05.040

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Please cite this article as: S. Harada et al., Gold-catalyzed chemoselective formal (3þ2)-Annulation reaction between
b-naphthols and methyl
aryldiazoacetate, Tetrahedron, https://doi.org/10.1016/j.tet.2019.05.040