Palladium-catalyzed α-ketocyclopropanation of norbornenes with propargyl acetates

Article abstract of DOI:10.1021/jo500357f

Propargyl acetates reacted with norbornene in the presence of a catalytic amount of tetrakis(tripheylphosphine)palladium to give cyclopropyl ketones. The reaction proceeded with high stereoselectivity, affording a single stereoisomer. The reaction of various substituted norbornenes gave the corresponding cyclopropanes in moderate to good yields.

Full text of DOI:10.1021/jo500357f

Note
pubs.acs.org/joc
Palladium-Catalyzed α‑Ketocyclopropanation of Norbornenes with
Propargyl Acetates
Yuta Tanioka† and Naofumi Tsukada*,†,‡
‡
†Department of Chemistry, Graduate School of Science and Research Institute of Green Science and Technology, Shizuoka
University, Shizuoka 422-8529, Japan
S
* Supporting Information
ABSTRACT: Propargyl acetates reacted with norbornene in the presence
of a catalytic amount of tetrakis(tripheylphosphine)palladium to give cyclo-
propyl ketones. The reaction proceeded with high stereoselectivity, affording
a single stereoisomer. The reaction of various substituted norbornenes gave
the corresponding cyclopropanes in moderate to good yields.
ransition-metal-catalyzed cycloaddition reactions are
powerful and versatile methods for the synthesis of cyclic
Table 1. Palladium-Catalyzed α-Ketocyclopropanation of
Norbornene with 3-Phenyl-2-propynyl Compounds
a
T
compounds.1,2 Among them, [3 + 2] cycloaddition reactions that
proceed via a trimethylenemethane palladium intermediate
represent an important method for preparation of five-
membered ring compounds.3,4 On the other hand, the oxygen
analogue, oxatrimethylenemethane palladium,5−9 reacts with
strained alkenes to give α-ketocyclopropanes with high regio-
and stereoselectivity.10−14 It is usual for the [2 + 1] cycloaddition
reactions15 to require that precursors of oxatrimethylene-
methane bear an oxygen substituent at the center carbon. For
example, 2-siloxy-13,14 and 2-alkoxy-allylic compounds11 or
methylene-1,3-dioxalan-2-ones12 have been used as the
precursor. Recently, it was reported that propargyl alcohols,
which have no oxygen substituent at the center carbon, reacted
with norbornene under oxygen to yield alkenyl cyclopropyl
ketones.16 The oxidative reaction was limited to tertiary
propargyl alcohols that have a methyl substituent at the propargyl
position. Herein we report a palladium-catalyzed α-ketocyclo-
propanation of norbornenes with primary propargyl esters
without oxygen as the oxidant.
b
entry
2
solvent
additive (mmol)
yield (%)
1
2
3
4
5
2a
2b
2c
2d
2e
2a
2a
2a
2a
2a
2a
2a
2a
2a
2a
2a
2a
2a
2a
2a
2a
2a
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
ethanol
DMF
44
31
0
0
trace
32
56
21
trace
0
c
6
d
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
AcOH
dioxane
toluene
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
0
0
Et3N (0.45)
Et2NiPr (0.45)
py (0.45)
59
7
6
e
2,6-Me2py (0.45)
4
AcOK (0.45)
H2O (0.3)
H2O (0.9)
7
54
37
15
63
0
We previously reported that the reaction of cinnamyl acetate
and norbornene gave a [2 + 2] cycloaddition product and a
[2 + 1] cycloaddition product in the presence of Pd(PPh3)4.17
Under the same reaction conditions, the reaction of 3-phenyl-2-
propynyl acetate 2a and norbornene 1a afforded benzyl
cyclopropyl ketone 3a in 44% yield with high stereoselectivity
(eq 1, Table 1, entry 1). No stereoisomer was observed in GC,
f
MS4Å (100 mg)
g
h
O2
a
A mixture of 1 (0.3 mmol), 2 (0.3 mmol), Pd(PPh3)4 (0.015 mmol),
and additives in acetonitrile (1.0 mL) was heated at 80 °C for 18 h
b
under nitrogen. Determined by GC using dodecane as an internal
c
d
standard. Excess amount of acetate (1.5 mmol) was used. Excess
e
amount of norbornene (1.5 mmol) was used. 2,6-Mepy = 2,6-
dimethylpyridine. MS4Å = 4Å molecular sieves. Degassed by freeze−
pump−thaw cycles. Carried out under oxygen (1 atm).
f
g
h
carbonate ester 2c or phosphate ester 2d did not afford 3a
(entries 3 and 4). In contrast to the oxidative cycloaddition,16 the
corresponding alcohol 2e was much less reactive than the ester
GC−MS, or NMR analysis. Although the benzoate ester 2b
reacted similarly (entry 2), the reaction of the corresponding
Received: February 13, 2014
Published: May 15, 2014
© 2014 American Chemical Society
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The Journal of Organic Chemistry
Note
2a (entry 5). While the use of excess amounts of the acetate 2a
did not improve the yield of 3a (entry 6), the reaction with excess
amounts of norbornene 2a gave 3a in better yield (entry 7). The
use of acetonitrile as a solvent is essential for the [2 + 1]
cycloaddition. The yield of 3a was lowered in the reaction in
ethanol and DMF (entries 8 and 9). No products were obtained
in the reaction in other solvents such as acetic acid, dioxane, and
toluene (entries 10−12). Next, the addition of base was
investigated because acetic acid is generated as the cycloaddition
progresses. While the addition of various bases decreased the
yield of 3a (entries 14−17), only triethylamine was effective for
the cycloaddition to afford 3a in 59% yield (entry 13). The
addition of 1 equiv of water slightly improved the yield of 3a
(entry 1 vs 18), although excess amounts of water exhibited the
opposite effect (entry 19). The addition of MS4Å in the reaction
decreased the yield of 3a (entry 20). The reaction in acetonitrile
degassed by freeze−pump−thaw cycles afforded 3a in higher
yield (entry 21). The cycloaddition did not proceed under
oxygen (entry 22)
excess amounts of norbornadiene 1f afforded monocyclopropa-
nated product 3f selectively (entry 6). No dicyclopropanated
product was obtained even if excess amounts of 2a were used.
Only unidentified oligomers were observed. The reaction of
other alkenes such as styrene, cyclohexene, 2-butene-1,4-diol,
dimethyl maleate, and benzalacetone gave no products.
The reactions of other propargyl acetates were also
investigated. Various 3-aryl-2-propynyl acetates 2g−k reacted
with 1a as well as 2a, giving cyclopropanes 3g−k with high
stereoselectivity in moderate to good yields (eq 2). Propargyl
Table 2 summarizes the results of the α-ketocyclopropanation
of several norbornene derivatives with 2a. In the reaction of
Table 2. Palladium-Catalyzed α-Ketocyclopropanation of
Norbornene Derivatives with 3-Phenyl-2-propynyl Acetate 2a
a
acetate 2l, bearing a terminal alkyne, also can be used for the
cycloaddition although the yield of cyclopropane 3l was not high
(eq 3). In the reaction of a 3-alkyl-substituted propargyl acetate
such as 2-pentynyl acetate, only a trace amount of product was
observed under the similar reaction conditions. In contrast to the
previous similar reaction of tertiary propargyl alcohols,16 the
reaction of acetate ester 2m, derived from tertiary propargyl
alcohol, gave dienynyl cyclopropane 4 in moderate yield instead
of a ketocyclopropane (eq 4).
a
A mixture of 1 (0.5 mmol), 2a (0.5 mmol), Pd(PPh3)4 (0.025 mmol),
Since the yield of 3a decreased under oxygen and increased in
degassed acetonitrile (Table 1, entries 21 and 22), the oxygen
atom of ketone does not seem to be derived from oxygen. The
source of the oxygen atom could be residual water in acetonitrile
or reagents because the yield of 3a increased by the addition of
water and decreased by the addition of MS4Å (Table 1, entries
18 and 20).18 Alternatively, the inter- or intramolecular addition
of an acetoxy group cannot be ruled out, although the use of
acetic acid as a solvent and the addition of potassium acetate are
not effective for the cycloaddition. A plausible mechanism for the
reaction of 1a, 2a, and water are shown in Scheme 1. Oxidative
addition of 2a to Pd(0) would afford allenylpalladium inter-
mediate 5, which reacts with water to afford 2-hydroxyallylpalla-
dium complex 6.19,20 Elimination of acetic acid from 6 would give
and triethylamine (0.75 mmol) in acetonitrile (1.5 mL) was heated
b
c
at 80 °C for 18 h under nitrogen. Isolated yields. Conducted with
d
e
1.0 mmol of 2a at 120 °C. Without triethylamine. Conducted with
f
1.5 mmol of 1e. Conducted with 1.5 mmol of 1f at 120 °C.
0.5 mmol of 1a and 2a, 3a was isolated in 68% yield (entry 1).
Methoxycarbonyl-substituted norbornene derivatives 1b, 1c, and
1d were less reactive, and therefore their cycloaddition needed
higher temperature to afford the corresponding cyclopropanes
3b, 3c, and 3d in high yields (entries 2−4). The products were
obtained with high stereoselectivity. In the reaction of dicyclo-
pentadiene 1e, one of two different double bonds selectively
reacted to give 3e as sole product (entry 5). The reaction using
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Note
Data for 3c. 119 mg, 69%. Brown amorphous solic. 1H NMR
(CDCl3): δ 7.32 (t, J = 7.2 Hz, 2H), 7.27−7.23 (m, 1H), 7.19 (d, J = 7.2
Hz, 2H), 3.74 (s, 2H), 3.66 (s, 6H), 3.01 (s, 2H), 2.71 (s, 2H), 2.04 (m,
1H), 1.93 (s, 2H), 1.10 (d, J = 11.4 Hz, 1H), 0.81 (d, J = 11.4 Hz, 1H).
13C NMR (CDCl3): δ 206.1, 171.8, 134.3, 129.4, 128.5, 126.8, 51.5, 50.4,
Scheme 1. Plausible Mechanism for the Cyclopropanation
+
47.8, 40.0, 29.3, 24.2, 23.1. HRMS (ESI): m/z calcd for C20H22NaO5
[M + Na]+ 365.1359, found 365.1373.
Data for 3d. 136 mg, 80%. Orange viscous oil. 1H NMR (CDCl3): δ
7.32−7.31 (m, 2H), 7.27−7.25 (m, 1H), 7.19−7.17 (m, 2H), 3.76 (s,
2H), 3.71 (s, 3H), 3.68 (s, 3H), 3.21 (s, 1H), 2.94 (s, 1H), 2.76 (s, 1H),
2.68 (s, 1H), 2.08 (s, 1H), 1.54 (s, 1H), 1.48 (s, 1H), 1.06 (d, J = 12.0 Hz,
1H), 0.96 (d, J = 11.4 Hz, 1H). 13C NMR (CDCl3): δ 206.0, 174.2,
172.5, 134.0, 129.3, 128.6, 126.9, 52.1, 52.0, 50.9, 50.2, 48.2, 41.4, 39.4,
27.9, 27.7, 25.3, 24.1. HRMS (ESI): m/z calcd for C20H22NaO5+ [M +
Na]+ 365.1359, found 365.1373.
1
Data for 3e. 84.9 mg, 64%. Pale brown amorphous solid. H NMR
(CDCl3): δ 7.31 (t, J = 7.2 Hz, 2H), 7.24 (t, J = 5.4 Hz, 1H), 7.18 (d, J =
7.8 Hz, 2H), 5.71 (m, 1H), 5.51 (m, 1H), 3.74 (s, 2H), 3.10−3.06 (m,
1H), 2.54 (dt, J = 7.2 Hz, J = 10.2 Hz, 1H), 2.38 (m, 1H), 2.29 (m, 2H),
2.23−2.17 (m, 1H), 1.99 (t, J = 2.4 Hz, 1H), 1.53 (d, J = 7.2 Hz, 1H),
1.24 (d, J = 6.6 Hz, 1H), 0.99 (d, J = 10.8 Hz, 1H), 0.89 (d, J = 10.8 Hz,
1H). 13C NMR (CDCl3): δ 207.8, 134.6, 132.7, 130.0, 129.4, 128.5,
126.7, 54.5, 50.9, 42.8, 39.6, 38.3, 31.6, 31.4, 27.4, 24.4, 23.3. HRMS
(ESI): m/z calcd for C19H20NaO+ [M + Na]+ 287.1406, found 287.1394
oxatrimethylenemethane palladium intermediate 7. Intermediate
9 would be formed by insertion of 1a to 8 and isomerized to 10
via a hydroxyallylpalladium intermediate. Reductive elimination
of 10 would afford 3a and Pd(0).
1
Data for 3f. 56.4 mg, 50%. Pale yellow amorphous solid. H NMR
(CDCl3): δ 7.33 (t, J = 7.8 Hz, 2H), 7.26 (t, J = 7.2 Hz, 1H), 7.20 (d, J =
6.6 Hz, 2H), 6.39 (s, 2H), 3.76 (s, 2H), 2.90 (t, J = 2.4 Hz, 1H), 2.86 (s,
2H), 1.68 (s, 2H), 1.10 (d, J = 9.0 Hz, 1H), 0.99 (d, J = 9.0 Hz, 1H). 13C
NMR (CDCl3): δ 204.7, 140.9, 134.3, 129.5, 128.6, 126.9, 50.4, 42.0,
40.2, 39.9, 34.7. HRMS (EI): m/z calcd for C16H16O+ M+ 224.1196,
found 224.1174.
EXPERIMENTAL SECTION
■
General. All reactions were carried out under nitrogen atmosphere.
Dry solvents were purchased and used directly as received. Propargyl
acetates were prepared by acetylation of corresponding alcohols.
Norbornene derivatives were prepared by Diels−Alder reaction or
purchased and used without further purification. 1H NMR spectra were
measured at 25 °C on a 600 MHz spectrometer. Chemical shifts are
reported in the scale relative to tetramethylsilane (0 ppm). 13C{1H}
NMR spectra were measured at 25 °C on a 151 MHz spectrometer.
Chemical shifts are reported in the scale relative to CDCl3 (77.1 MHz)
as an internal reference. High-resolution mass spectra were obtained by
electrospray ionization or electron ionization time-of-flight reflectron
experiments.
Data for 3g. 76.6 mg, 64%. Pale yellow amorphous solid. 1H NMR
(CDCl3): δ 7.18−7.11 (m, 4H), 3.77 (s, 2H), 2.30 (s, 2H), 2.23 (s, 3H),
1.91 (t, J = 1.8 Hz, 1H), 1.44 (m, 2H), 1.39 (d, J = 2.4 Hz, 2H), 1.28 (m,
2H), 0.85 (d, J = 10.2, 1H), 0.66 (d, J = 10.8 Hz, 1H). 13C NMR
(CDCl3): δ 207.6, 136.9, 133.4, 130.3, 130.3, 127.1, 126.1, 49.1, 36.0,
29.1, 28.8, 28.5, 23.9, 19.7. HRMS (ESI): m/z calcd for C17H20NaO+
[M + Na]+ 263.1406, found 263.1402.
Data for 3h. 66.2 mg, 55%. Pale yellow amorphous solid. 1H NMR
(CDCl3): δ 7.13 (d, J = 7.8 Hz, 2H), 7.08 (d, J = 7.8 Hz, 2H), 3.72 (s,
2H), 2.33 (s, 3H), 2.30 (s, 2H), 1.91 (s, 1H), 1.43 (m, 2H), 1.38 (s, 2H),
1.28 (m, 2H), 0.87 (d, J = 10.2 Hz, 1H), 0.67 (d, J = 10.8, 1H). 13C NMR
(CDCl3): δ 208.0, 136.3, 131.5, 129.3, 50.6, 36.0, 29.2, 28.8, 28.6, 24.0,
21.1. HRMS (ESI): m/z calcd for C17H20NaO+ [M + Na]+ 263.1406,
found 263.1417.
General Procedure for Cyclopropanation of Norbornenes
with Propargyl Acetates. To a mixture of Pd(PPh3)4 and norbornene
derivatives were added acetonitrile and then triethylamine and propargyl
acetates in a pressure vial. In all reactions in Tables 1 and 2 and eqs 2−4,
commercial dry acetonitrile was used without further drying. After
stirring at 80 or 120 °C for 18 h, the mixture was cooled to room
temperature and filtered through a short plug of silica gel using ether as
an eluent. The yield of 3a was determined by a GC analysis of the filtrate
using dodecane as an internal standard. For all products, the yields were
determined by isolation. After evaporation of volatiles in the filtrate,
the products were separated from the residue by silica gel column
chromatography (hexane/ethyl acetate). See Tables 1 and 2 and eqs
2−4 for specific solvent volumes, temperature, amounts of substrates,
and additives such as triethylamine for every example.
1
Data for 3i. 76.3 mg, 60%. Pale yellow amorphous solid. H NMR
(CDCl3): δ 7.26−7.22 (m, 1H), 6.81−6.79 (m, 2H), 6.75−6.74 (m,
1H), 3.79 (s, 3H), 3.73 (s, 2H), 2.31 (s, 2H), 1.92 (t, J = 3.0 Hz, 1H),
1.44 (m, 2H), 1.39 (d, J = 2.4 Hz, 2H), 1.28 (m, 2H), 0.87 (d, J = 10.8
Hz, 1H), 0.67 (d, J = 10.8, 1H). 13C NMR (CDCl3): δ 207.64, 159.68,
136.0, 129.5, 121.8, 115.0, 112.3, 55.1, 51.0, 36.0, 29.3, 28.8, 28.5, 24.1.
HRMS (ESI): m/z calcd for C17H20NaO2+ [M + Na]+ 279.1356, found
279.1366.
1
Data for 3j. 49.7 mg, 38%. Pale yellow amorphous solid. H NMR
(CDCl3): δ 7.11 (d, J = 7.2 Hz, 2H), 6.86 (d, J = 8.4 Hz, 2H), 3.79 (s,
3H), 3.70 (s, 2H), 2.30 (s, 2H), 1.91 (s, 1H), 1.43 (m, 2H), 1.38 (s, 2H),
1.28 (s, 2H), 0.87 (d, J = 10.2 Hz, 1H), 0.67 (d, J = 10.2 Hz, 1H). 13C
NMR (CDCl3): δ 208.1, 158.4, 130.4, 126.6, 114.0, 55.2, 50.0, 36.0, 29.2,
28.8, 28.5, 23.9. HRMS (ESI): m/z calcd for C17H20NaO2+ [M + Na]+
279.1356, found 279.1356.
1
Data for 3a. 76.8 mg, 68%. Pale yellow amorphous solid. H NMR
(CDCl3): δ 7.32 (t, J = 6.6 Hz, 2H), 7.26 (t, J = 4.8 Hz, 1H), 7.20 (d,
J = 7.2 Hz, 2H), 3.76 (s, 2H), 2.30 (s, 2H), 1.91 (t, J = 2.4 Hz, 1H), 1.44
(m, 2H), 1.39 (d, J = 2.4 Hz, 2H), 1.28 (m, 2H), 0.87 (d, J = 11.4 Hz,
1H), 0.67 (d, J = 10.8 Hz, 1H). 13C NMR (CDCl3): δ 207.8, 134.6,
129.4, 128.6, 126.8, 50.9, 36.0, 29.3, 28.8, 28.6, 24.2. HRMS (ESI): m/z
calcd for C16H19O+ [M + H]+ 227.1430, found 227.1442.
Data for 3k. 44.5 mg, 35%. Pale yellow amorphous solid. 1H NMR
(CDCl3): δ 7.61(d, J = 7.8 Hz, 2H), 7.30 (d, J = 8.4 Hz, 2H), 3.86 (s,
2H), 2.34 (s, 2H), 1.91 (t, J = 1.8 Hz, 1H), 1.46 (d, J = 7.8 Hz, 2H), 1.42
(m, 2H), 1.29 (m, 2H), 0.90 (d, J = 11.4 Hz, 1H), 0.72 (d, J = 10.2 Hz,
1H). 13C NMR (CDCl3): δ 206.0, 139.9, 132.3, 130.3, 118.8, 110.8, 50.5,
36.0, 29.7, 28.8, 28.5, 24.6. HRMS (ESI): m/z calcd for C17H16NO−
[M − H]− 250.1237, found 250.1215
1
Data for 3b. 96.2 mg, 68%. Orange amorphous solid. H NMR
(CDCl3): δ 7.32 (t, J = 7.2 Hz, 2H), 7.26 (t, J = 4.2 Hz, 1H), 7.19 (d, J =
7.8 Hz, 2H), 3.75 (s, 2H), 3.61 (s, 3H), 2.74 (dt, J = 9.6 Hz, J = 4.2 Hz,
1H), 2.69 (m, 1H), 2.38 (m, 1H), 1.97 (t, J = 2.4 Hz, 1H), 1.74 (m, 2H),
1.47 (q, J = 10.2 Hz, 2H), 0.99 (d, J = 11.1 Hz, 1H), 0.83 (d, J = 10.8 Hz,
1H). 13C NMR (CDCl3): δ 206.9, 174.1, 134.3, 129.4, 128.6, 126.8, 51.7,
50.8, 46.3, 39.6, 36.5, 31.3, 29.8, 28.3, 24.9, 23.4. HRMS (ESI): m/z
calcd for C18H20NaO3+ [M + Na]+ 307.1305, found 307.1283.
1
Data for 3l. 25.4 mg, 34%. Pale yellow amorphous solid. H NMR
(CDCl3): δ 2.36 (s, 2H), 2.19 (s, 3H), 1.89 (t, J = 2.4 Hz, 1H), 1.46 (m,
2H), 1.38 (d, J = 1.8 Hz, 2H), 1.30 (m, 2H), 0.95 (dt, J = 11.4 Hz, J = 4.2
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Note
Hz, 1H), 0.71 (d, J = 10.8 Hz, 1H). The NMR spectrum matches that
reported in the literature.21
(19) Daniel, K. L.; Furilla, J. L.; Wojcicki, A. J. Organomet. Chem. 2002,
655, 192−203.
(20) Huang, T.-M.; Hsu, R.-H.; Yang, C.-S.; Chen, J.-T.; Lee, G.-H.;
Wang, Y. Organometallics 1994, 13, 3657−3663.
(21) Matsushima, Y.; Kikuchi, H.; Uno, M.; Takahashi, S. Bull. Chem.
Soc. Jpn. 1999, 72, 2475−2482.
Data for 4. 21.5 mg, 38%. Yellow viscous oil. 1H NMR (CDCl3): δ
5.21 (s, 1H), 5.15 (m, 1H), 2.32 (s, 2H), 1.93 (s, 3H), 1.91 (s, 3H), 1.86
(s, 3H), 1.49 (m, 1H), 1.44 (m, 2H), 1.28 (m, 2H), 1.04 (d, J = 10.8 Hz,
1H), 1.01 (d, J = 2.4 Hz, 2H), 0.68 (d, J = 10.2 Hz, 1H). 13C NMR
(CDCl3): δ 140.6, 127.4, 119.9, 117.1, 93.7, 87.3, 43.8, 43.0, 36.0, 29.5,
28.6, 24.0, 23.8, 23.6, 20.2, 14.4. HRMS (EI): m/z calcd for C17H22+ M+
226.1717, found 226.1702.
ASSOCIATED CONTENT
■
S
* Supporting Information
1H and 13C NMR for all new compounds. This material is
available free of charge via the Internet at http://pubs.acs.org.
AUTHOR INFORMATION
■
Corresponding Author
*E-mail: sntsuka@ipc.shizuoka.ac.jp.
Notes
The authors declare no competing financial interest.
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(18) Water was demonstrated to be important for a successful reaction.
However, the amount of adventitious water entering the system from
the commercial dry solvents, reactor, and substrates was not defined.
Addition of water up to 1.0 equiv relative to the substrate may be
required for reproducibility depending on the solvent and substrate
quality as well as experimental techniques.
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