Ring-Expansion of MCPs in the Presence of DIAD or DEAD and Lewis Acids

Article abstract of DOI:10.1002/ejoc.200300515

Treatment of methylenecyclopropanes (MCPs) with DIAD or DEAD in MeCN under mild conditions in the presence of Lewis acid Zr(OTf)₄ gave the cyclobutanone ring-expansion products in good to high yields based on the employed DIAD or DEAD. From a d

Full text of DOI:10.1002/ejoc.200300515

FULL PAPER
Ring-Expansion of MCPs in the Presence of DIAD or DEAD and Lewis Acids
Li-Xiong Shao[a] and Min Shi*[b]
Keywords: Diethyl azodicarboxylate (DEAD) / Diisopropyl azodicarboxylate (DIAD) / Lewis acids / Ring expansion
Treatment of methylenecyclopropanes (MCPs) with DIAD or
DEAD in MeCN under mild conditions in the presence of
Lewis acid Zr(OTf)4 gave the cyclobutanone ring-expansion
products in good to high yields based on the employed DIAD
or DEAD. From a deuterium labeling experiment, the oxygen
atom is derived from ambient water.
( Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2004)
Introduction
Methylenecyclopropanes (MCPs) 1 are highly strained
but readily accessible molecules that have served as useful
building blocks in organic synthesis. MCPs 1 undergo a
variety of ring-opening reactions because the relief of ring
strain provides a potent thermodynamic driving force.[1]
Transition metal (such as Pd, Rh, Ru, and Pt) catalysis
of reactions of MCPs with various reactants has attracted
much attention,[2] first place being held by Pd0- or PdII-
catalyzed ring-opening reactions (Scheme 1). We recently
found that Lewis acid-catalyzed [M(OTf)n, M ϭ Yb, Sc, Sn,
etc.] ring-opening reactions between MCPs 1 and alcohols
and other nucleophiles took place in a different, novel man-
ner to give the corresponding ring-opened products in good
yields under mild conditions (Scheme 2).[3] This interesting
result encouraged us to investigate further the Lewis acid-
catalyzed reactions between MCPs 1 and other reactants.
In this paper we wish to report an unprecedented Lewis
acid-catalyzed ring-expansion reaction of MCPs 1 in the
presence of diisopropyl azodicarboxylate (DIAD) or diethyl
azodicarboxylate (DEAD).[4,5]
Scheme 1
Scheme 2
propyl azodicarboxylate (DIAD) in CH3CN as a solvent
produced a ring-expansion product cyclobutanone 2a
(MCP/DIAD, 2.5:1). The roles played by the Lewis acids in
this reaction were critical, no reaction occurring in their
absence (Table 1, entry 1). When Sn(OTf)2, Cu(OTf)2,
Sc(OTf)3, Zn(OTf)2, or BF3·Et2O (50 mol %) were em-
ployed as Lewis acids, 2a was obtained in low to moderate
yields based on the employed DIAD (Table 1, entries 2Ϫ3,
6Ϫ8). The Brønsted acid CF3SO3H (HOTf) did not cata-
lyze the reaction (Table 1, entry 5). Use of Zr(OTf)4 as a
Lewis acid at room temperature for 48 h, though, resulted
in 2a being produced in 100% yield based on the employed
DIAD (Table 1, entry 4). In other solvents such as acetone
or THF, 2a was obtained in 82% and 69% yields, respec-
tively, under otherwise the same conditions (Table 1, entries
9Ϫ10). Control experiment showed that: i) no reaction oc-
curred in the absence of DIAD, and ii) 2a was formed in
relatively lower yields (78% and 68% respectively) when an-
hydrous CH3CN was used as a solvent under the optimized
Results and Discussion
During our investigations into the ring-opening reaction
of MCPs 1 in the presence of various Lewis acids (50 mol
%), we found that the Lewis acid-catalyzed reaction of di-
phenylmethylenecyclopropane 1a in the presence of diiso-
[a]
State Key Laboratory of Organometallic Chemistry,
Shanghai Institute of Organic Chemistry, Chinese Academy of
Sciences,
354 Fenglin Lu, Shanghai 200032, China
[b]
School of Chemistry & Pharmaceutics, East China University
of Science and Technology,
130 MeiLong Road, Shanghai 200237, China,
Fax: (internat.) ϩ 86-21-64166128
Supporting information for this article is available on the
WWW under http://www.eurjoc.org or from the author.
426
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
DOI: 10.1002/ejoc.200300515
Eur. J. Org. Chem. 2004, 426Ϫ430

Ring Expansion of MCPs
FULL PAPER
˚
conditions or in the presence of molecular sieves (4 A), even equiv. of water being enough to give 2a in high yield in the
with prolonged reaction times. In addition, no reaction oc- ring-expansion reaction.
curred when the procedure was carried out under oxygen
Table 2. The effect of different concentrations of water in the reac-
tion between MCP 1a and DIAD in the presence of Zr(OTf)4; a)
all reactions were carried out with MCP 1a/DIAD ϭ 0.5:0.2 mmol
atmosphere in the absence of catalyst. These results suggest
that the oxygen atom of 2a might be derived from water
present in solvent and the ambient environment. In order
to clarify the source of the oxygen in this reaction, we car-
ried out the Zr(OTf)4-catalyzed reaction of MCP 1a in the
presence of 18OH2 and DIAD (Scheme 3).[6] As a result, we
found that 2a-18O was formed in 75% yield,[7] its 18O con-
tent being 47% (Scheme 3)[8] (see Supporting Information).
From this result we can conclude that the oxygen atom is
derived from the ambient water during the reaction.
in the presence of Zr(OTf)4 (0.1 mol) under an argon atmosphere
at room temperature for 36 h; b) isolated yields based on em-
ployed DIAD
Table 1. The effects of various Lewis acids in the reaction between
MCP 1a and DIAD; a) the reaction was carried out with MCP 1a/
DIAD ϭ 5:2 in the presence of Lewis acid (50 mol %) at room
temperature for 48 h; b) isolated yields based on employed DIAD;
c) the reaction was carried out in THF; d) the reaction was carried
out in acetone
Moreover, to gauge the repeatability of this interesting
ring-expansion reaction, we used freshly distilled MeCN as
the solvent and carried out this reaction three times under
argon atmosphere with subsequent hydrolysis of the reac-
tion mixture with water. It was found that 2a was formed
in 80~84% yields.[9] All these results suggest that this inter-
esting ring expansion reaction is reproducible.
For other aromatic MCPs 1b-g (both R1 and R2 are aro-
matic groups), the reactions proceeded very well to give the
corresponding cyclobutanones 2b-g in good to high yields
based on the employed DIAD under the optimized con-
ditions (Table 3, entries 1Ϫ6). For MCPs 1h-k (R1 is an
aromatic group and R2 is an aliphatic group), the corre-
Table 3. The ring-expansion of MCPs 1 in the presence of DIAD
and Zr(OTf)4; a) isolated yields based on DIAD
Scheme 3
In order further to clarify the effect of water on this ring-
expansion of MCPs 1, we also carried out the reaction in
freshly distilled MeCN containing various concentrations
of water. The results, including the result without the ad-
dition of water (Table 2, entry 1), are summarized in
Table 2. As can be seen, the concentration of water has only
a slight effect on this reaction (Table 2, entries 2Ϫ5), 1.0
Eur. J. Org. Chem. 2004, 426Ϫ430
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427

L.-X. Shao, M. Shi
FULL PAPER
sponding cyclobutanones 2h-k were also obtained in mod- 1,2-dicarboxylate (see Supporting Information).[10] Quanti-
erate to high yields under the same conditions (Table 3, en- tative GLC analysis showed that in the reaction mixture,
tries 7Ϫ10).
the molar ratio of product 2a to the formed diethyl hydra-
On the other hand, we also found that the MCPs are zine-1,2-dicarboxylate was 1.25 to 1 (see Supporting Infor-
rather sensitive to the Lewis acid employed in this reaction. mation).
With MCPs 1b and 1h, use of Sc(OTf)3 (50 mol %) Ϫ which
is not as effective as Zr(OTf)4 in the case of MCP 1a Ϫ as
a Lewis acid gave the corresponding cyclobutanones 2b and
2h in higher yields than were obtained by use of Zr(OTf)4
under the same conditions (Table 4, entries 1 and 4), al-
though it was still not effective for MCPs 1d and 1f
(Table 4, entries 2 and 3). Thus, for other MCP substrates
not examined in this paper, a careful survey of the Lewis
acid catalyst is likely to be required for this novel ring-ex-
pansion reaction to achieve higher yields.
Table 4. Reactions between MCPs 1 and DIAD in the presence of
Sc(OTf)3; a) isolated yields based on DIAD
The same ring-expansion reaction can also take place
with diethyl azodicarboxylate (DEAD, 40% in toluene) as
a reagent; the results are shown in Table 5. However, we
found that the yields of cyclobutanones 2 in the presence of
Lewis acid Zr(OTf)4 under the same conditions were
slightly decreased (Table 5, entries 1Ϫ3). This may be be-
cause the less polar toluene solvent used for the DEAD
solution disturbs this reaction to some extent.
Scheme 4. Plausible reaction mechanism
In conclusion, we found that MCPs in the presence of
DIAD or DEAD as a reagent and Zr(OTf)4 as catalyst in
MeCN undergo ring-expansion reactions to give cyclobut-
anones 2 in good to high yields. This method provides a
safer and more convenient synthetic route for the synthesis
of substituted cyclobutanones 2 under mild conditions than
traditional procedures such as epoxidation of MCPs fol-
lowed by rearrangement.[5] The Lewis acid, DIAD, and am-
bient moisture are crucial for this interesting ring-expansion
reaction of MCPs. Efforts to elucidate the mechanistic de-
tails of this reaction and to delineate its scope and limi-
tations are underway.
Table 5. Reactions between MCPs 1 and DEAD in the presence of
Zr(OTf)4; a) isolated yields based on DEAD
Experimental Section
1
General Remarks: H NMR spectra were recorded on a 300 MHz
spectrometer in CDCl3 with tetramethylsilane as the internal stand-
ard. Infrared spectra were measured on a PERKIN-ELMER 983
spectrometer. Mass spectra were recorded with a HP-5989 instru-
ment and HRMS was measured on a Finnigan MAϩ mass spec-
trometer. Satisfactory CHN microanalyses were obtained with a
Carlo-Erba 1106 analyzer. Melting points are uncorrected. All re-
actions were monitored by TLC with Huanghai GF254 silica gel-
coated plates. Flash column chromatography was carried out on
A plausible mechanism for this ring-expansion reaction
of MCPs 1 promoted by DEAD and Zr(OTf)4 is shown
in Scheme 4. The Lewis acid activates the DEAD towards
reaction with the MCPs 1 to afford a zwitterion A. The
rearrangement of A gave a ring-expansion zwitterion B,
which is neutralized to give the intermediate C. Hydrolysis
of C by ambient water produces 2 and diethyl hydrazine- 300Ϫ400 mesh silica gel.
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Eur. J. Org. Chem. 2004, 426Ϫ430

Ring Expansion of MCPs
FULL PAPER
General Procedure: The MCPs (0.50 mmol), DIAD (0.20 mmol),
Lewis acid catalyst (0.10 mmol), and distilled acetonitrile (CH3CN)
(1.0 mL) were placed in a Schlenk reaction tube under ambient
atmosphere. The mixture was stirred at room temperature. The sol-
vent was removed under reduced pressure and the residue was puri-
fied by flash column chromatography (SiO2).
1H NMR (CDCl3, 300 MHz, TMS): δ ϭ 2.80 (t, J ϭ 8.4 Hz, 2 H),
3.19 (t, J ϭ 8.4 Hz, 2 H), 7.28 (s, 8 H, Ar) ppm. 13C NMR (CDCl3,
75 MHz, TMS): δ ϭ 25.55, 43.54, 74.67, 127.68, 128.97, 132.94,
139.99, 207.87 ppm. MS (%): m/z ϭ 290 [Mϩ] (0.50), 248 (100).
C16H12Cl2O: calcd. C 66.00, H 4.15%; found C 66.20, H 4.07%.
2,2-Bis(4-flurophenyl)cyclobutanone (2g): Colorless liquid, IR
(CH2Cl2): ν˜ ϭ 1782, 1597, 1266, 742 cmϪ1 1H NMR (CDCl3,
.
The Ring-Expansion of MCP 1a in the Presence of Zr(OTf)4,
DIAD, and H218O: MCP 1a (0.5 mmol), DIAD (0.2 mmol),
Zr(OTf)4 (0.1 mmol), freshly distilled acetonitrile (CH3CN)
(1.0 mL), and H218O (0.5 mmol) were placed in a Schlenk reaction
tube under argon atmosphere. The mixture was stirred at room
temperature under argon atmosphere. The solvent was removed un-
der reduced pressure, and the residue was purified by flash column
chromatography (SiO2).
300 MHz, TMS): δ ϭ 2.80 (t, J ϭ 8.7 Hz, 2 H, CH2), 3.19 (t, J ϭ
8.7 Hz, 2 H, CH2), 6.95Ϫ7.06 (m, 4 H, Ar), 7.28Ϫ7.35 (m, 4 H,
Ar) ppm. 13C NMR (CDCl3, 75 MHz, TMS): δ ϭ 25.80, 43.41,
74.66, 115.60 (d, JC,F ϭ 20.6 Hz), 127.94 (d, JC,F ϭ 8.8 Hz), 137.71,
161.67 (d, JC,F ϭ 245.9 Hz), 208.30 ppm. MS (%): m/z ϭ 258 [Mϩ]
(0.51), 216 (100). HRMS calcd. for C16H12F2O: 258.0856; found:
258.0879.
2-(4-Ethoxyphenyl)-2-methylcyclobutanone (2h): Colorless liquid,
2,2-Diphenylcyclobutanone (2a): Colorless liquid and a known com-
pound. 1H NMR (CDCl3, 300 MHz, TMS): δ ϭ 2.83 (t, J ϭ
8.1 Hz, 2 H, CH2), 3.15 (t, J ϭ 8.1 Hz, 2 H, CH2), 7.17Ϫ7.39 (m,
10 H, Ar) ppm [ref.: J. K. Crandall, W. W. Conover, J. Org. Chem.
1978, 43, 3533]. 1H NMR (CDCl3, 60 MHz, TMS): δ ϭ 2.76 (t,
J ϭ 8.5 Hz, 2 H, CH2), 3.08 (t, J ϭ 8.5 Hz, 2 H, CH2), 7.0Ϫ7.8
(m, 10 H, Ar)] ppm. 13C NMR (CDCl3, 75 MHz, TMS): δ ϭ 25.50,
43.33, 76.05, 126.32, 126.85, 128.66, 142.00, 209.09 ppm. MS (%):
m/z ϭ 222 [Mϩ] (1.68), 180 (100).
1
IR (CH2Cl2): ν˜ ϭ 1778, 1509, 1266, 739 cmϪ1. H NMR (CDCl3,
300 MHz, TMS): δ ϭ 1.40 (t, J ϭ 6.9 Hz, 3 H, CH3), 1.43 (s, 3 H,
CH3), 2.12 (dt, J ϭ 10.5, 6.9 Hz, 1 H), 2.48 (dt, J ϭ 10.8, 6.6 Hz,
1 H), 2.98Ϫ3.22 (m, 2 H), 4.01 (q, J ϭ 6.9 Hz, 2 H, OCH2), 6.86
(d, J ϭ 9.0 Hz, 2 H, Ar), 7.26 (d, J ϭ 8.4 Hz, 2 H, Ar) ppm. 13C
NMR (CDCl3, 75 MHz, TMS): δ ϭ 14.83, 25.53, 26.18, 42.56,
63.40, 67.33, 114.48, 126.65, 134.27, 157.63, 212.67 ppm. MS (%):
m/z ϭ 204 [Mϩ] (17.98), 162 (100). HRMS calcd. for C13H16O2:
204.1150; found: 204.1163.
2,2-Bis(4-methoxyphenyl)cyclobutanone (2b): White solid, M.p.
63Ϫ64 °C. IR (CH2Cl2): ν˜ ϭ 1778, 1509, 1409, 1266, 739 cmϪ1. 1H
NMR (CDCl3, 300 MHz, TMS): δ ϭ 2.75 (t, J ϭ 8.4 Hz, 2 H,
CH2), 3.14 (t, J ϭ 8.4 Hz, 2 H, CH2), 3.75 (s, 6 H, 2 CH3O), 6.83
(d, J ϭ 9.0 Hz, 4 H, Ar), 7.25 (d, J ϭ 9.0 Hz, 4 H, Ar) ppm.
13C NMR (CDCl3, 75 MHz, TMS): δ ϭ 25.70, 43.21, 55.12, 74.64,
113.90, 127.43, 134.35, 158.25, 209.73 ppm. MS (%): m/z ϭ 282
[Mϩ] (4.74), 240 (98.20), 223 (100). C18H18O3: calcd. C 76.57, H
6.42%; found C 76.28, H 6.28%.
2-Benzo[1,3]dioxol-5-yl-2-methylcyclobutanone
(2i):
Colorless
liquid, IR (CH2Cl2): ν˜ ϭ 2959, 2923, 2864, 1781, 1514, 1446, 1394,
1
1109, 1095, 1055, 817 cmϪ1. H NMR (CDCl3, 300 MHz, TMS):
δ ϭ 1.50 (s, 3 H), 2.07Ϫ2.17 (m, 1 H), 2.40Ϫ2.49 (m, 1 H),
2.98Ϫ3.22 (m, 2 H), 5.93 (dd, J ϭ 1.5, 2.1 Hz, 2 H, Ar), 6.75Ϫ6.82
(m, 2 H, Ar), 6.86 (d, J ϭ 1.5 Hz, 1 H) ppm. 13C NMR (CDCl3,
75 MHz, TMS): δ ϭ 25.76, 26.39, 42.47, 67.63, 100.96, 106.48,
108.21, 118.51, 136.30, 146.21, 147.76, 212.11 ppm. MS (%): m/z ϭ
204 [Mϩ] (18.06), 162 (100). HRMS calcd. for C12H12O3: 204.0786;
found: 204.0778.
2-(4-Methoxyphenyl)-2-phenylcyclobutanone (2c): Colorless liquid,
IR (CH2Cl2): ν˜ ϭ 1779, 1608, 1510, 1266, 739 cmϪ1 1H NMR
.
2-Methyl-2-p-tolylcyclobutanone (2j): Colorless liquid, IR
(CH2Cl2): ν˜ ϭ 2960, 2922, 1773, 1608, 1505, 1485, 1434, 1239,
(CDCl3, 300 MHz, TMS): δ ϭ 2.81 (t, J ϭ 9.8 Hz, 2 H, CH2),
3.17(t, J ϭ 9.8 Hz, 2 H, CH2), 3.77 (s, 3 H, OCH3), 6.85 (d, J ϭ
9 Hz, 2 H, Ar), 7.28Ϫ7.38 (m, 7 H, Ar) ppm. 13C NMR (CDCl3,
75 MHz, TMS): δ ϭ 25.62, 43.30, 55.19, 75.43, 113.99, 126.32,
126.78, 127.50, 128.63, 134.14, 142.29, 158.37, 209.22 ppm. MS
(%): m/z ϭ 252 [Mϩ] (5.84), 210 (100). HRMS calcd. for
C17H16O2: 252.1150; found: 252.1138.
1108, 1038, 936, 811 cmϪ1 1H NMR (CDCl3, 300 MHz, TMS):
.
δ ϭ 1.52 (s, 3 H), 2.09Ϫ2.18 (m, 1 H), 2.33 (s, 3 H), 2.45Ϫ2.55 (m,
1 H), 2.98Ϫ3.22 (m, 2 H), 7.15 (d, J ϭ 8.4 Hz, 2 H, Ar), 7.25 (d,
J ϭ 8.1 Hz, 2 H, Ar) ppm. 13C NMR (CDCl3, 75 MHz, TMS): δ ϭ
20.98, 25.50, 26.25, 42.58, 67.75, 125.50, 129.27, 136.33, 139.40,
212.51 ppm. MS (%): m/z ϭ 174 (Mϩ) [4.11], 132 (100). HRMS
calcd. for C12H14O: 174.1045; found: 174.1023.
2,2-Bis(4-methylphenyl)cyclobutanone (2d): Colorless liquid, IR
(CH2Cl2): ν˜ ϭ 1781, 1510, 1266, 739 cmϪ1 1H NMR (CDCl3,
.
2-(4-Bromophenyl)-2-methylcyclobutanone (2k): Yellow liquid, IR
(CH2Cl2): ν˜ ϭ 2961, 2924, 2859, 1775, 1489, 1396, 1245, 1096,
300 MHz, TMS): δ ϭ 2.28 (s, 6 H, 2 CH3), 2.78 (t, J ϭ 8.7 Hz, 2
H), 3.13 (t, J ϭ 8.7 Hz, 2 H), 7.10 (d, J ϭ 8.7 Hz, 4 H, Ar), 7.24
(d, J ϭ 8.7 Hz, 4 H, Ar) ppm. 13C NMR (CDCl3, 75 MHz, TMS):
δ ϭ 21.26, 25.87, 43.57, 75.88, 126.52, 129.63, 136.73, 139.60,
209.72 ppm. MS (%): m/z ϭ 250 [Mϩ] (2.28), 208 (100). HRMS
calcd. for C18H18O: 250.1358; found: 250.1330.
1
1009, 823 cmϪ1. H NMR (CDCl3, 300 MHz, TMS): δ ϭ 1.52 (s,
3 H), 2.12Ϫ2.21 (m, 1 H), 2.42Ϫ2.51 (m, 1 H), 2.98Ϫ3.26 (m, 2
H), 7.24 (d, J ϭ 8.7 Hz, 2 H, Ar), 7.46 (d, J ϭ 8.4 Hz, 2 H, Ar)
ppm. 13C NMR (CDCl3, 75 MHz, TMS): δ ϭ 25.32, 26.34, 42.60,
67.40, 120.58, 127.37, 131.63, 141.34, 211.51 ppm. MS (%): m/z ϭ
238 [Mϩ] (100), 196 (66.00). HRMS calcd. for C11H11BrO:
237.9993; found: 237.9996.
2-(2-Chlorophenyl)-2-phenylcyclobutanone (2e): Pale yellow liquid,
1
IR (CH2Cl2): ν˜ ϭ 1780, 1597, 1265, 739 cmϪ1. H NMR (CDCl3,
300 MHz, TMS): δ ϭ 2.71Ϫ2.78 (m, 1 H), 3.15Ϫ3.31 (m, 3 H),
7.21Ϫ7.39 (m, 8 H, Ar), 7.77Ϫ7.79 (m, 1 H, Ar) ppm. 13C NMR
(CDCl3, 75 MHz, TMS): δ ϭ 24.35, 43.01, 75.15, 120.34, 126.79,
126.95, 128.13, 128.43, 128.48, 131.15, 133.28, 137.83, 139.40,
207.70 ppm. MS (%): m/z ϭ 221 [Mϩ Ϫ Cl] (36.98), 179 (100).
Supporting Information Available: 13C NMR charts of spectroscopic
data of 2aϪk and GLC and GC-MS data for the formation of
diethyl hydrazine-1,2-dicarboxylate and 18O-labeled cyclobutanone
(see also the footnote on the first page of this article).
HRMS calcd. for C16H13ClO: 221.0966; found: 221.0990 (Mϩ
Cl).
Ϫ
Acknowledgments
2,2-Bis(4-chlorophenyl)cyclobutanone (2f): White solid, M.p.
103Ϫ105 °C. IR (CH2Cl2): ν˜ ϭ 1784, 1491, 1401, 1093, 825 cmϪ1
We thank the State Key Basic Research Project (Project 973) (No.
G2000048007), Shanghai Municipal Committee of Science and
.
Eur. J. Org. Chem. 2004, 426Ϫ430
www.eurjoc.org
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
429

L.-X. Shao, M. Shi
FULL PAPER
Technology, and the National Natural Science Foundation of
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Received August 13, 2003
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