Facile and efficient synthesis of hydrophenanthren-1(2H)-ones and naphtho[2,1-c]furan-3(1H)-ones by a palladium-catalyzed aryne annulation strategy

Article abstract of DOI:10.1002/adsc.200900703

Novel palladium-catalyzed carboannulation reactions of arynes with functionalized vinyl iodides are reported. By applying allyl-substituted iodocycloenones and iodofuranones, a series of hydrophenanthren-1(2H)-ones and naphtho[2,1-c]furan-3(1H)-ones were efficiently constructed in one pot under mild conditions.

Full text of DOI:10.1002/adsc.200900703

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DOI: 10.1002/adsc.200900703
Facile and Efficient Synthesis of Hydrophenanthren-1(2H)-ones
and Naphtho[2,1-c]furan-3(1H)-ones by a Palladium-Catalyzed
G
Aryne Annulation Strategy
Xian Huang,a,b,* Feng Sha,a and Jiawei Tonga
a
Department of Chemistry, Zhejiang University (Xixi Campus), Hangzhou 310028, Peopleꢀs Republic of China
Fax : (+86)-571-8880-7077; phone: (+86)-571-8880-7077; e-mail: huangx@mail.hz.zj.cn
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of
b
Sciences, Shanghai 200032, Peopleꢀs Republic of China
Received: October 10, 2009; Published online: February 9, 2010
Supporting information for this article is available on the WWW under
http://dx.doi.org/10.1002/adsc.200900703.
Abstract: Novel palladium-catalyzed carboannula-
tion reactions of arynes with functionalized vinyl io-
dides are reported. By applying allyl-substituted io-
docycloenones and iodofuranones, a series of hy-
oped to synthesize a variety of multicyclic compounds
and this strategy has been extended to arynes in the
last decades.[7] Particularly, the convenient generation
of arynes from the precursors ortho-silylaryl triflates
has been developed recently,[8,9] which facilitates the
Pd-catalyzed annulation reactions of arynes and
avoids the harsh conditions and the limitation of func-
tional group compatibility. Pd-catalyzed annulations
of arynes with aryl, vinylic and allylic halides have
been reported previously, providing efficient methods
for the construction of heterocycles and carbocy-
cles.[10] However, examples of these reactions are still
very limited, mainly due to the obvious problem asso-
ciated with the high reactivity of arynes, which leads
to cyclotrimerization in Pd-catalyzed reactions to
drophenanthren-1(2H)-ones
and
naphthoACTHNGUTERNNU[G 2,1-
c]furan-3(1H)-ones were efficiently constructed in
one pot under mild conditions.
Keywords: allylvinyl iodides; annulation; arynes;
hydrophenanthren-1(2H)-ones;
c]furan-3(1H)-ones; palladium
naphthoACTHNGUTERNNU[G 2,1-
Polysubstituted naphthalenes, including hydrophen- form the polycyclic aromatic hydrocarbons.[11] In this
anthren-1(2H)-ones and naphtho[2,1-c]furan-3(1H)- paper, we wish to report a mild and highly efficient
ones, are not only the fundamental structural unit of approach for the synthesis of hydrophenanthren-
N
ACHTUNGTRENNUNG
biologically active compounds, but also building 1(2H)-ones and naphthoACTHNUTRGNE[NUG 2,1-c]furan-3(1H)-ones via a
blocks in organic synthesis.[1,2] Therefore, considerable Pd-catalyzed annulation reaction of arynes with allyl-
efforts have been devoted to develop efficient meth- substituted, functionalized vinyl iodides.
ods for their preparation.[2c–g,3] According to the litera-
Initially, the reaction of 2-allyl-3-iodocyclohex-2-
ture, unsubstituted hydrophenanthren-1(2H)-one can enone 1a and 1.5 equivalents of 2-(trimethylsilyl)-
be easily obtained by Friedel–Crafts-type cyclization phenyl triflate 2a was carried out in the presence of
of 4-(naphthalen-1-yl)butanoic acid derivatives; also, 10 mol% of Pd
starting from naphtho[2,1-c]furan-1,3-dione, unsubsti- 3.0 equivalents of CsF in MeCN at room temperature
tuted naphthoACHTUNGTRENNUNG[2,1-c]furan-3(1H)-ones can be fur- for 24 h. The desired annulation product 3a was ob-
ACHTNUGTRNEUN(GN PPh3)4, 1.5 equivalents of K2CO3, and
AHCTUNGTRENNUNG
nished conveniently.[2e,4] However, analogues substi- tained in 60% yield, but a considerable amount of tri-
tuted in the aromatic rings are less common, and the phenylene 4 was also generated (Table 1, 38%,
reported syntheses are somewhat laborious and, in entry 1). By changing the catalyst to Pd2dba3·CHCl3,
some cases, involve multistep processes.[5] Therefore, the reaction gave 3a in a higher yield (Table 1, 67%,
a direct and efficient procedure for these classes of entry 4). Employing the mixed solvent CH3CN/tolu-
compounds remains elusive.
ene in a 1:1 ratio could slow the generation of the
Transition metal-catalyzed annulation reactions of benzyne, resulting in a decreased yield of 4 (Table 1,
unsaturated compounds are of great synthetic value.[6] compare entries 2 with 3, 4 with 5).[10d,12] When using
For example, the Pd-catalyzed annulation of alkynes Cs2CO3 as the base instead of K2CO3, a better result
by substituted aryl and vinylic halides has been devel- was obtained (Table 1, compare entries 5 with 6). Fi-
Adv. Synth. Catal. 2010, 352, 379 – 385
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379

Xian Huang et al.
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Table 1. Optimization of the Pd-catalyzed annulation of benzyne.[a]
Entry
PdLn
Ligand
Base
Solvent ratio [v:v]
3a [%][b]
4 [%][c]
1
2
3
4
5
6
7
8
Pd
Pd
Pd
Pd2dba3[d]
Pd2dba3[d]
Pd2dba3[d]
Pd2dba3
N
–
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
1:0
1:0
1:1
1:0
1:1
1:1
1:1
1:1
1:1
1:1
1:1
60
50
54
67
65
72
75
31
28
10
49
38
29
13
28
8
11
5
66
53
46
–
PPh3
–
–
–
–
[d]
dba[e]
BINAP
dppp
dppf
dba[e]
[d]
Pd2dba3[d]
9
10
11
Pd2dba3[d]
Pd2dba3[f]
Pd2dba3
[a]
The reactions were carried out in 0.5 mmol of 1a, 0.75 mmol of 2a and 6 mL of solvent at room termperature overnight.
Yield of isolated product based on 1a.
[b]
[c]
[d]
[e]
[f]
Yield of isolated product based on 2a.
.
5 mol% Pd2dba3 CHCl3 were employed.
5 mol% dba were employed.
.
2 mol% Pd2dba3 CHCl3 were employed. dba=dibenzylideneacetone, BINAP=2,2’-bis(diphenylphosphino)-1,1’-binaph-
ACHTUNGTRENNUNGthyl, dppp=1,3-bis(diphenylphosphino)propane, dppf=1,1’-bis(diphenylphosphino)ferrocene.
nally, the effect of ligands was investigated (Table 1, tries 7 and 8). It is notable that when the o-methoxy-
entries 7–10). The yield of 3a was slightly higher benzyne precursor 2e was allowed to react with 1c,
(75%) in the presence of 5 mol% of dba and 4 de- the reaction showed good regioselectivity giving 3ia
creased to 5% yield (Table 1, entry 7). However, as the major product (Table 2, entry 9), which may be
changing dba for other ligands such as BINAP, dppp, explained by the coordination of the methoxy group
and dppf was less effective (Table 1, entries 8–10). with the palladium atom (Scheme 1) in the step of in-
Thus, the optimized reactions were to employ sertion of an aryne to form the arylpalladium inter-
1.0 equivalent of 1a, 1.5 equivalents of 2a, 5 mol% of mediate C (Scheme 3).[12,13] The configurations of 3ga,
Pd2dba3·CHCl3 and dba, 1.5 equivalents of Cs2CO3, 3ha and 3ia were established by the NOESY spec-
and 3.0 equivalents of CsF in CH3CN/toluene (1:1) at trum studies (Scheme 1).
room temperature.
Considering that naphthoACTHNGUTRENNU[G 2,1-c]furan-3(1H)-ones
With the optimized reaction conditions in hand, the are also an important structural unit in pharmaceuti-
scope and limitations of this reaction were next exam- cally active compounds and valuable building blocks
ined using 2-allyl-3-iodocycloenones 1 and aryne pre- in organic synthesis,[2e–g] we next expanded the reac-
cursors 2. The results summarized in Table 2 demon- tion scope to substituted allyliodofuranones 5. Firstly,
strated that the yields and regioselectivity were affect- when the reaction of 5a with 2a was carried out at
ed by the structures of the two reaction partners to room temperature, naphthoACHTNUGTRENNUNG
some extent.
As shown in Table 2, when substituted five- or six-
membered ring enones 1a–d and symmetrical arynes
2a, b were employed, the reaction proceeded smooth-
ly to give corresponding hydrophenanthren-1(2H)-
ones 3 in good yields (Table 2, entries 1–6). When
asymmetric arynes 2c–e were used, regioisomeric
compounds could be afforded (Table 2, entries 7–9).
When the reaction was carried out with p-fluoro- or
o-methylaryne, the regioselectivity is poor affording a
mixture of 3ga and 3gb or 3ha and 3hb (Table 2, en- Scheme 1. Configuration of the products.
380
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Adv. Synth. Catal. 2010, 352, 379 – 385

Efficient Synthesis of Hydrophenanthren-1(2H)-ones and Naphtho
ACHTUNGERTN[NUNG 2,1-c]furan-3(1H)-ones
Table 2. Pd-catalyzed synthesis of substituted hydrophenanthren-1(2H)-ones.[a]
Entry
1
1 [R1, R2]
2
Time [h]
Product 3
Yield [%][b]
2a 15
3a
75
1a [H, H]
2
3
4
2b 18
2a 12
2b 17
2a 12
3b
3c
3d
70
71
69
1b [H, H]
5
6
7
1c [Me, H]
3e
79
72
73
1d [Me, Me] 2a 15
3f
1c
1a
2c 12
3ga/3gb [57:43][c]
8
2d 18
3ha/3hb [46:54][c]
64
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381

Xian Huang et al.
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Table 2. (Continued)
Entry
1 [R1, R2]
2
Time [h]
Product 3
Yield [%][b]
9
1c
2e 17
3ia/3ib [91:9][c]
55
[a]
Reaction conditions: 1 (0.3 mmol), 2 (0.45 mmol), CsF (0.9 mmol), Cs2CO3 (0.45 mmol), Pd2dba3·CHCl3 (5 mol%), dba (5
mol%), MeCN (2 mL), toluene (2 mL), room temperature.
[b]
[c]
Yield of isolated product based on 1.
1
The ratio of isomers was calculated on H NMR spectrum and the configuration was confirmed by the NOESY spectrum.
Table 3. Pd-catalyzed synthesis of substituted naphthoACTHNUTRGNEUNG
[2,1-c]furan-3(1H)-ones.[a]
Entry
1
5 [R1, R2, R3]
2
Time [h]
Product 6
Yield [%][b]
62
5a [Me, Me, H] 2a 20
6a
6b
2
3
5b [Me, H, H]
2a 20
55
57
5c [Me, Me, Ph] 2b 24
6c
4
5c
5a
2d 28
6da/6db [14:86][c]
53
25
28
6ea/6eb [74:26][c]
6ea/6eb [85:15][c]
54
49[d]
5
2e
[a]
Reaction conditions: 5 (0.3 mmol), 2 (0.45 mmol), CsF (0.9 mmol), Cs2CO3 (0.45 mmol), Pd2dba3·CHCl3 (5 mol%), dba (5
mol%), MeCN (2 mL), toluene (2 mL), 508C.
[b]
[c]
[d]
Yield of isolated product based on 5.
The ratio of isomers was calculated on H NMR spectrum and the configuration was confirmed by the NOESY spectrum.
1
The reaction was conducted at 358C.
ature to 508C, the reaction gave a better result tions proceeded smoothly to give the corresponding
(Table 3, 62%, entry 1). When the mono-, di-, or tri- naphtho[2,1-c]furan-3(1H)-ones 6 in moderate yields
substituted iodofuranones 5 were employed, the reac- with good regioselectivity (Table 3, entries 2–5).
AHCTUNGTRENNUNG
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Adv. Synth. Catal. 2010, 352, 379 – 385

Efficient Synthesis of Hydrophenanthren-1(2H)-ones and NaphthoACHTNUTRGNEUNG[2,1-c]furan-3(1H)-ones
It is noteworthy that when the o-methylbenzyne
precursor was employed (Table 3, entry 4), the regio-
selectivity was much higher than when using 1a as the
starting material (Table 2, entry 8) and 6da, 6db were
obtained in a 14:86 ratio. This result indicated that in-
termediate B or D (Scheme 3) would preferentially
undergo carbopalladation to form 6db overwhelming-
ly as major product, possibly due to the steric hin-
drance between the benzyl group and the methyl
group in 6da (Scheme 2). It is the similar case with
the o-methoxybenzyne precursor in entry 9, Table 2;
using iodofuranone 5a as substrate, the reaction gave
Scheme 4.
two regioisomers in a ratio of 74:26 (Table 3, entry 5).
Interestingly, the reaction showed better regioselec-
titvity when the reaction was carried out at 358C,
giving 6ea and 6eb in an 85:15 ratio, although the D, which might subsequently add to the benzyne to
yield was slightly lower. give arylpalladium intermediate C. Regardless of how
On the basis of the known chemistry of arynes and intermediate C is formed, the palladium-carbon bond
previous work on the Pd-catalyzed annulation of alk- in this intermediate can then undergo a intramolecu-
ACHTUNGTRENNUNG
ynes,[7] we proposed two plausible mechanisms (paths lar Heck coupling to afford intermediate E.[10a,b,f]
I and II) for this reaction (Scheme 3). In path I, the After b-hydride elimination and subsequent aromati-
benzyne generated from the triflate in the presence of zation, the reaction affords the final product 3.
the CsF coordinates with Pd(0), giving palladacycle
Bearing a methyl group on the 2 position of the
A.[14] Oxidative addition of the vinyl iodide 1 to A allyl moiety, 1e could not undergo b-hydride elimina-
might generate an arylpalladium(IV) complex B,[10a] tion in this reaction (Scheme 4). The same as predict-
which could lead to a new arylpalladium intermediate ed, when 1e reacted with benzyne (from precursor
C via reductive elimination. Alternatively, according 2a), the reaction gave a mixture of complex com-
to path II, Pd(0) might add oxidatively to the vinyl pounds. Interestingly, by employing butyl acrylate as
iodide 1 to afford the arylpalladium(II) intermediate trapping agent to terminate the reaction of intermedi-
ate E (Scheme 3), we obtained 7 in 67% yield. By
comparsion, the reaction of 1a, 2a and butyl acrylate
afforded 3a only in 70% yield, with no other product
formed (Scheme 4).
In conclusion, we have disclosed a novel, facile
method for the synthesis of hydrophenanthren-1(2H)-
ones and naphthoACTHNUTRGNEUNG[2,1-c]furan-3(1H)-ones, which in-
volves the Pd-catalyzed carboannulation of arynes
with allyl-substituted iodocycloenones and iodofura-
nones. This methodology provides an exceptionally
efficient route to a variety of polysubstituted naphtha-
lene derivatives, which would have potential utiliza-
tion in the construction of bioactive compounds and
valuable building blocks. Further extensions of these
annulation reactions into different multiple carbon-
carbon and carbon-heteroatom bonds are in progress.
Scheme 2. Disfavored 6da.
Experimental Section
Typical Procedure for the Synthesis of Hydrophen-
anthren-1(2H)-ones 3 via Pd-Catalyzed Aryne
Annulation
To a stirred solution of iodocycloenone 1 (0.3 mmol), 2-(tri-
methylsilyl)aryl triflate
2
(0.45 mmol), Pd2dba3·CHCl3
Scheme 3. Mechanistic proposal for Pd-catalyzed aryne an-
nulation reactions.
(16 mg, 0.015 mmol), 1,5-diphenylpenta-1,4-dien-3-one (dba,
3.5 mg, 0.015 mmol) and Cs2CO3 (147 mg, 0.45 mmol) in dry
Adv. Synth. Catal. 2010, 352, 379 – 385
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Xian Huang et al.
COMMUNICATIONS
MeCN (2 mL) and dry toluene (2 mL), CsF (137 mg,
0.9 mmol) was added under nitrogen atmosphere. The reac-
tion mixture was then allowed to stir at room termerature
for 12–18 h. When the reaction was judged to be complete
(as evident by TLC), the reaction mixture was filtered
through a layer of silica gel and eluted with Et2O. The fil-
trate was concentrated under reduced pressure, and the resi-
due was purified by column chromatography on silica gel
(petroleum ether/ethyl acetate, 20:1) to afford 3.
9-Methyl-3,4-dihydrophenanthren-1(2H)-one (3a): mp
100–1028C. 1H NMR (400 MHz, CDCl3): d=8.15 (d, J=
8.4 Hz, 1H), 8.03 (d, J=8.4 Hz, 1H), 7.95 (s, 1H), 7.65 (t,
J=8.4 Hz, 1H), 7.59 (t, J=8.4 Hz, 1H), 3.36 (t, J=6.0 Hz,
2H), 2.72 (t, J=6.0 Hz, 2H), 2.69 (s, 3H), 2.32–2.25 (m,
2H); 13C NMR (100 MHz, CDCl3): d=198.8, 141.2, 135.1,
133.0, 131.5, 129.5, 128.1, 126.3, 125.3, 124.9, 122.8, 38.3,
25.4, 22.8, 19.3; IR (KBr): n=2924, 1674, 1469, 1210,
1188 cmÀ1; MS: m/z (%)=210 [M+, 100], 154 (94), 182 (63);
HR-MS (EI): m/z=210.1046, calcd. for C15H14O: 210.1045.
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Acknowledgements
We are grateful to the National Natural Science Foundation
of China (Project Nos. 20872127, 20732005 and J0830431)
and National Basic Research Program of China (973 Pro-
gram, 2009CB825300) and CAS Academician Foundation of
Zhejiang Province for financial support.
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Efficient Synthesis of Hydrophenanthren-1(2H)-ones and NaphthoACHTNUTRGNEUNG[2,1-c]furan-3(1H)-ones
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