Palladium-catalyzed intermolecular allylic dearomatization reaction of α-substituted β-naphthol derivatives: Scope and mechanistic investigation

Article abstract of DOI:10.1002/adsc.201400154

A highly efficient dearomatization reaction of α-substituted β-naphthols with excellent chemoselectivity and regioselectivity has been developed. Mechanistic studies demonstrated that the dearomatized alkylation product is the thermodynamically more stable compound. The etherification product could be further transformed to the dearomatization product.

Full text of DOI:10.1002/adsc.201400154

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DOI: 10.1002/adsc.201400154
Palladium-Catalyzed Intermolecular Allylic Dearomatization
Reaction of a-Substituted b-Naphthol Derivatives: Scope and
Mechanistic Investigation
Chun-Xiang Zhuoa and Shu-Li Youa,*
a
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of
Sciences, 345 Lingling Lu, Shanghai 200032, Peopleꢀs Republic of China
Fax : (+86)-21-5492-5087; phone: (+86)-21-5492-5085; e-mail: slyou@mail.sioc.ac.cn
Received: February 20, 2014; Revised: March 15, 2014; Published online: && &&, 0000
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201400154.
Abstract: A highly efficient dearomatization reaction could be further transformed to the dearomatization
of a-substituted b-naphthols with excellent chemose- product.
lectivity and regioselectivity has been developed.
Mechanistic studies demonstrated that the dearomat- Keywords: allylic substitution; chemoselectivity;
ized alkylation product is the thermodynamically dearomatization; naphthalenones; naphthols; palla-
more stable compound. The etherification product dium
Introduction
ing highly enantioenriched b-naphthalenone deriva-
tives.[9] Good chemoselectivities were obtained only
The dearomatization reaction of simple planar aro- with the 1,3-disubstituted 2-naphthols in which the
matic compounds is a powerful and straightforward steric hindrance of the disubstituted groups would
strategy for the preparation of highly functionalized prevent the competitive O-alkylation [Eq. (1),
ring structures.[1] In this regard, the transition metal- Scheme 1]. The chemoselectivity for substrates with-
catalyzed dearomatization reaction has received great out substituent at the C-3 position suffered greatly. In
attention and enormous efforts have been devoted to addition, R3 is limited with alkyl group, and electron-
this area in recent years.[2]
deficient substituents cannot be tolerated. In this
Phenols are particular interesting in dearomatiza- paper, we present a highly efficient dearomatization
tion reactions because of their abundance as starting reaction of simple 1-substituted 2-naphthol substrates
materials and utility of the products.[3,4] However, due with excellent chemoselectivity and regioselectivity
to the high energy barrier for breaking the aromatici- and the related mechanistic study [Eq. (2),
ty and the competitive O-alkylation or Friedel–Crafts Scheme 1].
alkylation reaction pathways, chemoselectivity and
stereoselectivity remain challenging issues in the cata-
lytic intermolecular dearomatization reaction. One so- Results and Discussion
lution to the problems mentioned above is to utilize
the oxidative protocol to furnish the efficient dearo- The initial exploration of the reaction conditions was
matization process of phenols.[5] The other is the in- performed using methyl 2-hydroxy-1-naphthoate (1a)
tramolecular design that benefits the selectivities.[6] and allylic carbonate (2a) as the model substrates.
Despite the progress in the intramolecular dearomati- The results are summarized in Table 1. In the pres-
zation of phenols, catalytic intermolecular dearomati- ence of 5 mol% of Pd
zation reactions of phenol derivatives under the non- Li2CO3, the reaction proceeded smoothly in DCM for
oxidative conditions have been rarely explored.[7]
21 h to provide 3aa and 4aa in a ratio of 88/12 with
ACHTUNGTREN(NUNG PPh3)4 and 2.0 equiv. of
The transition metal-catalyzed allylic substitution 72% conversion (entry 1, Table 1). To optimize the re-
reaction is one of the most powerful methods for the action conditions, various solvents such as CCl4, ben-
[8]
À
À
construction of C C and C X bonds. Recently, we zene, toluene, THF and dioxane were screened (en-
reported a palladium-catalyzed intermolecular asym- tries 2–6, Table 1). The results showed that chemose-
metric allylic dearomatization of b-naphthols, afford- lectivity and conversion of this reaction varied re-
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Chun-Xiang Zhuo and Shu-Li You
Scheme 1. Palladium-catalyzed intermolecular allylic dearomatization reaction of naphthols.
Table 1. Investigation of the reaction conditions.[a]
Entry
Solvent
Base
X
Time [h]
Conversion [%][b]
Ratio of 3aa/4aa[b]
1
2
3
4
5
6
7
8
DCM
CCl4
benzene
toluene
THF
dioxane
dioxane
dioxane
dioxane
dioxane
dioxane
dioxane
dioxane
dioxane
Li2CO3
Li2CO3
Li2CO3
Li2CO3
Li2CO3
Li2CO3
Cs2CO3
LiO-t-Bu
DBU
LiHMDS
Li2CO3
Li2CO3
Li2CO3
Li2CO3
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
2.0
0.64
0.5
0.33
21
21
21
21
21
21
41
41
41
41
27
27
27
27
72
35
71
76
42
79
68
48
>95
84
>95
82
89
91
88/12
<5/95
>95/5
79/21
71/29
>95/5
>95/5
95/5
17/83
<5/95
45/55
>95/5
>95/5
>95/5
9
10[c]
11
12
13[d]
14
[a]
Reaction conditions: 5 mol% of Pd
temperataure (for entries 1–10); 5 mol% of Pd
(2.0 mL) at room temperature (for entry 11); 5 mol% of PdAHCTUNGTRENNUNG
ACHTUNGTRENNUNG
AHCTUNGTRENNUNG
Li2CO3 in dioxane (2.0 mL) at room temperature (for entries 12–14).
Determined by H NMR of the crude reaction mixture.
1 equiv. of base was used.
Isolated yield of 3aa is 85%.
[b]
[c]
[d]
1
markably in different solvents. Dioxane was found to stitution reaction but with low selectivity for 3aa (en-
be the optimal solvent (79% conversion, 3aa/4aa: tries 9 and 10, Table 1). Li2CO3 was found to be the
>95/5, entry 6, Table 1). The effect of base was exam- optimal base (entry 6, Table 1). Investigation of the
ined next. Cs2CO3 and LiO-t-Bu could promote the loading of 2a demonstrated that an excess amount of
reaction with good chemoselectivity, but in only mod- 1a gave satisfactory results in terms of yield and che-
erate conversions (entries 7 and 8, Table 1). DBU and moselectivity (entries 11–14, Table 1). Overall, the op-
LiHMDS were effective in promoting the allylic sub- timized conditions for the reaction are the following:
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Palladium-Catalyzed Intermolecular Allylic Dearomatization Reaction
Table 2. The substrate scope – allyl carbonates.[a]
Entry
2, R1, R2
Time [h]
Ratio of 3/4[b]
3, Yield [%][c]
1[d]
2[d]
3
2a, H, H
2b, Ph, H
2b, Ph, H
2b, Ph, H
2c, 4-MeOC6H4, H
2d, 3-MeOC6H4, H
2e, 2-ClC6H4, H
2f, 4-ClC6H4, H
2g, 4-CF3C6H4, H
2h, 2-thienyl, H
2i, H, Ph
27
28
34
24
11
7
11
18
7
>95/5
75/25
95/5
3aa, 85
3ab, 72
3ab, 94
3ab, 84
3ac, 98
3ad, 87
3ae, 90
3af, 83
3ag, 69
3ah, 85
3ai, 60
4[e]
5
>95/5
>95/5
>95/5
>95/5
>95/5
>95/5
>95/5
78/22
6
7
8
9
10
11
11
18
[a]
Reaction conditions: 5 mol% of Pd
808C.
Determined by H NMR of the crude reaction mixture.
Isolated yield.
ACHTNUGTNERN(NUG PPh3)4, 0.4 mmol of 1a, 0.2 mmol of 2, 0.4 mmol of Li2CO3 in dioxane (2.0 mL) at
[b]
[c]
[d]
[e]
1
Reaction was conducted at room temperature.
Reaction conditions: 1 mol% of Pd
808C.
ACHTNUGTNERN(NUG PPh3)4, 1.0 mmol of 1a, 0.5 mmol of 2b, 1.0 mmol of Li2CO3 in dioxane (5.0 mL) at
5 mol% of PdACHTUNGTRENNUNG(PPh3)4, 2 equiv. of Li2CO3, 2 equiv. of with moderate chemoselectivity (3ai/4ai: 78/22, 60%
1a and 1 equiv. of 2a at room temperature in dioxane isolated yield of 3ai, entry 11, Table 2). To be noted,
(3aa was obtained in 85% yield with a ratio of 3aa/ when the reaction was performed with 1 mol% of
4aa as >95/5, entry 13, Table 1).
PdACTHUNGTERUNN(G PPh3)4 on a 0.5 mmol scale, the reaction proceed-
Under the optimized reaction conditions, various ed with excellent chemoselectivity in favor of dearom-
substituted allylic carbonates 2 were reacted with atized product 3ab (3ab/4ab >95/5, 84% yield,
methyl 2-hydroxy-1-naphthoate (1a) to examine the entry 4, Table 2).
generality of the process (Table 2). When cinnamyl
In addition, various b-naphthol derivatives 1b–
carbonate (2b) was utilized, the reaction occurred e were also tested in this reaction (Scheme 2). When
smoothly at room temperature in 72% yield with 3/ the a-methyl ketone-bearing substrate (1b) was used,
1 chemoselectivity in favor of the dearomatized prod- the reaction also occurred smoothly with either allyl
uct (entry 2, Table 2). The yield and chemoselectivity carbonate (2a) or cinnamyl carbonate (2b) in excel-
could be improved to 94% and 95/5, respectively, lent yields and chemoselectivity (85–99% yield,
when the reaction temperature was elevated to 808C Scheme 2). b-Naphthol derivatives bearing either
(entry 3, Table 2). The reactions of allylic carbonates electron-withdrawing groups or electron-donating
containing para-, meta-methoxyphenyl groups (2c and groups generally led to moderate to excellent yields
2d) occurred smoothly to give the desired products (3ca–3db, 66–95% yield, Scheme 2) and excellent che-
(3ac and 3ad) in 98% and 87% yield with excellent moselectivity (>95/5). Notably, the reaction could
chemoselectivity (entries 5 and 6, Table 2). Aryl allyl- also occur smoothly when a-methyl-b-naphthol (1e)
ic carbonates bearing an electron-withdrawing group was utilized, affording the a-methyl-b-naphthalenone
on the aromatic ring (o-Cl, p-Cl, p-CF3; 2e–g) all gave in good yields and chemoselectivity (3ea and 3eb, 75–
their corresponding products (3ae–ag) in good to ex- 83% yield, Scheme 2).[10,11]
cellent yields with exclusive formation of the dearom-
To gain insights into the reaction mechanism, we
atized product (entries 7–9, Table 2). The reaction of carried out the following experiments (Scheme 3). In
2-thienyl allyl carbonate (2h) with 1a afforded prod- the presence of the palladium catalyst and Li2CO3,
uct 3ah in 85% yield with excellent chemoselectivity product 4aa could be converted to 3aa and 1a with
(entry 10, Table 2). When methyl 2-(phenylallyl) car- a ratio of 89/11 [Eq. (1), Scheme 3]. Notably, no reac-
bonate (2i) was used, the reaction also went smoothly tion occurred in the absence of the palladium catalyst.
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Scheme 2. The substrate scope – naphthols. Reaction conditions: 5 mol% of PdCAHTUNGTERNU(GNN PPh3)4, 0.4 mmol of 1, 0.2 mmol of 2,
1
0.4 mmol of Li2CO3 in dioxane (2.0 mL) at 808C. Ratio of 3/4 was determined by H NMR of the crude reaction mixture.
Scheme 3. Mechanistic study.
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Palladium-Catalyzed Intermolecular Allylic Dearomatization Reaction
Figure 1. 1H NMR monitoring of the reaction (the peak at 3.69 ppm refers to the chemical shift of the methyl group in 4aa,
the peak at 3.37 ppm refers to the chemical shift of the methyl group in 1a, the peak at 3.12 ppm refers to the chemical shift
of the methyl group in 3aa).
In addition, product 3aa could not be transformed to
Based on the above experimental observations,
4aa under the same reaction conditions. Monitoring a plausible reaction mechanism was proposed, as de-
the reaction process in deuterated benzene by picted in Scheme 4. Firstly, oxidative addition of allyl-
1H NMR was then carried out. The result also demon-
strated that product 4aa could be completely convert-
ed to 3aa as the reaction proceeded (Figure 1). How-
ever, when product 4eb was utilized in the presence
of the palladium catalyst and Li2CO3, no reaction oc-
curred [Eq. (2), Scheme 3). Product 4eb could be con-
verted to 3eb with only 6% conversion even when the
temperature was elevated to 808C. This phenomenon
indicated the reversible ionization of O-allylated
product was greatly influenced by the induced effect
of the a-substituted group of the b-naphthol. Interest-
ingly, in the presence of an excess amount of a-
methyl-b-naphthol, the O-allylated product 4eb could
be converted to the C-allylated product 3eb with 86%
conversion at 808C [Eq. (3), Scheme 3]. A cross-over
experiment proved that the conversion from O-alky-
lated compounds to dearomatization products is not
an intramolecular transformation or a contact ion pair
process [Eq. (4), Scheme 3].
Scheme 4. A plausible reaction pathway.
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Scheme 5. Attempt for the enantioselective reaction
ic carbonate 2a to Pd(0) forms the p-allyl palladium
species. Then nucleophilic attack by 1 gives products
3 and 4, respectively. Product 4 can be further con-
verted to p-allyl palladium species through oxidative
addition to Pd(0).[12] The p-allyl palladium species
leads to product 3 upon the nucleophilic attack by 1.
Next, an initial attempt for the development of an
asymmetric intermolecular allylic dearomatization re-
action of 1a was carried out. To our disappointment,
low enantioselective control was observed when sev-
eral readily available chiral ligands (L1–L4) were uti-
lized in the reaction (Scheme 5).
(29.6 mg, 0.40 mmol, 200 mol%), b-naphthol derivatives
1 (0.40 mmol, 200 mol%), allyl carbonate 2 (0.20 mmol,
100 mol%), dioxane (2 mL). The reaction mixture was
stirred at 808C. After the reaction was complete (monitored
by TLC), the crude reaction mixture was filtrated with celite
and washed with DCM. The solvents were removed under
reduced pressure. The ratio of 3/4 was determined by
1H NMR of the crude reaction mixture. Then the residue
was purified by silica gel column chromatography (PE/
EtOAc=23/1) to afford the desired product 3. The charac-
terization data of the products are summarized below.
3aa: Yield: 41.0 mg (85%); yellow solid; mp 95.1–97.58C;
1H NMR (300 MHz, CDCl3): d=7.48 (d, J=10.2 Hz, 1H),
7.42–7.27 (m, 4H), 6.21 (d, J=10.2 Hz, 1H), 5.35–5.21 (m,
1H), 4.91–4.81 (m, 2H), 3.62 (s, 3H), 3.19–3.12 (m, 1H),
3.04–2.97 (m, 1H); 13C NMR (75 MHz, CDCl3): d=197.4,
170.9, 146.1, 139.2, 130.7, 130.4, 129.7, 129.6, 128.0, 126.9,
125.4, 119.3, 62.3, 52.9, 44.6; IR (thin film): nmax =3075,
Conclusions
In summary, we have developed an efficient palladi-
um-catalyzed intermolecular allylic dearomatization
reaction of b-naphthol derivatives to provide b-naph-
thalenones bearing an all-carbon quaternary center in
good to excellent yields and chemoselectivity. Mecha-
nistic studies demonstrated that the reaction for
methyl 2-hydroxy-1-naphthoate went through both
etherification and alkylation at first. Then the etherifi-
cation product could be further transformed to the
dearomatization product. For 1-alkylnaphthalen-2-ols,
the transformation from their allylic etherification
products to dearomatization products requires harsh
reaction conditions.
2953, 2921, 1730, 1661, 1619, 1414, 1225, 934, 773, 693 cmÀ1
;
MS (EI): m/z= 242 [M]+; HR-MS (EI): m/z=242.0945,
calcd. for C15H14O3 [M]+: 242.0943.
3ab: Yield: 63.0 mg (94%); yellow oil; 1H NMR
(300 MHz, CDCl3): d=7.49–7.37 (m, 5H), 7.22–7.10 (m,
5H), 6.23–6.00 (m, 2H), 5.73–5.63 (m, 1H), 3.67 (s, 3H),
3.36–3.28 (m, 1H), 3.21–3.14 (m, 1H); 13C NMR (75 MHz,
CDCl3): d=197.5, 171.0, 146.1, 139.2, 137.0, 134.1, 130.5,
129.7, 129.6, 128.3, 128.1, 127.2, 126.9, 126.0, 125.3, 122.2,
62.7, 53.0, 44.0; IR (thin film): nmax =3026, 2951, 2849, 1740,
1660, 1619, 1565, 1493, 1220, 1017, 742, 694 cmÀ1; MS (EI):
m/z=318 [M]+; HR-MS (EI): m/z=318.1260, calcd. for
C21H18O3 [M]+: 318.1256.
3ac: Yield: 62.5 mg (98%); yellow solid; mp 101.3–103.5;
1H NMR (300 MHz, CDCl3): d=7.47–7.34 (m, 5H), 7.02 (d,
J=8.7 Hz, 2H), 6.72 (d, J=8.7 Hz, 2H), 6.18 (d, J=9.9 Hz,
1H), 6.12 (d, J=15.6 Hz, 1H), 5.56–5.45 (m, 1H), 3.73 (s,
3H), 3.63 (s, 3H), 3.30–3.23 (m, 1H), 3.15–3.08 (m, 1H);
13C NMR (100 MHz, CDCl3): d=197.5, 171.0, 158.9, 146.0,
139.3, 133.4, 130.3, 129.8, 129.7, 129.6, 128.0, 127.2, 126.9,
125.3, 119.8, 113.7, 62.8, 55.1, 52.9, 44.0. IR (thin film):
nmax =2966, 2850, 1739, 1658, 1617, 1565, 1487, 1227, 1033,
762 645 cmÀ1; MS (EI): m/z=348 [M]+; HR-MS (EI): m/z=
348.1364, calcd. for C22H20O4 [M]+: 348.1362.
Experimental Section
General Procedure for Palladium-Catalyzed
Intermolecular Allylic Dearomatization Reaction of
Naphthol Derivatives
A flame-dried Schlenk tube was cooled to room tempera-
ture and filled with argon. To this flask were added Pd-
ACHTUNGTRENNUNG(PPh3)4 (11.5 mg, 0.010 mmol, 5 mol%), lithium carbonate
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3ad: Yield: 61.1 mg (87%); yellow oil; 1H NMR
(300 MHz, CDCl3): d=7.46–7.42 (m, 5H), 7.11 (t, J=
7.8 Hz, 1H), 6.71–6.62 (m, 3H), 6.20–6.13 (m, 2H), 5.70–
5.59 (m, 1H), 3.73 (s, 3H), 3.64 (s, 3H), 3.32–3.24 (m, 1H),
3.17–3.10 (m, 1H); 13C NMR (75 MHz, CDCl3): d=197.5,
170.9, 159.5, 146.1, 139.1, 138.4, 133.9, 130.4, 129.7, 129.5,
129.2, 128.1, 126.9, 125.2, 122.5, 118.7, 112.6, 111.6, 62.6,
55.1, 52.9, 43.9; IR (thin film): nmax =2965, 1740, 1661, 1619,
1580, 1488, 1221, 1046, 765, 646 cmÀ1; MS (EI): m/z=348
[M]+; HR-MS (EI): m/z=348.1366, calcd. for C22H20O4
[M]+: 348.1362.
1055, 769, 700 cmÀ1; MS (EI): m/z=318 [M]+; HR-MS (EI):
m/z=318.1260, calcd for C21H18O3 [M]+: 318.1256.
4ai: Yield: 12.4 mg (19%); colorless oil; 1H NMR
(400 MHz, CDCl3): d=7.88 (d, J=9.2 Hz, 1H), 7.79 (d, J=
8.0 Hz, 1H), 7.53–7.49 (m, 3H), 7.40–7.33 (m, 4H), 7.30 (d,
J=9.2 Hz, 1H), 5.61 (s, 1H), 5.50 (s, 1H), 5.08 (s, 2H), 3.89
(s, 2H); 13C NMR (100 MHz, CDCl3): d=168.3, 153.4, 142.7,
138.2, 131.6, 131.0, 128.7, 128.4, 128.0, 128.0, 127.6, 126.0,
124.3, 123.8, 118.2, 114.8, 114.4, 71.0, 52.2; IR (thin film):
nmax =3081, 3030, 1723, 1626, 1511, 1437, 1282, 1229, 1136,
1062, 779, 704 cmÀ1; HR-MS (ESI): m/z=319.1330, calcd.
for C21H19O3 [M+H]+: 319.1329.
3ae: Yield: 63.8 mg (90%); yellow oil; 1H NMR
(300 MHz, CDCl3): d=7.49–7.35 (m, 5H), 7.20–7.06 (m,
4H), 6.50 (d, J=15.9 Hz, 1H), 6.21 (d, J=10.2 Hz, 1H),
5.72–5.62 (m, 1H), 3.64 (s, 3H), 3.37–3.30 (m, 1H), 3.20–
3.12 (m, 1H); 13C NMR (100 MHz, CDCl3): d=197.2, 170.8,
146.1, 139.1, 135.2, 132.6, 130.6, 130.5, 129.8, 129.5, 129.4,
128.2, 126.9, 126.8, 126.6, 125.4, 125.2, 62.7, 52.9, 43.8; IR
(thin film): nmax =3064, 2960, 1741, 1661, 1620, 1565, 1489,
1221, 1050, 752, 644 cmÀ1; MS (EI): m/z=352 [M]+; HR-MS
(EI): m/z=352.0867, calcd. for C21H17O3Cl [M]+: 352.0866.
3af: Yield: 72.1 mg (83%); yellow oil; 1H NMR
(300 MHz, CDCl3): d=7.47–7.34 (m, 5H), 7.15 (d, J=
8.7 Hz, 2H), 7.00 (d, J=8.4 Hz, 2H), 6.20–6.11 (m, 2H),
5.69–5.59 (m, 1H), 3.64 (s, 3H), 3.31–3.24 (m, 1H), 3.15–
3.08 (m, 1H); 13C NMR (75 MHz, CDCl3): d=197.3, 170.9,
146.1, 139.1, 135.3, 132.8, 130.5, 129.8, 129.5, 128.4, 128.2,
127.2, 126.9, 125.2, 123.0, 62.6, 53.0, 43.8; IR (thin film):
nmax =3028, 2963, 1740, 1661, 1620, 1565, 1490, 1221, 1052,
761, 644 cmÀ1; MS (EI): m/z=352 [M]+; HR-MS (EI): m/z=
352.0864, calcd. for C21H17O3Cl [M]+: 352.0866.
3ba: Yield: 53.4 mg (85%); yellow oil; 1H NMR
(300 MHz, CDCl3): d=7.59 (d, J=9.9 Hz, 1H), 7.48–7.40
(m, 3H), 7.17 (d, J=7.5 Hz, 1H), 6.29 (d, J=9.9 Hz, 1H),
5.33–5.19 (m, 1H), 4.87–4.77 (m, 2H), 3.08–3.01 (m, 1H),
2.96–2.89 (m, 1H), 1.84 (s, 3H); 13C NMR (75 MHz,
CDCl3): d=200.3, 198.6, 146.6, 138.3, 131.3, 130.7, 130.0,
129.9, 128.3, 127.2, 126.0, 118.7, 69.8, 44.1, 27.5; IR (thin
film): nmax =3074, 2976, 2923, 1741, 1628, 1514, 1438, 1264,
986, 783, 669 cmÀ1; MS (EI): m/z=226 [M]+; HR-MS (EI):
m/z=226.0998, calcd. for C15H14O2 [M]+: 226.0994.
3bb: Yield: 60.6 mg (99%); yellow oil; 1H NMR
(300 MHz, CDCl3): d=7.54 (d, J=9.6 Hz, 1H), 7.47–7.39
(m, 3H), 7.26–7.05 (m, 6H), 6.26 (d, J=10.2 Hz, 1H), 6.16
(d, J=15.3 Hz, 1H), 5.69–5.58 (m, 1H), 3.22–3.15 (m, 1H),
3.09–3.03 (m, 1H), 1.86 (s, 3H); 13C NMR (75 MHz,
CDCl3): d=200.5, 198.7, 146.6, 138.4, 137.0, 133.6, 130.7,
130.1, 130.0, 128.3, 128.2, 127.2, 127.1, 126.0, 125.9, 122.9,
70.1, 43.4, 27.6; IR (thin film): nmax =3058, 3025, 2920, 1721,
1655, 1563, 1468, 1208, 965, 745, 694 cmÀ1; MS (EI): m/z=
302 [M]+; HR-MS (EI): m/z=302.1302, calcd. for C21H18O2
[M]+: 302.1307.
3ag: Yield: 53.2 mg (69%); yellow oil; 1H NMR
(300 MHz, CDCl3): d=7.50–7.36 (m, 7H), 7.17 (d, J=
8.1 Hz, 1H), 6.25–6.18 (m, 2H), 5.82–5.72 (m, 1H), 3.66 (s,
3H), 3.35–3.27 (m, 1H), 3.18–3.11 (m, 1H); 13C NMR
(75 MHz, CDCl3): d=197.3, 170.8, 146.1, 140.3, 139.0, 132.8,
130.6, 129.8, 129.7, 129.5, 129.3, 128.8, 128.4, 128.3, 126.9,
126.2, 125.9, 125.6, 125.3, 125.2, 124.1 (q, J=270.3 Hz), 62.6,
53.1, 43.8; 19F NMR (282 MHz, CDCl3): d=À62.92 (3F); IR
(thin film): nmax =2964, 1742, 1662, 1617, 1566, 1489, 1223,
1066, 762, 647 cmÀ1; MS (EI): m/z=386 [M]+; HR-MS (EI):
m/z=386.1131, calcd. for C22H17O3F [M]+: 386.1130.
3ah: Yield: 46.0 mg (85%); yellow solid; mp 86.3–88.58C;
1H NMR (300 MHz, CDCl3): d=7.47–7.32 (m, 5H), 7.01 (d,
J=5.1 Hz, 1H), 6.85–6.82 (m, 1H), 6.71 (d, J=3.6 Hz, 1H),
6.29 (d, J=15.3 Hz, 1H), 6.19 (d, J=9.6 Hz, 1H), 5.53–5.43
(m, 1H), 3.63 (s, 3H), 3.27–3.20 (m, 1H), 3.13–3.06 (m,
1H); 13C NMR (75 MHz, CDCl3): d=197.4, 170.9, 146.1,
141.9, 139.1, 130.4, 129.8, 129.6, 128.2, 127.2, 126.9, 125.2,
3ca: Yield: 39.4 mg (71%); yellow oil; 1H NMR
(300 MHz, CDCl3): d=8.32 (s, 1H), 7.59–7.52 (m, 2H),
7.48–7.43 (m, 1H), 7.19 (d, J=7.5 Hz, 1H), 5.37–5.23 (m,
1H), 4.87–4.79 (m, 2H), 3.90 (s, 3H), 3.10–3.03 (m, 1H),
2.94–2.87 (m, 1H), 1.87 (s, 3H); 13C NMR (75 MHz,
CDCl3): d=200.3, 194.2, 164.6, 151.7, 140.0, 132.6, 131.9,
130.8, 128.7, 128.6, 127.2, 126.6, 119.2, 71.1, 52.5, 44.6, 27.9;
IR (thin film): nmax =3077, 3004, 2953, 1722, 1678, 1616,
1438, 1220, 965, 761, 642 cmÀ1; MS (EI): m/z=284 [M]+;
HR-MS (EI): m/z=284.1052, calcd. for C17H16O4 [M]+:
284.1049.
3cb: Yield: 22.4 mg (66%); yellow oil; 1H NMR
(300 MHz, CDCl3): d=8.27 (s, 1H), 7.59–7.56 (m, 2H),
7.48–7.43 (m, 1H), 7.27–7.16 (m, 4H), 7.08–7.06 (m, 2H),
6.18 (d, J=15.6 Hz, 1H), 5.72–5.62 (m, 1H), 3.85 (s, 3H),
3.24–3.17 (m, 1H), 3.08–3.01 (m, 1H), 1.90 (s, 3H);
13C NMR (75 MHz, CDCl3): d=200.3, 194.5, 164.5, 151.6,
139.9, 136.8, 134.1, 132.6, 132.0, 128.7, 128.6, 128.3, 127.2,
126.6, 126.0, 122.3, 71.4, 52.5, 43.7, 28.0; IR (thin film):
nmax =3058, 3026, 2952, 1721, 1667, 1615, 1495, 1217, 966,
746, 648 cmÀ1; MS (EI): m/z=360 [M]+; HR-MS (EI): m/z=
360.1358, calcd. for C23H20O4 [M]+: 360.1362.
125.1, 123.7, 122.0, 62.6, 52.9, 43.8; IR (thin film): nmax
=
;
2964, 1730, 1656, 1619, 1564, 1488, 1220, 1044, 764, 647 cmÀ1
MS (EI): m/z=324 [M]+; HR-MS (EI); m/z=324.0818,
calcd. for C19H16O3S [M]+: 324.0820.
3ai: Yield: 38.3 mg (60%); white solid; mp 59.3–61.18C;
1H NMR (300 MHz, CDCl3): d=7.25–7.04 (m, 8H), 6.91–
6.88 (m, 2H), 5.91 (d, J=9.9 Hz, 1H), 4.92 (d, J=1.5 Hz,
1H), 4.74 (s, 1H), 3.74 (d, J=14.1 Hz, 1H), 3.62–3.57 (m,
4H); 13C NMR (75 MHz, CDCl3): d=197.4, 171.2, 145.5,
143.5, 140.9, 138.8, 129.9, 129.7, 129.4, 127.8, 127.5, 127.2,
127.0, 126.8, 125.4, 117.7, 62.2, 53.0, 45.0; IR (thin film):
nmax =3024, 2964, 2851, 1734, 1651, 1624, 1566, 1491, 1240,
3da: Yield: 36.0 mg (77%); yellow oil; 1H NMR
(300 MHz, CDCl3): d=7.53 (d, J=9.6 Hz, 1H), 7.08 (d, J=
8.4 Hz, 1H), 7.07–6.94 (m, 2H), 6.28 (d, J=10.2 Hz, 1H),
5.33–5.19 (m, 1H), 4.88–4.78 (m, 2H), 3.87 (s, 3H), 3.05–
2.98 (m, 1H), 2.94–2.87 (m, 1H), 1.83 (s, 3H); 13C NMR
(75 MHz, CDCl3): d=200.5, 198.8, 159.2, 146.4, 131.5, 131.0,
130.0, 128.3, 126.4, 118.6, 116.3, 114.8, 69.2, 55.4, 43.9, 27.3;
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IR (thin film): nmax =3077, 3004, 2935, 1721, 1656, 1599,
1432, 1251, 997, 715, 668 cmÀ1; MS (EI): m/z=256 [M]+;
HR-MS (EI): m/z=256.1104, calcd. for C16H16O3 [M]+:
256.1099.
1H NMR (400 MHz, CDCl3): d=11.00 (s, 1H), 8.52–8.51 (m,
1H), 7.84–7.78 (m, 2H), 7.55 (dt, J=6.8, 1.2 Hz, 1H), 7.35
(t, J=7.2 Hz, 1H), 4.02 (s, 3H), 2.72 (s, 3H); 13C NMR
(100 MHz, CDCl3): d=204.0, 170.0, 154.0, 134.6, 133.8,
130.5, 129.8, 126.9, 124.4, 123.6, 123.3, 113.5, 52.8, 32.4; IR
(thin film): nmax =3112, 3038, 2962, 2919, 1678, 1631, 1602,
3db: Yield: 65.4 mg (95%); yellow oil; 1H NMR
(300 MHz, CDCl3): d=7.48 (d, J=9.9 Hz, 1H), 7.21–7.07
(m, 6H), 7.02–6.98 (m, 1H), 6.92–6.91 (m, 1H), 6.25 (d, J=
10.2 Hz, 1H), 6.18 (d, J=15.9 Hz, 1H), 5.69–5.59 (m, 1H),
3.85 (s, 3H), 3.19–3.12 (m, 1H), 3.08–3.01 (m, 1H), 1.85 (s,
3H); 13C NMR (75 MHz, CDCl3): d=200.6, 198.9, 159.2,
146.5, 137.0, 133.3, 130.9, 129.9, 128.3, 128.2, 127.1, 126.3,
126.0, 123.1, 116.4, 114.9, 69.4, 55.4, 43.1, 27.3; IR (thin
film): nmax =3057, 3026, 2919, 1720, 1652, 1599, 1448, 1246,
966, 743, 694 cmÀ1; MS (EI): m/z=332 [M]+; HR-MS (EI):
m/z=332.1418, calcd. for C22H20O3 [M]+: 332.1412.
1508, 1435, 1272, 1082, 791, 752 cmÀ1; HR-MS (ESI): m/z=
245.0816, calcd. for C14H13O4 [M+H]+: 245.0808.
3ea:[10] Yield: 32.9 mg (75%); 1H NMR (300 MHz,
CDCl3): d=7.44–7.41 (m, 3H), 7.34–7.26 (m, 2H), 6.17 (d,
J=9.9 Hz, 1H), 5.37–5.23 (m, 1H), 4.87–4.79 (m, 2H), 2.89–
2.82 (m, 1H), 2.60–2.53 (m, 1H), 1.47 (s, 3H); 13C NMR
(75 MHz, CDCl3): d=203.8, 145.6, 145.1, 133.0, 129.9, 129.6,
129.4, 126.7, 125.2, 117.9, 51.5, 46.7, 26.8; IR (thin film):
nmax =3058, 3026, 2971, 1720, 1656, 1620, 1448, 1240, 966,
745, 694 cmÀ1; MS (EI): m/z=198 [M]+; HR-MS (EI): m/z=
198.1047, calcd. for C14H14O [M]+: 198.1045.
Procedure for the Synthesis of 1-(2-Hydroxy-6-
methoxynaphthalen-1-yl)ethanone (1d)
A flame-dried reaction flask was cooled to room tempera-
ture and filled with argon. To this flask were added 6-me-
thoxynaphthalen-2-ol (700 mg, 4.0 mmol), chloroform
(10 mL), boron trifluoride diethyl etherate (0.7 mL,
5.5 mmol). The reaction mixture was cooled to 08C, and
acetic anhydride (0.5 mL, 5.3 mmol) was added slowly. After
that, the reaction mixture was stirred at room temperature
for 4 days. After the reaction was complete (monitored by
TLC), the reaction mixture was cooled to 08C and quenched
with water. The product was partitioned between water and
CHCl3. The layers were separated, and the aqueous layer
was extracted with DCM. The combined organic layers were
washed with brine, dried over Na2SO4, and concentrated
under vacuum. The crude material was purified by column
chromatography using PE/EtOAc (20:1) to give 1d as
a brown solid; yield: 589 mg (68%); mp 67.9–70.18C.
1H NMR (300 MHz, CDCl3): d=13.16 (s, 1H), 7.80 (d, J=
9.3 Hz, 1H), 7.59 (d, J=9.3 Hz, 1H), 7.10–7.07 (m, 1H),
6.99–6.96 (m, 2H), 3.78 (s, 3H), 2.67 (s, 3H); 13C NMR
(100 MHz, CDCl3): d=204.3, 162.2, 155.7, 136.3, 129.7,
126.5, 125.7, 120.2, 119.4, 115.1, 108.5, 55.3, 32.6; IR (thin
film): nmax =3139, 3087, 2965, 2918, 1756, 1609, 1573, 1507,
1209, 1028, 809 cmÀ1; HR-MS (ESI): m/z=217.0863, calcd.
for C13H13O3 [M+H]+: 217.0859.
3eb:[9] Yield: 42.7 mg (83%); colorless oil; 1H NMR
(300 MHz, CDCl3): d=7.52–7.45 (m, 2H), 7.42 (d, J=
10.2 Hz, 1H), 7.34–7.30 (m, 2H), 7.27–7.11 (m, 5H), 6.20 (d,
J=15.9 Hz, 1H), 6.17 (d, J=9.6 Hz, 1H), 5.71 (d, J=15.0,
7.2 Hz, 1H), 3.03–2.96 (m, 1H), 2.74–2.67 (m, 1H), 1.54 (s,
3H); 13C NMR (75 MHz, CDCl3): d=204.0, 145.6, 145.2,
137.2, 133.0, 130.0, 129.7, 129.6, 128.4, 127.1, 126.9, 126.8,
126.1, 125.2, 124.7, 52.0, 46.3, 26.5.
Procedure for the Synthesis of Methyl
4-Acetyl-3-hydroxy-2-naphthoate (1c)
A flame-dried reaction flask was cooled to room tempera-
ture and filled with argon. To this flask were added methyl
3-hydroxy-2-naphthoate (2.02 g, 10.0 mmol), aluminum chlo-
ride (2.6 g, 19.5 mmol), 1,2-dichloroethane (DCE) (30 mL).
The reaction mixture was cooled to 08C, and acetic anhy-
dride (0.8 mL, 8.5 mmol) was added slowly. After that, the
reaction mixture was stirred and heated to reflux for 46 h.
After the reaction was complete (monitored by TLC), the
reaction mixture was cooled to 08C and quenched with
water. The product was partitioned between water and
DCE. The layers were separated, and the aqueous layer was
extracted with DCM. The combined organic layers were
washed with brine, dried over Na2SO4, and concentrated
under vacuum. The crude material was purified by column
chromatography using PE/EtOAc (40:1) to give 1c as
a yellow solid; yield: 961 mg (40%); mp 136.0–138.28C.
Acknowledgements
We thank the National Basic Research Program of China
(973 Program 2010CB833300), the National Natural Science
Foundation of China (21025209, 21121062, 21332009), and
the Science and Technology Commission of Shanghai Munic-
ipality (13JC1406900) for generous financial support.
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Chun-Xiang Zhuo and Shu-Li You
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asc.wiley-vch.de
ꢁ 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 0000, 000, 0 – 0
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These are not the final page numbers!