Intermolecular sequential [4 + 2]-cycloaddition-aromatization reaction of aryl-substituted allenes with DMAD affording phenanthrene and naphthalene derivatives

Article abstract of DOI:10.1039/b808767a

An efficient entry to phenanthrene and naphthalene derivatives through intermolecular sequential [4 + 2]-cycloaddition-aromatization reactions of aryl-substituted allenes with DMAD in the absence of any catalyst was discovered. In this reaction the aromat

Full text of DOI:10.1039/b808767a

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www.rsc.org/obc | Organic & Biomolecular Chemistry
Intermolecular sequential [4 + 2]-cycloaddition–aromatization reaction of
aryl-substituted allenes with DMAD affording phenanthrene and
naphthalene derivatives†
Xuefeng Jiang,a Wangqing Kong,b Jie Chena and Shengming Ma*a,b
Received 23rd May 2008, Accepted 23rd June 2008
First published as an Advance Article on the web 31st July 2008
DOI: 10.1039/b808767a
An efficient entry to phenanthrene and naphthalene derivatives through intermolecular sequential [4 +
2]-cycloaddition–aromatization reactions of aryl-substituted allenes with DMAD in the absence of any
catalyst was discovered. In this reaction the aromatic ring and the adjacent carbon–carbon double bond
of the allene unit acted as the 1,3-diene.
Introduction
Results and discussion
Phenanthrene is a very important structural unit responsible for
various biological effects.1 Many naturally occurring compounds
of biological and therapeutic interest contain a phenanthrene or re-
duced phenanthrene nucleus.2–9 Thus, many synthetic routes have
been developed for the preparation of phenanthrene derivatives.10
On the one hand, Diels–Alder reactions involving allene units
are well documented.11–13 For example, electron-deficient allenes
participate in the Diels–Alder-type [4 + 2]-cycloaddition mostly
We started our study by mixing a-allenyl naphthalenes 1a and 1b
with DMAD, however, no reaction occurred. When we introduced
an electron-withdrawing ethoxycarbonyl group to the allene
moiety, i.e., 1c, the corresponding reaction afforded phenanthrene
derivative 2c in 50% yield (Scheme 1).
=
as a dienophile, in which the electron-deficient internal C C bond
of the allene reacts highly selectively;12 [4 + 2]-cycloadditions of
alkynes with the 1,3-diene unit in conjugated allenenes are also
known processes.13 However, only scattered reports have appeared
=
in which an aryl group and the conjugated C C bond of an allene
were incorporated as the 1,3-diene unit: Pasto and Yang reported
an intermolecular cycloaddition reaction between phenylpropadi-
ene and maleimide, affording [4 + 2]-cycloaddition–aromatization
products together with [2 + 2]-cycloaddition adducts as minor
products;14 Ollis and Laird discovered the intramolecular [4 +
2]-cycloaddition–aromatization of phenylallene activated by het-
eroatoms with an acetylene moiety.15 Recently, Brummond and
Chen,16a Ohno et al.,16b Mukai et al.,17 and ourselves18 observed
intramolecular [2 + 2]-cycloadditions involving alkynes and the
Scheme 1
With these primary results in hand, we screened the reaction
conditions by changing the solvents. The results in Table 1
indicated that dioxane is the best solvent, affording 2c in 72%
yield (entry 12, Table 1). At a lower temperature, the yield of 2c
dropped dramatically (entries 13–15, Table 1). The structure of 2
was confirmed by an X-ray diffraction study of 2c19 (Fig. 1)†.
With the optimized reaction conditions, we investigated the
scope of the intermolecular [4 + 2]-cycloaddition–aromatization
reactions of a-naphthyl allenes. From the results presented in
Table 2, the following items should be noted: (1) the electron-
withdrawing group of the a-allenyl naphthalenes could be CO2Et
(entries 1–5, Table 2) and P(O)Ph2 (entries 6–10, Table 2); (2)
the stability of the 4-naphthyl-2,3-allenoate 1g is low under the
standard conditions, which may explain the low-yielding nature
of this reaction (entry 5, Table 2); (3) other alkynes, such as
diphenylalkyne, bis(trimethylsilyl)acetylene and dec-5-yne, are not
effective.
=
conjugated C C bond of an aryl allene unit. In the studies
by Mukai et al.17 and us,18a it is interesting to observe the
formation of Diels–Alder products of the alkyne with the vinyl
arene unit in 1-aryl-1,2-allenes as the minor products. In trying to
obtain solely the Diels–Alder reaction between the alkyne and the
vinyl arene unit in 1-aryl-1,2-allenes, we observed intermolecular
[4 + 2]-cycloaddition reactions of 1-aryl-1,2-allenes with DMAD
(dimethyl acetylenedicarboxylate) affording phenanthrene and
naphthalene derivatives efficiently.
aState Key Laboratory of Organometallic Chemistry, Shanghai Institute of
Organic Chemistry, Chinese Academy of Sciences, 354 Fenglin Lu, Shanghai
200032, P. R. China. E-mail: masm@mail.sioc.ac.cn; Fax: 86-21-64167510
bLaboratory of Molecular Recognition and Synthesis, Department of
Chemistry, Zhejiang University, Hangzhou 310027, Zhejiang, P. R. China
When we used an allene with a phenyl group and a P(O)Ph2
group on the same end, i.e., 3, the [4 + 2]-cycloaddition–
aromatization reaction could also proceed to afford naphthalene
derivative 4 (Scheme 2). An X-ray diffraction study confirmed the
† Electronic supplementary information (ESI) available: NMR (1H, 13C
and 31P) spectroscopic data for all the new compounds. CCDC reference
numbers 648596 and 648597. For ESI and crystallographic data in CIF or
other electronic format see DOI: 10.1039/b808767a
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Table 1 Intermolecular [4 + 2]-cycloaddition–aromatization reactions of
ethyl 4-(a-naphthyl)-2-methylbutadienoate 1c with DMAD under different
conditionsa
Table 2 Intermolecular [4 + 2]-cycloaddition–aromatization reactions of
electron-deficient a-naphthyl allenes 1 with DMADa
1
Entry Solvent
Temperature/◦C Time/h Isolated yield of 2c (%)
Entry R1
R2
Time/h
1c 10
1d 24
1e 24
1f 24
1g 19
2
Isolated yield of 2 (%)
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
Toluene
DMF
i-C8H18
DME
THF
150
150
150
150
150
14
3
54
39
43
30
46
39
46
45
60
66
52
72
33
35
18
1
2
3
4
5
Me
CO2Et
CO2Et
CO2Et
CO2Et
CO2Et
P(O)Ph2 1h 72
P(O)Ph2 1i 72
P(O)Ph2 1j 72
P(O)Ph2 1k 72
2c 72
2d 64
2e 58
2f 40
2g 40
2h 76
2i 80
2j 70
2k 73
2l 65
n-Pr
12
12
13
13
12
12
15
10
15
10
10
10
12
n-Bu
i-Bu
Allyl
t-BuOMe 150
6b
7b
8b
9b
10b
n-Pr
n-Bu
n-C5H11
n-C6H13
n-Bu2O
Anisole
CH3CN
150
150
150
CCl3CH3 150
Xylene
Dioxane
Dioxane 130
Dioxane 110
PhCH2CH2 P(O)Ph2 1l 72
150
150
a The reaction was conducted using 1.5 equiv. of 1 and 1 equiv. of DMAD
in a reaction tube with a screw cap. b The reaction was conducted using
1 equiv. of 1 and 2 equiv. of DMAD.
Dioxane
90
a The reaction was conducted using 1.5 equiv. of 1c and 1 equiv. of DMAD
in a reaction tube with a screw cap.
Scheme 2
Fig. 1 ORTEP drawing of 2c.
structure of 420 (Fig. 2)†. This reaction could potentially be used
to establish a new library of phosphine ligands.21
Conclusions
Fig. 2 ORTEP drawing of 4.
In conclusion, we have developed an efficient entry to phenan-
threne and naphthalene derivatives through intermolecular [4 + 2]-
cycloaddition–aromatization reactions of aryl-substituted allenes
with DMAD in the absence of any catalyst. Due to the potential
utility of these compounds, this method will be useful in organic
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synthesis and medicinal chemistry. Further studies in this area are
being pursued in our group.
7.5 Hz, 3 H); 13C NMR (75.4 MHz, CDCl3) d 173.7, 168.5, 168.3,
134.9, 132.1, 131.6, 131.3, 130.6, 129.2, 129.1, 128.6, 127.9, 127.5,
127.3, 124.3, 123.1, 122.9, 60.9, 52.8, 52.7, 47.3, 36.2, 20.9, 14.0,
13.8; MS (ESI) m/z (%) 440 (M + NH4 , 100), 423 (M + H+, 14);
+
Experimental section
IR (neat) m 2955, 2873, 1732, 1592, 1440, 1349, 1292, 1224, 1176,
1116 cm−1; anal. calcd for C25H26O6: C, 71.07; H, 6.20. Found: C,
70.93; H, 6.17.
Starting materials
2,3-Allenoic esters 1c–g were prepared according to the published
procedure by treatment of the acyl chlorides with ethyl 2-
(triphenylphosphoranylidene)alkanoates.22 1,2-Allenyl phosphine
oxides 1h–l and 3 were prepared according to the known method
by the reaction of chlorodiphenylphosphine with propargylic
alcohols in the presence of Et3N.23
(3) 1,2-Bis(methoxycarbonyl)-3-(1-ethoxycarbonyl-
pentyl)phenanthrene (2e)
A solution of 1e (100 mg, 0.340 mmol) and DMAD (35 mg,
0.25 mmol) in 2 mL of dry 1,4-dioxane was heated to 150 ◦C for
24 hours to afford 62 mg (58%) of 2e: Rf (petroleum ether–ethyl
acetate, 5 : 1) = 0.33; liquid; 1H NMR (300 MHz, CDCl3) d 8.94
(s, 1 H), 8.71 (d, J = 8.1 Hz, 1 H), 7.94 (d, J = 9.3 Hz, 1 H), 7.88
(dd, J = 7.5, 0.9 Hz, 1 H), 7.80 (d, J = 9.3 Hz, 1 H), 7.73–7.62 (m,
2 H), 4.24–4.02 (m, 3 H), 4.02 (s, 3 H), 3.97 (s, 3 H), 2.32–2.20 (m,
1 H), 2.05–1.92 (m, 1 H), 1.50–1.27 (m, 4 H), 1.20 (t, J = 6.9 Hz,
3 H), 0.90 (t, J = 6.9 Hz, 3 H); 13C NMR (75.4 MHz, CDCl3) d
173.7, 168.5, 168.3, 134.9, 132.1, 131.6, 131.3, 130.6, 129.2, 129.0,
128.6, 127.9, 127.5, 127.3, 124.3, 123.1, 122.9, 60.9, 52.8, 52.6,
47.6, 33.8, 29.8, 22.4, 14.1, 13.8; MS (ESI) m/z (%) 475 (M + K+,
31P NMR (121.5 MHz, CDCl3) spectra were recorded using 85%
H3PO4 as the external standard.
General procedure
To a solution of a-naphthyl allene 1 (0.375 mmol) in 1 mL
of 1,4-dioxane were added DMAD (34 mg, 0.25 mmol) and
1 mL of 1,4-dioxane. The mixture was heated to 150 ◦C in a
reaction tube with a screw cap. After complete conversion of the
starting material (monitored by TLC, eluent: petroleum ether–
ethyl acetate = 5 : 1), the reaction mixture was concentrated and
purified by flash chromatography on silica gel (eluent: petroleum
ether–ethyl ether = 10 : 1) to afford the product 2.
8), 459 (M + Na+, 15), 454 (M + NH4 , 100), 437 (M + H+, 18),
+
405 (M+ − OMe, 35); IR (neat) m 2954, 2931, 2872, 1732, 1592,
1516, 1440, 1349, 1293, 1260, 1222, 1176, 1117, 1024, 1007 cm−1;
HRMS (EI) calcd for C26H28O6Na (M + Na+) 459.1778. Found
459.1778.
The following compounds were prepared according to the
General procedure:
(1) 1,2-Bis(methoxycarbonyl)-3-(1-ethoxycarbonyl-
ethyl)phenanthrene (2c)
(4) 1,2-Bis(methoxycarbonyl)-3-(1-ethoxycarbonyl-3-
methylbutyl)phenanthrene (2f)
A solution of 1c (187 mg, 0.74 mmol) and DMAD (69 mg,
0.49 mmol) in 3 mL of dry 1,4-dioxane was heated to 150 ◦C for
10 hours to afford 111 mg (72%) of 2c: Rf (petroleum ether–ethyl
acetate, 5 : 1) = 0.33; solid, mp 94–95 ◦C (petroleum ether–ethyl
acetate); 1H NMR (300 MHz, CDCl3) d 8.83 (s, 1 H), 8.67 (d, J =
8.1 Hz, 1 H), 7.92 (d, J = 9 Hz, 1 H), 7.87 (dd, J = 8.1, 1.5 Hz,
1 H), 7.79 (d, J = 9 Hz, 1 H), 7.72–7.60 (m, 2 H), 4.38 (q, J =
7.2 Hz, 1 H), 4.22–4.07 (m, 2 H), 4.02 (s, 3 H), 3.96 (s, 3 H), 1.71 (d,
J = 7.5 Hz, 3 H), 1.19 (t, J = 7.2 Hz, 3 H); 13C NMR (75.4 MHz,
CDCl3) d 174.0, 168.5, 168.1, 136.2, 132.1, 131.73, 131.67, 129.8,
129.1, 129.0, 128.6, 127.8, 127.4, 127.2, 124.0, 122.9, 122.8, 61.0,
52.8, 52.6, 42.2, 18.7, 14.0; MS (EI) m/z (%) 394 (M+, 2.53), 41
(100); IR (neat) m 2982, 2952, 2925, 1732, 1593, 1441, 1294, 1223,
1210, 1195, 1176, 1106 cm−1; anal. calcd for C23H22O6: C, 70.04;
H, 5.62. Found: C, 70.11; H, 5.91.
A solution of 1f (115 mg, 0.391 mmol) and DMAD (36 mg,
0.25 mmol) in 2 mL of dry 1,4-dioxane was heated to 150 ◦C
for 24 hours to afford 44 mg (40%) of 2f: Rf (petroleum ether–
ethyl acetate, 5 : 1) = 0.33; liquid; H NMR (300 MHz, CDCl3)
1
d 8.94 (s, 1 H), 8.71 (d, J = 7.8 Hz, 1 H), 7.94 (d, J = 9.3 Hz,
1 H), 7.89 (dd, J = 7.2, 0.9 Hz, 1 H), 7.81 (d, J = 9.0 Hz, 1 H),
7.74–7.65 (m, 2 H), 4.32 (dd, J = 8.7, 6.3 Hz, 1 H), 4.25–4.02 (m,
2 H), 4.02 (s, 3 H), 3.97 (s, 3 H), 2.25–2.13 (m, 1 H), 1.85–1.75 (m,
1 H), 1.68–1.57 (m, 1 H), 1.20 (q, J = 7.2 Hz, 3 H), 0.96 (d, J =
6.6 Hz, 6 H); 13C NMR (75.4 MHz, CDCl3) d 173.8, 168.5, 168.4,
135.0, 132.2, 131.7, 131.3, 130.6, 129.3, 129.1, 128.6, 127.9, 127.5,
127.3, 124.4, 123.2, 122.9, 61.0, 52.9, 52.7, 45.5, 43.2, 26.3, 22.6,
22.4, 14.1; MS (EI) m/z (%) 437 (M + H+, 12.95), 346 (100); IR
(neat) m 2954, 1732, 1463, 1455, 1435, 1292, 1222, 1176, 1005 cm−1;
HRMS (EI) calcd for C26H28O6 (M+) 436.1886. Found 436.1878.
(2) 1,2-Bis(methoxycarbonyl)-3-(1-ethoxycarbonyl-
butyl)phenanthrene (2d)
(5) 1,2-Bis(methoxycarbonyl)-3-(1-ethoxycarbonylbut-3-
enyl)phenanthrene (2g)
A solution of 1d (105 mg, 0.375 mmol) and DMAD (34 mg,
0.25 mmol) in 2 mL of dry 1,4-dioxane was heated to 150 ◦C for
24 hours to afford 65 mg (64%) of 2d: Rf (petroleum ether–ethyl
acetate, 5 : 1) = 0.33; solid, mp 87–88 ◦C (petroleum ether–ethyl
A solution of 1g (106 mg, 0.375 mmol) and DMAD (37 mg,
0.25 mmol) in 2 mL of dry 1,4-dioxane was heated to 150 ◦C for
19 hours to afford 44 mg (40%) of 2g together with an unidentified
product (34 mg). 2g: Rf (petroleum ether–ethyl acetate, 5 : 1) =
1
1
acetate); H NMR (300 MHz, CDCl3) d 8.94 (s, 1 H), 8.71 (d,
0.33; liquid; H NMR (300 MHz, CDCl3) d 8.91 (s, 1 H), 8.69
J = 8.1 Hz, 1 H), 7.95 (d, J = 9.0 Hz, 1 H), 7.88 (d, J = 7.8 Hz,
1 H), 7.80 (d, J = 9.6 Hz, 1 H), 7.73–7.62 (m, 2 H), 4.25–4.02 (m,
3 H), 4.02 (s, 3 H), 3.97 (s, 3 H), 2.30–2.21 (m, 1 H), 2.00–1.91 (m,
1 H), 1.50–1.32 (m, 2 H), 1.20 (t, J = 7.5 Hz, 3 H), 0.96 (t, J =
(d, J = 8.1 Hz, 1 H), 7.94 (d, J = 9.0 Hz, 1 H), 7.89 (dd, J =
9.0, 1.2 Hz, 1 H), 7.81 (d, J = 9.3 Hz, 1 H), 7.74–7.62 (m, 2 H),
5.89–5.74 (m, 1 H), 5.15 (d, J = 17.1 Hz, 1 H), 5.05 (d, J =
10.5 Hz, 1 H), 4.33 (dd, J = 8.4, 6.9 Hz, 1 H), 4.24–4.06 (m,
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2 H), 4.02 (s, 3 H), 3.97 (s, 3 H), 3.08–2.96 (m, 1 H), 2.80–2.70
(m, 1 H), 1.20 (t, J = 6.9 Hz, 3 H); 13C NMR (75.4 MHz, CDCl3)
d 173.0, 168.5, 168.1, 134.9, 134.1, 132.2, 131.6, 130.3, 129.21,
129.16, 128.6, 127.9, 127.6, 127.3, 124.4, 123.1, 122.9, 117.4, 61.1,
52.8, 52.7, 47.5, 37.9, 14.1; MS (EI) m/z (%) 420 (M+, 16.51),
291 (100); IR (neat) m 2952, 1732, 1441, 1350, 1293, 1261, 1224,
1176 cm−1; HRMS (EI) calcd for C25H24O6Na (M + Na+) 443.1465.
Found 443.1473.
(9) 1,2-Bis(methoxycarbonyl)-3-(1-diphenylphosphino-
ylheptyl)phenanthrene (2k)
A solution of 1k (111 mg, 0.25 mmol) and DMAD (70 mg,
0.49 mmol) in 2 mL of dry 1,4-dioxane was heated to 150 ◦C for
72 hours to afford 107 mg (73%) of 2k: Rf (petroleum ether–ethyl
acetate, 1 : 1) = 0.67; solid, mp 99–101 ◦C (petroleum ether–ethyl
acetate); 1H NMR (300 MHz, CDCl3) d 9.49 (d, J = 2.1 Hz, 1 H),
8.85 (d, J = 8.4 Hz, 1 H), 8.05–7.95 (m, 2 H), 7.89–7.63 (m, 5 H),
7.63–7.45 (m, 5 H), 7.26–7.16 (m, 1 H), 7.16–7.08 (m, 2 H), 4.61–
4.50 (m, 1 H), 3.96 (s, 3 H), 3.81 (s, 3 H), 2.35–2.20 (m, 1 H),
2.15–1.90 (m, 1 H), 1.30–0.98 (m, 8 H), 0.74 (t, J = 7.2 Hz, 3 H);
31P NMR (121.5 MHz, CDCl3) d 34.8; MS (ESI) m/z (%) 615 (M +
Na+, 20), 593 (M + H+, 100); IR (neat) m 3610, 3405, 2951, 2930,
1729, 1712, 1658, 1588, 1437, 1294, 1224, 1178, 1163, 1116 cm−1;
HRMS (ESI) calcd for C37H37PO5Na (M + Na+) 615.2271. Found
615.2273.
(6) 1,2-Bis(methoxycarbonyl)-3-(1-diphenylphosphino-
ylbutyl)phenanthrene (2h)
A solution of 1h (99 mg, 0.24 mmol) and DMAD (68 mg,
0.48 mmol) in 2 mL of dry 1,4-dioxane was heated to 150 ◦C
for 72 hours to afford 102 mg (76%) of 2h: Rf (petroleum ether–
ethyl acetate, 1 : 1) = 0.67; solid, mp 170–171 ◦C (petroleum
ether–ethyl acetate); 1H NMR (300 MHz, CDCl3) d 9.52 (d, J =
2.4 Hz, 1 H), 8.85 (d, J = 8.1 Hz, 1 H), 8.06–7.97 (m, 2 H), 7.86–
7.50 (m, 10 H), 7.17–7.08 (m, 3 H), 4.65–4.54 (m, 1 H), 3.96 (s,
3 H), 3.82 (s, 3 H), 2.32–2.20 (m, 1 H), 2.02–1.92 (m, 1 H), 1.26–
1.16 (m, 2 H), 0.76 (t, J = 7.5 Hz, 3 H); 31P NMR (121.5 MHz,
CDCl3) d 34.5; MS (ESI) m/z (%) 551 (M + H+, 100); IR (neat) m
2955, 1724, 1589, 1437, 1350, 1296, 1229, 1197, 1163, 1117 cm−1;
anal. calcd for C34H31O5P: C 74.17; H 5.68. Found: C 74.00; H
5.73.
(10) 1,2-Bis(methoxycarbonyl)-3-(3-phenyl-1-
diphenylphosphinoylpropyl)phenanthrene (2l)
A solution of 1l (120 mg, 0.26 mmol) and DMAD (70 mg,
0.49 mmol) in 2 mL of dry 1,4-dioxane was heated to 150 ◦C for
72 hours to afford 101 mg (65%) of 2l: Rf (petroleum ether–ethyl
acetate, 1 : 1) = 0.67; solid, mp 182–183 ◦C (petroleum ether–ethyl
acetate); 1H NMR (300 MHz, CDCl3) d 9.57 (s, 1 H), 8.88 (d, J =
8.4 Hz, 1 H), 8.02–7.92 (m, 2 H), 7.92–7.64 (m, 5 H), 7.64–7.45
(m, 5 H), 7.25–7.05 (m, 6 H), 6.93 (d, J = 7.8 Hz, 2 H), 4.70–4.62
(m, 1 H), 3.97 (s, 3 H), 3.76 (s, 3 H), 2.69–2.34 (m, 4 H); 31P NMR
(121.5 MHz, CDCl3) d 34.5; MS (ESI) m/z (%) 613 (M + H+, 100);
IR (neat) m 3058, 2945, 1734, 1718, 1589, 1454, 1437, 1296, 1224,
1190, 1170, 1116 cm−1; anal. calcd for C39H33O5P: C 76.46; H 5.43.
Found: C 76.35; H 5.41.
(7) 1,2-Bis(methoxycarbonyl)-3-(1-diphenylphosphino-
ylpentyl)phenanthrene (2i)
A solution of 1i (107 mg, 0.25 mmol) and DMAD (72 mg,
0.51 mmol) in 2 mL of dry 1,4-dioxane was heated to 150 ◦C for
72 hours to afford 114 mg (80%) of 2i: Rf (petroleum ether–ethyl
acetate, 1 : 1) = 0.67; solid, mp 181–182 ◦C (petroleum ether–ethyl
acetate); 1H NMR (300 MHz, CDCl3) d 9.53 (s, 1 H), 8.85 (d, J =
8.4 Hz, 1 H), 8.05–7.96 (m, 2 H), 7.86–7.77 (m, 2 H), 7.75–7.66
(m, 2 H), 7.66–7.50 (m, 6 H), 7.17–7.05 (m, 3 H), 4.63–4.55 (m,
1 H), 3.93 (s, 3 H), 3.81 (s, 3 H), 2.45–2.20 (m, 1 H), 2.12–1.95
(m, 1 H), 1.25–1.02 (m, 4 H), 0.67 (t, J = 7.2 Hz, 3 H); 31P NMR
(121.5 MHz, CDCl3) d 34.6; MS (ESI) m/z (%) 565 (M + H+,
100); IR (neat) m 2953, 1727, 1590, 1514, 1438, 1294, 1226, 1210,
1187, 1172, 1117 cm−1; anal. calcd for C35H33O5P: C 74.45; H 5.89.
Found: C 74.57; H 6.00.
(11) 1,2-Bis(methoxycarbonyl)-4-(diphenylphosphino-yl)-3-
methylnaphthalene (4)
A solution of 3 (125 mg, 0.40 mmol) and DMAD (37 mg,
0.26 mmol) in 2 mL of dry 1,4-dioxane was heated to 150 ◦C
for 36 hours to afford 85 mg (71%) of 4: Rf (ethyl ether) = 0.25;
◦
1
solid, mp 169–170 C (petroleum ether–ethyl acetate); H NMR
(300 MHz, CDCl3) d 8.56 (d, J = 8.7 Hz, 1 H), 8.05 (d, J = 8.7 Hz,
1 H), 7.70–7.60 (m, 4 H), 7.55–7.38 (m, 7 H), 7.35–7.24 (m, 1 H),
4.01 (s, 3 H), 3.88 (s, 3 H), 2.29 (s, 3 H); 31P NMR (121.5 MHz,
CDCl3) d 31.9; MS (ESI) m/z (%) 458 (M + H+, 100); IR (neat) m
3058, 2945, 1734, 1437, 1339, 1301, 1251, 1183 cm−1; anal. calcd
for C27H23O5P: C 70.74; H 5.06. Found: C 70.54; H 5.20.
(8) 1,2-Bis(methoxycarbonyl)-3-(1-diphenylphosphino-
ylhexyl)phenanthrene (2j)
A solution of 1j (102 mg, 0.23 mmol) and DMAD (76 mg,
0.53 mmol) in 2 mL of dry 1,4-dioxane was heated to 150 ◦C for
72 hours to afford 94 mg (70%) of 2j: Rf (petroleum ether–ethyl
acetate, 1 : 1) = 0.67; solid, mp 138–140 ◦C (petroleum ether–ethyl
acetate); 1H NMR (300 MHz, CDCl3) d 9.51 (s, 1 H), 8.86 (d, J =
8.4 Hz, 1 H), 8.05–7.96 (m, 2 H), 7.88–7.50 (m, 10 H), 7.20–7.06
(m, 3 H), 4.64–4.54 (m, 1 H), 3.93 (s, 3 H), 3.81 (s, 3 H), 2.35–2.22
(m, 1 H), 2.06–1.90 (m, 1 H), 1.25–1.00 (m, 6 H), 0.70 (t, J =
5.7 Hz, 3 H); 31P NMR (121.5 MHz, CDCl3) d 34.8; MS (ESI)
m/z (%) 579 (M + H+, 100); IR (neat) m 3423, 3053, 2951, 2928,
2856, 1737, 1719, 1590, 1439, 1352, 1295, 1223, 1211, 1187, 1163,
1150, 1116, 1008 cm−1; HRMS (ESI) calcd for C36H35PO5Na (M +
Na+) 601.2114. Found 601.2093.
Acknowledgements
Financial support from the National Natural Science Foundation
of China (20423001, and 20332060) and State Key Basic Research
& Development Program (2006CB06105) is greatly appreciated.
We thank Tao Bai in our research group for reproducing the results
presented in entries 4, 7, and 10 in Table 2.
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19 Crystal data for compound 2c: C23H22O6, MW = 394.41, triclinic, P–1,
◦
˚
˚
˚
a = 7.7495(7) A, b = 10.1805(9) ◦A, c = 13.3793(12) A, a = 93.494(2) ,
◦
3
˚
b = 91.931 (2) , c = 109.458 (2) , V = 991.77 (15) A , T = 293(2) K,
Z = 2, final R indices [I >2r(I)], R1 = 0.0525, wR2 = 0.1429, reflections
collected/unique: 5856/4188 (Rint= 0.0382). CCDC: 648596.
20 Crystal data for compound 4: C27H23O5P, MW = 458.42, monoclini◦c,
˚
˚
˚
˚
P21/c, a = 11.330(10) A,◦b = 22.000(19) A, c = 9.420(8) A, a = 90 ,
◦
3
b = 98.108(15) , c = 90 , V = 2324(4) A , T = 293(2) K, Z = 4,
final R indices [I >2r(I)], R1 = 0.0560, wR2 = 0.1453, reflections
collected/unique: 13454/5044 (Rint= 0.0786). CCDC: 648597.
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3610 | Org. Biomol. Chem., 2008, 6, 3606–3610
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