Hypervalent iodine(iii)-mediated cyclopropa(e)nation of alkenes/alkynes under mild conditions

Article abstract of DOI:10.1039/c3ob42123f

Hypervalent iodine(iii)-mediated dioxygenation and diamination of alkenes have been previously developed. In this study, the potential application of hypervalent iodine(iii) reagent was successfully extended to the dialkylation and cyclopropa(e)nation of

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Hypervalent iodine(III)-mediated
cyclopropa(e)nation of alkenes/alkynes under mild
conditions
Cite this: DOI: 10.1039/x0xx00000x
Shaoxia Lin,a Mengru Li,a Zhiyong Dong,a Fushun Liang*a,b and Jingping Zhang*a
Hypervalent iodine(III)-mediated dioxygenation and diamination of alkenes have been
previously developed. In this study, the potential application of hypervalent iodine(III)
reagent was successfully extended to the dialkylation and cyclopropa(e)nation of unsaturated
alkenes and alkynes. The reactions of alkenes with malononitrile and other active methylene
compounds as the carbon nucleophiles, give access to multisubstituted cyclopropane
derivatives in moderate to excellent yields. Both electron–rich and electron–deficient
alkenes are suitable substrates. Alkynes, no matter terminal or internal alkynes, work well,
affording the corresponding highly functionalized cyclopropenes efficiently. A plausible
mechanism of iodo(III)cyclopropanation, ring opening attacked by the carbon-nucleophile,
and recyclization was proposed for the cyclopropanation of trans-alkene substrates. The
cyclopropenation was supposed to proceed via iodo(III)cyclopropanetion, ring-opening
attacked by the carbon-nucleophile, recyclization into a four-membered iodo(III)cyclobutene
and final reductive elimination. The protocol might provide a complementary route to
cyclopropanation/cyclopropenation.
Received 00th January 2012,
Accepted 00th January 2012
DOI: 10.1039/x0xx00000x
www.rsc.org/
Introduction
Cyclopropane derivatives are present in a large number of natural
and biologically important products. They are also versatile building
blocks in organic transformation. Their unique reactivity and
structural properties lead to a range of interesting and characteristic
transformations.1 Various synthetic methods for their preparation
have been developed (Scheme 1), such as Simmons-Smith reaction,2
transitional-metal-catalyzed addition of diazo compounds3a-e or
iodonium ylides3f-h to an alkene, organocatalyzed addition-
cyclization of β-halogenated carbonyl compounds or a sulfur ylide to
an activated double bond.4 On the other hand, cyclopropenes, as
another important three-membered carbocycles, have broad utility as
synthons in organic synthesis.5 Typical synthetic methods include a
carbene or carbenoid addition to alkynes6 catalyzed by Rh(II),6b-i
Ir(II),6j Co(II),6k,l and Ag(I),6m,n and elimination of substituted
aDepartment of Chemistry, Northeast Normal University, Changchun
130024,
China.
Email:
liangfs112@nenu.edu.cn.
zhangjp66@nenu.edu.cn. Fax: (+86) 431-85099759
bKey Laboratory for UV-Emitting Materials and Technology of Ministry
of Education Northeast Normal University 5268 Renmin St., Changchun
130024, China
† Electronic Supplementary Information (ESI) available: 1H and 13C
NMR copies of all products . See DOI: 10.1039/b000000x/
Scheme 1. Approaches for the cyclopropanation and
cyclopropenation
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cyclopropanes under basic conditions.7 Despite significant progress and DCE, the yields were improved to some extent (entries 3-5).
o
made in this area, some of the methods might suffer from substrate Raising the temperature to 80 C gave a yield of 51% (entry 6).
limitation, functional group tolerance, and the employment of Excess malononitrile was not beneficial for the explored reaction
transition metal catalyst, which is highly toxic and environmentally (entry 7). 2.2 equiv of PhI(OAc)2 gave 2a in an improved yield
unfriendly. Therefore, to match the increasing scientific and of 67% (entry 8). The introduction of external additive such as
pharmaceutical demands, it is still of continued interest and great K2CO3 made the system cleaner and 71% yield was achieved
importance to develop facile and efficient approaches towards (entry 9). Other bases like Cs2CO3, K3PO4 and Na2CO3 were also
cyclopropa(e)nation.
screened, but gave unsatisfied result (entries 10-12). The role of
In our previous research, we communicated the reaction of the base was supposed to remove the acid (2 equiv) generated in
chalcones with malononitrile in the open air, which provided an the reaction system. Other hypervalent iodine(III) reagents were
unprecedented β-cyanation products (Scheme 2).8 To explore the also examined, however, PhI(OTf)2 and PhI(OPiv)2 proved to be
role of molecular oxygen in the reaction and further elucidate the inferior and PhI(OTs)OH inert (entries 13-15). The structure of
plausible mechanism, in the continued work, external oxidants like 2a and its stereochemistry were confirmed by the single-crystal
hypervalent iodine(III) reagents9 were introduced. As a result, X-ray diffraction (Figure 1).13
cyanated products were completely suppressed and cyclopropane
derivatives were produced exclusively. Further work indicates that Table 1. Optimization of the reaction conditionsa
this protocol could be applicable to general alkene and alkyne
substrates,
furnishing
the
corresponding
cyclopropanes/cyclopropenes in good efficiency. Noteworthy that,
although the diamination10 and dioxygenation11 of alkenes/alkynes
by the hypervalent iodine(III) reagents have been well-documented,
the potential of iodine(III) reagents in oxidative dialkylation and/or
cyclopropanation remains scarce. Literature search revealed that
only one example of PhI(OAc)2-mediated cyclopropanation was
reported by Wirth and co-workers early in 2003 (eq. 1).12 However,
the reaction was restricted by limited scope and poor yields.
Compared with the common routes toward cyclopropanes and
cyclopropenes, i.e., addition reaction of an alkene or alkyne with
metal carbenes derived from the decomposition of diazo compounds
or iodonium ylides,3,6b-n this methodology has the advantage of
avoiding the utilization of transition metal catalysts.
Entry Oxidant (equiv)
Additive Solvent
T (oC)
Yield [%]c
1
PhI(OAc)2 (1.2)
PhI(OAc)2 (1.2)
PhI(OAc)2 (1.2)
PhI(OAc)2 (1.2)
PhI(OAc)2 (1.2)
PhI(OAc)2 (1.2)
PhI(OAc)2 (1.2)
PhI(OAc)2 (2.2)
PhI(OAc)2 (2.2)
PhI(OAc)2 (2.2)
PhI(OAc)2 (2.2)
PhI(OAc)2 (2.2)
PhI(OTf)2 (2.2)
PhI(OPiv)2 (2.2)
―
DMF
MeCN
toluene
DCM
DCE
DCE
DCE
DCE
DCE
DCE
DCE
DCE
DCE
DCE
DCE
30
30
30
30
30
80
80
80
80
80
80
80
80
80
80
0
2
―
5
3
―
9
4
―
38
44
51
43b
67
71
42
68
51
39
59
0
5
―
6
―
7
―
8
―
9
K2CO3
Cs2CO3
K3PO4
NaOAc
K2CO3
K2CO3
10
11
12
13
14
Scheme 2. Reactions of chalcones with malononitrile under different
oxidation conditions
15
PhI(OTs)OH (2.2) K2CO3
a
Reactions were carried out with chalcone (1.0 mmol),
malononitrile (1.2 equiv), hypervalent iodine(III) in solvent (4
b
c
mL) unless other noted. 3.0 equiv malononitrile. Isolated
yield.
Results and Discussion
Reaction optimization
Initially, the model reaction of chalcone 1a and malononitrile in
the presence of PhI(OAc)2 was examined under various
conditions (Table 1). No cyclopropane product was detected
when the reaction was performed in DMF at room temperature
(entry 1). The highly substituted cyclopropane 2a was observed
in MeCN (entry 2). With other solvents such as toluene, DCM
2 | Org. Biomol. Chem., 2013, 00, 1-9
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Figure 1. X-ray Crystal Structures of 2a and 2n.
Substrate scopes
Under the optimized conditions (Table 1, entry 9), selected
chalcones reacted with malononitirle in DCE at 80 oC to give
highly substituted cyclopropanes 2a-d in moderate yields (Table
2, entries 1-4). To our delight, a wide variety of alkenes were
also suitable for the cyclopropanation reaction. Both styrene and
styrene derivatives with substituents such as methyl-, tert-, butyl-
and bromo- at the para-position of the phenyl ring proceeded
efficiently,
cyclopropanes 2e-h in high yields (81-88%, entries 5-8). 2-
Thienylethylene afforded 2-thienylcyclopropane-1,1-
affording
the
corresponding
substituted
dicarbonitrile (2i) in 92% yield (entry 9). 1,1-Disubstituted
alkenes like -methylstyrene was found to be compatible under
the explored reactions, giving tetrasubstituted cyclopropane 2j in
89% yield (entry 10). The reaction with aliphatic terminal alkene
proceeded smoothly and product 2k was obtained in 87% yield
(entry 11). Diene can react one of the double bonds, affording
cyclopropane 2l with one terminal double bond intact even under
more forcing conditions. (entry 12). Internal alkenes also worked
well. Substrates including acyclic-styrene, trans-stilbene, and
cyclic indene, 1,2-dihydro-naphthalene, 2-norbornene, 1-methyl-
cyclohexene and 1-phenylhexene produced multisubstituted
cyclopropanes 2m-s in 51-96% yields (entries 13-19). On the
basis of 1H NMR spectroscopy and the single-crystal X-ray
diffraction of 2a and 2n (Figure 1),13 the relative configuration of
2a-c, 2m and 2n are assigned to be trans stereoisomers. However,
compound 2d was obtained as a mixture of diastereoisomers
(with around 7% cis-isomers observed based on 1H NMR
analysis). All of the above results indicate the efficiency of the
hypervalent iodine(III)-mediated cyclopropanation reaction.
Contrary to that with 1-methyl-cyclohexene and 1-
phenylhexene (Table 2, entries 18 and 19), in the reactions of
parent cyclohexene and cyclopentene with malononitrile (1.2
equiv), no corresponding cyclopropane products were detected.
Instead, dialkylation products 3a and 3b were obtained as the
main products. When 2.2 equiv of malononitrile was used, the
yields of 3a and 3b reached up to 85% and 87% yields,
respectively (eqs. 2 and 3 in Scheme 3).14,15
Table 2. PhI(OAc)2-mediated cyclopropanation of alkenes with
malononitrilea
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Scheme 3. Dialkylation of cyclopentene and cyclohexene with phenylacetylene afforded the desired cyclopropanes 6a-c and
malononitrile in the presence of PhI(OAc)2.
cyclopropenes 7, respectively, albeit in low to moderate yields
(Table 4, entries 1-4).
The hypervalent iodine(III)-mediated
cyclopropanation
strategy was also applicable to alkyne substrates (Table 3). It was
found that, in this case, no extra base was necessary.
Phenylacetylene and substituted phenylacetylenes gave the
corresponding cyclopropenes 5a-e in excellent yields (entries 1-
5). The substituents on the phenyl ring may be alkyls (methyl
and t-butyl), and halogen atoms (Cl and F) etc.. Similar to that of
diene substrate (Table 2, entry 12), bisacetylene can react with
one carbon–carbon triple bond and the other one intact, giving
cyclopropene 5f in 91% yield (entry 6). In addition to the
terminal alkynes, internal alkynes were also examined. The
reactions based on alkyl aryl alkyne, like 1-phenyl-1-pentyne and
dialkyl alkyne, like 2-pentyne proceeded efficiently, giving the
corresponding tetrasubstituted cyclopropenes 5g and 5h in high
to excellent yields (entries 7 and 8). However, diarylalkyne, e.g.
diphenylethyne and electron-deficient alkyne like ethyl 3-
phenylpropiolate, gave low to moderate yields (28% and 47%,
respectively, entries 9 and 10).16,17
Table 4. Cyclopropanation/Cyclopropenation of selected alkenes and
alkynes with ethyl nitroacetatea
Table 3. PhI(OAc)2-Mediated cyclopropenation of alkynes and
malononitrilea
Proposed mechanism
In order to elucidate the possible mechanism for the
cyclopropa(e)nation reaction, several control experiments were
carried out. Upon treatment of PhI(OAc)2 with K2CO3, no PhIO
was formed. In the mixture of malononitirle, PhI(OAc)2 and
K2CO3 in DCE, no ligand exchange between acetate anion and
malononitrile was detected, same as that reported by Wirth et
al.12 (see the supporting information). Moreover, both cis-
stilbene (eq. 4) and trans-stilbene (Table 2, entry 14) afforded
trans-2,3-diphenylcyclopropane-1,1-dicarbonitrile
2n,
as
evidenced by their X-ray crystal structures. Based on the above
control experiments, along with the fact that some of the reaction
proceeded smoothly in the absence of K2CO3 (Table 1, entry 8
and Table 3), the mechanism of iodo-ylide pathway was ruled out.
A plausible mechanism for the formation of cyclopropane 2
was proposed, as depicted in Scheme 4 (with trans-alkenes as an
example).19 Initially, the electrophilic addition between
PhI(OAc)2 and the alkene 1 generates iodo(III)cyclopropane I,10
followed by the formation of ion pair II, with the elimination of
In the following work, other active methylene compounds
were investigated as the carbon-nucleophile.18 Ethyl nitroacetate
proved to be suitable and the reactions with alkenes such as
styrene, 2-norbornene and chalcone, and alkyne such as
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acetic acid. Then, a nucleophilic ring opening takes place, giving hypervalent iodine(III)-mediated dialkylation of unsaturated
3
alkenes and alkynes are in progress.
rise to  -iodane III. With the elimination of the second
molecular acetic acid, zwitterionic IV is formed, which
undergoes cyclopropanation to furnish the final product 2.12
Acknowledgements
Financial support from the National Natural Science Foundation
The possible mechanism for the cyclopropenation of alkynes
of China (21172034), Program for New Century Excellent
was depicted in Scheme 5, although the exact mechanism is still
Talents in University (NCET-11-0611), the Department of
not clear. The procedure involves iodo(III)cyclopropenation, ring
Science and Technology of Jilin Province (201215002), and the
Fundamental Research Funds for the Central Universities
(12SSXT132) is gratefully acknowledged.
opening attacked by the malononitrile anion to give intermediate
III, tautemerization (IV-IV’) via elimination of HOAc and ring-
closure into four-membered iodo(III)cyclobutene V, and final
formation of cyclopropenation product via hypervalent
iodine(III)-mediated reductive elimination.20
Experimental section
General experimental
For general experimental details see ESI. The ESI also contains
spectroscopic data for compounds 2, 3, 5, 6 and 7.
Representative procedure for cyclopropanation. Synthesis of 2a:
Complex PhI(OAc)2 (354 mg, 1.1 mmol), K2CO3 (152 mg, 1.1
mmol), malononitrile (40 mg, 0.6 mmol) and chalcone 1a (104 mg,
0.5 mmol) were dissolved in DCE (2.0 mL) in a 25 mL flask. The
mixture was stirred at 80 °C for 1 h (monitored by TLC). Then the
reaction mixture was cooled to room temperature, poured into the
water and extracted with CH2Cl2 (3 × 10 mL). The combined
organic phase was washed with water (3 × 10 mL). The solvent was
removed under reduced pressure, and the residue was purified by a
flash silica gel column chromatography (EtOAc/petroleum ether =
1:10) to give 2a as colorless crystals in 71% yield.
Scheme 4. Proposed mechansim for the cyclopropanation with trans-
alkene substrates
2-Benzoyl-3-phenylcyclopropane-1,1-dicarbonitrile
(2a):
Colorless
crystals. m.p. 129-131 ºC. 1H NMR (500 MHz, CDCl3): δ = 3.92-3.93 (d, J =
8.0 Hz, 1H), 4.04-4.06 (d, J = 8.0 Hz, 1H), 7.38-7.40 (m, 2H), 7.46-7.48 (t, J
= 6.5 Hz, 3H), 7.60-7.63 (t, J = 8.0 Hz, 2H), 7.73-7.75 (d, J = 7.5 Hz, 1H),
8.11-8.13 (m, 2H). 13C NMR (CDCl3, 125 MHz): δ = 15.3, 35.4, 38.6, 111.5,
112.1, 128.3, 128.7, 129.3, 129.4, 129.8, 135.1, 135.3, 188.8. MS calcd m/z
272.09, found 273.09 [(M + 1)]+. Anal. Calcd for C18H12N2O: C, 79.39; H,
4.44; N, 10.39; Found: C, 79.53; H, 4.47; N, 10.48.
2-Benzoyl-3-(p-tolyl)cyclopropane-1,1-dicarbonitrile (2b): White solid.
m.p. 145-147 ºC. 1H NMR (500 MHz, CDCl3): δ = 2.39 (s, 3H), 3.88-3.89 (d,
J = 8.0 Hz, 1H), 4.02-4.03 (d, J = 8.0 Hz, 1H), 7.59-7.63 (t, J = 8.0 Hz, 2H),
7.73-7.76 (t, J = 7.5 Hz, 1H), 8.10-8.12 (t, J = 7.5 Hz, 2H). 13C NMR (CDCl3,
125 MHz): δ = 15.3, 21.3, 35.6, 38.7, 111.7, 112.3, 126.4, 130.0, 135.1,
140.0, 188.9. MS calcd m/z 286.11, found 287.11 [(M + 1)]+. Anal. Calcd for
C19H14N2O: C, 79.70; H, 4.93; N, 9.78; Found: C, 79.56; H, 4.90; N, 9.71.
2-Benzoyl-3-(3-nitrophenyl)cyclopropane-1,1-dicarbonitrile (2c): White
Scheme 5. Proposed mechanism for the cyclopropenation
1
solid. m.p. 168-170 ºC. H NMR (500 MHz, CDCl3): δ = 4.05-4.07 (d, J =
8.0 Hz, 1H), 4.14-4.16 (d, J = 8.0 Hz, 1H), 7.63-7.66 (t, J = 8.0 Hz, 2H),
7.69-7.73 (t, J = 8.0 Hz, 1H), 7.76-7.81 (m, 2H), 8.14-8.15 (d, J = 7.5 Hz,
2H), 8.25 (s, 1H), 8.33-8.34 (d, J = 8.0 Hz, 1H) . 13C NMR (CDCl3, 125
MHz): δ = 15.3, 35.4, 37.1, 110.8, 111.6, 123.2, 124.8, 128.9, 129.5, 130.6,
131.7, 134.8, 134.9, 135.5, 148.6, 187.9. MS calcd m/z 317.08, found 318.08
[(M + 1)]+. Anal. Calcd for C18H11N3O3: C, 68.14; H, 3.49; N, 13.24; Found:
C, 68.25; H, 3.51; N, 13.31.
Conclusions
In summary, we have developed
a new and efficient
cyclopropa(e)nation method by the utilization of PhI(OAc)2
reagent. The reaction features broad substrate scope (both
electron-deficent and -rich alkenes/alkynes), relatively mild
conditions, and high efficiency. The beauty of the chemistry
relies on the straightforward transformation of the initial iodo-
heterocyclopropa(e)ne into the final cyclopropa(e)ne over the
unique reactivity of hypervalent iodine reagent as both excellent
electrophile and hypernucleofuge.9 Further studies to explore the
scope of the carbon nucleophile in the cyclopropanation and
(E)-2-Benzoyl-3-styrylcyclopropane-1,1-dicarbonitrile (2d): Brown oil.
1
(the following H NMR and 13C NMR data are based on the trans-isomers):
1H NMR (500 MHz, CDCl3): δ = 3.45-3.48 (t, J = 8.5 Hz, 1H), 3.74-3.75 (d,
J = 7.5 Hz, 1H), 5.98-6.03 (m, 1H), 6.92-6.95 (d, J = 16.0 Hz, 1H), 7.31-7.36
(m, 3H). 7.37-7.43 (m, 2H), 7.57-7.59 (m, 2H), 7.69-7.73 (m, 1H), 8.05-8.07
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(m, 2H). 13C NMR (CDCl3, 125 MHz): δ = 14.2, 14.9, 36.1, 36.9, 37.8, 40.6, 2-Methyl-2-(3-(prop-1-en-2-yl)phenyl)cyclopropane-1,1-dicarbonitrile
1
111.4, 112.2, 112.7, 112.9, 118.6, 125.8, 126.8, 128.3, 128.8, 128.8, 128.9, (2l): White solid. m.p. 85-87 ºC. H NMR (500 MHz, CDCl3): δ = 1.78 (s,
129.2, 129.3, 129.4, 129.4, 129.7, 129.8, 130.8, 131.9, 133.7, 135.0, 188.5, 3H), 1.97-1.98 (d, J = 6.0 Hz, 1H), 2.16 (s, 3H), 2.32-2.33 (d, J = 6.0 Hz, 1H),
188.9. MS calcd m/z 298.11, found 299.11 [(M + 1)]+. Anal. Calcd for 5.14 (s, 1H), 5.39 (s, 1H), 7.24-7.26 (t, J = 4.0 Hz, 1H), 7.36-7.47 (m, 3H).
C20H14N2O: C, 80.52; H, 4.73; N, 9.39; Found: C, 80.66; H, 4.75; N, 9.47.
13C NMR (CDCl3, 125 MHz): δ = 11.5, 21.8, 24.5, 29.9, 40.4, 113.6, 113.9,
2-Phenylcyclopropane-1,1-dicarbonitrile (2e): Colorless crystals. m.p. 60- 114.4, 125.4, 126.4, 127.2, 129.2, 136.9, 142.4, 142.6. MS calcd m/z 222.12,
62 ºC. 1H NMR (500 MHz, CDCl3): δ = 2.23-2.28 (m, 2H), 3.29-3.32 (t, J = found 223.12 [(M + 1)]+. Anal. Calcd for C15H14N2: C, 81.05; H, 6.35; N,
9.0 Hz, 1H), 7.29-7.31 (m, 2H), 7.41-7.45 (m, 3H). 13C NMR (CDCl3, 125 12.60; Found: C, 81.19; H, 6.37; N, 12.68.
1
MHz): δ = 7.0, 22.0, 34.9, 112.9, 115.2, 128.2, 128.7, 129.2, 130.4. MS calcd 2-Methyl-3-phenylcyclopropane-1,1-dicarbonitrile (2m): Colorless oil. H
m/z 169.07, found 170.07 [(M + 1)]+. Anal. Calcd for C11H8N2: C, 78.55; H, NMR (500 MHz, CDCl3): δ = 1.53-1.54 (d, J = 9.0 Hz, 3H), 2.43-2.46 (m,
4.79; N, 16.66; Found: C, 78.44; H, 4.76; N, 16.54.
1H), 2.90-2.91 (d, J = 8.0 Hz, 1H), 7.22 (m, 2H), 7.36-7.40 (m, 3H). 13C
2-(p-Tolyl)cyclopropane-1,1-dicarbonitrile
(2f)
and
2-(m- NMR (CDCl3, 125 MHz): δ = 13.2, 14.8, 29.7, 42.3, 113.4, 113.9, 128.4,
tolyl)cyclopropane-1,1-dicarbonitrile (2f’): Colorless oil. 1H NMR (500 129.1, 129.1, 129.3, 131.1. MS calcd m/z 182.08, found 183.08 [(M + 1)]+.
MHz, CDCl3): δ = 2.21-2.26 (m, 4H), 2.36-2.38 (d, J = 8.5Hz, 6H), 3.26-3.27 Anal. Calcd for C12H10N2: C, 79.10; H, 5.53; N, 15.37; Found: C, 79.21; H,
(d, J = 2.0 Hz, 2H), 7.08-7.10 (d, J = 10.5 Hz, 2H), 7.16-7.25 (m, 5H), 7.29- 5.54; N, 15.45.
7.30 (d, J = 8.0 Hz, 1H). 13C NMR (CDCl3, 125 MHz): δ = 7.0, 7.1, 21.1, 2,3-Diphenylcyclopropane-1,1-dicarbonitrile (2n): Colorless crystal. m.p.
21.2, 22.1, 22.2, 34.9, 35.0, 113.0, 113.1, 115.3, 115.3, 125.1, 127.4, 128.0, 131-133 ºC. 1H NMR (500 MHz, CDCl3): δ = 3.68 (s, 2H), 7.41-7.49 (m,
128.8, 129.0, 129.7, 130.0, 130.0, 138.8, 139.4. MS calcd m/z 183.08, found 10H). 13C NMR (CDCl3, 125 MHz): δ = 15.3, 38.6, 113.0, 128.3, 129.1,
184.08 [(M + 1)]+. Anal. Calcd for C12H10N2: C, 79.10; H, 5.53; N, 15.37; 129.5, 130.6. IR (KBr, cm-1): v = 697, 1446, 1490, 2246, 2994, 3054. MS
Found: C, 79.21; H, 5.55; N, 15.44.
calcd m/z 244.10, found 245.10 [(M + 1)]+. Anal. Calcd for C17H12N2: C,
2-(4-(tert-Butyl)phenyl)cyclopropane-1,1-dicarbonitrile (2g): Colorless 83.58; H, 4.95; N, 11.47; Found: C, 83.48; H, 4.93; N, 11.41.
crystal. m.p. 149-151 ºC. 1H NMR (500 MHz, CDCl3): δ = 1.31 (s, 9H), 2.22- 6,6a-Dihydrocyclopropa[a]indene-1,1(1aH)-dicarbonitrile (2o): White
1
2.24 (m, 2H), 3.24-3.28 (t, J = 9.0 Hz, 1H), 7.21-7.23 (d, J = 8.5 Hz, 2H), solid. m.p. 93-95 ºC. H NMR (500 MHz, CDCl3): δ = 3.02-3.05 (t, J = 6.5
7.42-7.44 (d, J = 8.5 Hz, 2H). 13C NMR (CDCl3, 125 MHz): δ = 7.0, 22.3, Hz, 1H), 3.29-3.33 (d, J = 14.0 Hz, 1H), 3.52-3.56 (t, J = 12.5 Hz, 1H), 3.70-
31.1, 34.6, 34.9, 113.1, 115.4, 125.9, 127.4, 127.9, 152.5. IR (KBr, cm-1): v = 3.71 (d, J = 6.5 Hz, 1H), 7.28-7.35 (m, 3H), 7.51-7.52 (d, J = 7.0 Hz, 1H).
642, 839, 1368, 1464, 1514, 2247, 2875, 2965,3034, 3100. MS calcd m/z 13C NMR (CDCl3, 125 MHz): δ = 11.9, 33.6, 33.9, 42.1, 111.1, 114.7, 125.1,
224.13, found 225.13 [(M + 1)]+. Anal. Calcd for C15H16N2: C, 80.32; H, 7.19; 125.8, 127.7, 129.6, 135.4, 140.9. IR (KBr, cm-1): v = 670, 764, 1464, 1518,
N, 12.49; Found: C, 80.48; H, 7.22; N, 12.59.
1647, 1697, 2244, 2932, 3059. MS calcd m/z 180.07, found 181.07 [(M +
Colorless 1)]+. Anal. Calcd for C12H8N2: C, 79.98; H, 4.47; N, 15.55; Found: C, 79.88;
2-(4-Bromophenyl)cyclopropane-1,1-dicarbonitrile
(2h):
1
crystals. m.p. 140-142 ºC. H NMR (500 MHz, CDCl3): δ = 2.22-2.29 (m, H, 4.45; N, 15.47.
2H), 3.24-3.27 (t, J = 9.0 Hz, 1H), 7.17-7.19 (d, J = 8.5 Hz, 2H), 7.55-7.57 2,3-Dihydro-1H-cyclopropa[a]naphthalene-1,1(1aH,7bH)-dicarbonitrile
(m, 2H). 13C NMR (CDCl3, 125 MHz): δ = 7.1, 22.2, 34.3, 112.8, 114.9, (2p): Needle crystals. m.p. 92-94 ºC. 1H NMR (500 MHz, CDCl3): δ = 2.18-
123.7, 129.5, 129.9, 132.2. IR (KBr, cm-1): v = 599, 633, 836, 1452, 1493, 2.20 (m, 1H), 2.21-2.23 (m, 1H), 2.34-2.39 (m, 1H), 2.64-2.68 (m, 1H), 2.78-
1542, 1650, 1697, 2245, 2930. MS calcd m/z 245.98, found 246.98 [(M + 2.89 (m, 1H), 3.21-3.23 (d, J = 9.5 Hz, 1H), 7.13-7.15 (t, J = 4.5 Hz, 1H),
1)]+. Anal. Calcd for C11H7BrN2: C, 53.47; H, 2.86; N, 11.34; Found: C, 7.28-7.29 (t, J = 4.0 Hz, 2H), 7.43-7.44 (t, J = 5.0 Hz, 1H). 13C NMR
53.56; H, 2.87; N, 11.42.
(CDCl3, 125 MHz): δ = 12.2, 18.7, 25.2, 30.6, 33.2, 112.8, 115.6, 126.2,
2-(Thiophen-2-yl)cyclopropane-1,1-dicarbonitrile (2i): Brown oil. 1H 127.4, 129.1, 129.2, 135.9. IR (KBr, cm-1): v = 673, 1453, 1516, 1651, 1698,
NMR (500 MHz, CDCl3): δ = 2.19-2.23 (m, 1H), 2.27-2.29 (m, 1H), 3.38- 2247, 2941, 3046. MS calcd m/z 194.08, found 195.08 [(M + 1)]+. Anal.
3.42 (t, J = 9.5 Hz, 1H), 7.02-7.05 (m, 2H), 7.34-7.36 (m, 1H). 13C NMR Calcd for C13H10N2: C, 80.39; H, 5.19; N, 14.42; Found: C, 80.48; H, 5.21; N,
(CDCl3, 125 MHz): δ = 8.3, 23.8, 30.2, 112.7, 114.7, 127.3, 127.4, 127.9, 14.49.
133.5. IR (KBr, cm-1): v = 688, 1442, 1517, 1640, 1687, 2243, 2971, 3439. Tricyclo[3.2.1.02,4]octane-3,3-dicarbonitrile (2q): White solid. m.p. 86-88
MS calcd m/z 174.03, found 175.03 [(M + 1)]+. Anal. Calcd for C9H6N2S: C, ºC. 1H NMR (500 MHz, CDCl3): δ = 0.96-0.99 (d, J = 13.0 Hz, 1H), 1.33-
62.05; H, 3.47; N, 16.08; Found: C, 62.18; H, 3.49; N, 16.17.
1.36 (m, 2H), 1.65-1.67 (d, J = 7.5 Hz, 2H), 1.92-1.94 (d, J = 12.5 Hz, 1H),
2-Methyl-2-phenylcyclopropane-1,1-dicarbonitrile (2j): Colorless crystals. 2.07 (s, 2H), 2.79 (s, 2H). 13C NMR (CDCl3, 125 MHz): δ = 2.6, 27.7, 28.2,
m.p. 87-89 ºC. 1H NMR (500 MHz, CDCl3): δ = 1.79 (s, 3H), 1.98-1.99 (d, J 35.0, 35.9, 114.4, 115.9. IR (KBr, cm-1): v = 657, 1461, 1512, 1645, 2239,
= 6.0 Hz, 1H), 2.34-2.35 (d, J = 6.0 Hz, 1H), 7.35-7.42 (m, 5H). 13C NMR 2882, 2974. MS calcd m/z 157.08, found 158.08 [(M + 1)]+. Anal. Calcd for
(CDCl3, 125 MHz): δ = 11.5, 24.2, 29.6, 40.2, 113.8, 114.3, 128.0, 129.0, C10H10N2: C, 75.92; H, 6.37; N, 17.71; Found: C, 76.04; H, 6.40; N, 17.82.
129.1, 136.6. IR (KBr, cm-1): v = 695, 769, 1446, 1500, 1650, 1699, 2243, 1-Methylbicyclo[4.1.0]heptane-7,7-dicarbonitrile (2r): Colorless oil. 1H
2935, 2989. MS calcd m/z 182.08, found 183.08 [(M + 1)]+. Anal. Calcd for NMR (500 MHz, CDCl3): δ = 1.25-1.39 (m, 2H), 1.43-1.47 (m, 1H), 1.48 (s,
C12H10N2: C, 79.10; H, 5.53; N, 15.37; Found: C, 79.00; H, 5.51; N, 15.27.
3H), 1.51-1.57 (m, 1H), 1.84-1.95 (m, 4H), 1.97-2.19 (m, 1H). 13C NMR
2-Hexylcyclopropane-1,1-dicarbonitrile (2k): Yellow oil. 1H NMR (500 (CDCl3, 125 MHz): δ = 14.5, 19.4, 19.9, 20.2, 24.8, 27.3, 34.3, 36.7, 113.8,
MHz, CDCl3): δ = 0.89-0.91 (t, J = 7.0 Hz, 3H), 1.25-1.40 (m, 6H), 1.49-1.64 115.1. MS calcd m/z 160.10, found 161.10 [(M + 1)]+. Anal. Calcd for
(m, 5H), 1.90-2.01 (m, 2H). 13C NMR (CDCl3, 125 MHz): δ = 3.8, 13.9, 22.5, C10H12N2: C, 74.97; H, 7.55; N, 17.48; Found: C, 74.90; H, 7.52; N, 17.39.
24.8, 27.9, 28.7, 30.0, 31.4, 31.5, 114.0, 115.7. MS calcd m/z 176.13, found 1-Phenylbicyclo[4.1.0]heptane-7,7-dicarbonitrile (2s): White solid. m.p.
177.13 [(M + 1)]+. Anal. Calcd for C11H16N2: C, 74.96; H, 9.15; N, 15.89; 45-47 ºC. 1H NMR (500 MHz, CDCl3): δ = 1.43-1.48 (m, 2H), 1.57-1.65 (m,
Found: C, 74.87; H, 9.17; N, 15.96.
2H), 2.01-2.06 (m, 1H), 2.17-2.23 (m, 1H), 2.34-2.41 (m, 2H), 2.60-2.62 (m,
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1H), 7.29-7.42 (m, 5H). 13C NMR (CDCl3, 125 MHz): δ = 16.1, 19.6, 20.2, 71.74; H, 2.74; N, 15.21; Found: C,71.86; H, 2.76; N, 15.31.
20.5, 29.5, 34.1, 42.8, 113.8, 114.6, 120.0, 127.7, 128.8, 129.3, 140.5. IR 2-(4-Ethynylphenyl)cycloprop-2-ene-1,1-dicarbonitrile (5f): Brown solid.
(KBr, cm-1): v = 697, 764, 1450, 1500, 1697, 2237, 2871, 2947, 3025. MS m.p. 113-115 ºC. 1H NMR (500 MHz, CDCl3): δ = 3.33 (s, 1H), 7.15 (s, 1H).
calcd m/z 222.12, found 223.12 [(M + 1)]+. Anal. Calcd for C15H14N2: C, 7.68 (s, 4H). 13C NMR (CDCl3, 125 MHz): δ = 3.7, 30.9, 81.4, 82.1, 93.6,
81.05; H, 6.35; N, 12.60; Found: C, 81.17; H, 6.36; N, 12.69.
111.3, 115.9, 120.2, 126.9, 130.3, 133.2. MS calcd m/z 190.05, found 191.05
2,2'-(Cyclopentane-1,2-diyl)dimalononitrile (3a): Yellow oil. 1H NMR [(M + 1)]+. Anal. Calcd for C13H6N2: C, 82.09; H, 3.18; N, 14.73; Found: C,
(500 MHz, CDCl3): δ = 1.68-1.75 (m, 1H), 1.84-1.95 (m, 2H), 2.12-2.26 (m, 82.21; H, 3.20; N, 14.80.
4H), 2.56-2.58 (m, 2H), 2.80-2.83 (m, 1H). 13C NMR (CDCl3, 125 MHz): δ = 2-Phenyl-3-propylcycloprop-2-ene-1,1-dicarbonitrile (5g): Yellow oil. H
1
8.7, 21.3, 25.8, 26.2, 36.0, 38.6, 111.7, 112.9, 115.1. MS calcd m/z 198.09, NMR (500 MHz, CDCl3): δ = 1.11-1.14 (t, J = 7.5 Hz, 3H), 1.87-1.92 (m,
found 199.09 [(M + 1)]+. Anal. Calcd for C11H10N4: C, 66.65; H, 5.08; N, 2H), 2.29-2.83 (t, J = 7.5 Hz, 2H), 7.54-7.62 (m, 5H). 13C NMR (CDCl3, 125
28.26; Found: C, 66.74; H, 5.09; N, 28.40.
MHz): δ = 5.4, 13.9, 19.9, 26.0, 103.8, 106.7, 116.4, 121.5, 129.6, 129.7,
2,2'-(Cyclohexane-1,2-diyl)dimalononitrile (3b): Colorless oil. 1H NMR 131.6. MS calcd m/z 208.10, found 209.10 [(M + 1)]+. Anal. Calcd for
(500 MHz, CDCl3): δ = 1.36-1.38 (t, J = 7.0 Hz, 2H), 1.45-1.50 (m, 2H), C14H12N2: C, 80.74; H, 5.81; N, 13.45; Found: C, 80.87; H, 5.84; N, 13.57.
1.81-1.90 (m, 3H), 2.16-2.25 (m, 4H), 2.65-2.68 (t, J = 6.5 Hz, 1H). 13C 2-Ethyl-3-methylcycloprop-2-ene-1,1-dicarbonitrile (5h): Yellow oil. 1H
NMR (CDCl3, 125 MHz): δ = 9.1, 19.6, 19.7, 24.9, 27.9, 29.6, 34.7, 111.8, NMR (500 MHz, CDCl3): δ = 1.29-1.32 (m, 3H), 2.25 (s, 3H), 2.59-2.64 (m,
113.6, 116.4. MS calcd m/z 212.11, found 213.11 [(M + 1)]+. Anal. Calcd for 2H). 13C NMR (CDCl3, 125 MHz): δ = 8.2, 10.3, 16.9, 101.8, 107.0, 116.9.
C12H12N4: C, 67.90; H, 5.70; N, 26.40; Found: C, 67.99; H, 5.72; N, 26.51.
MS calcd m/z 132.07, found 133.07 [(M + 1)]+. Anal. Calcd for C8H8N2: C,
Representative procedure for cyclopropenation. Synthesis of 5a: 72.70; H, 6.10; N, 21.20; Found: C, 72.84; H, 6.12; N, 21.31.
Complex PhI(OAc)2 (177 mg, 0.6 mmol), malononitrile (40 mg, 0.6 mmol) 2,3-Diphenylcycloprop-2-ene-1,1-dicarbonitrile (5i): Needle crystals. m.p.
1
and alkyne 4a (0.55 mL, 0.5 mmol) were dissolved in DCE (2.0 mL) in a 25 138-140 ºC. H NMR (500 MHz, CDCl3): δ = 7.59-7.62 (t, J = 7.0 Hz, 3H),
mL flask. The mixture was stirred at 50 °C for 2 h (monitored by TLC). The 7.79-7.81 (d, J = 7.0 Hz, 2H). 13C NMR (CDCl3, 125 MHz): δ = 5.1, 103.6,
reaction mixture was cooled to room temperature, poured into the water and 115.7, 121.9, 129.7, 130.0, 132.0. MS calcd m/z 242.08, found 243.08 [(M +
extracted with CH2Cl2 (3 × 10 mL). The combined organic phase was washed 1)]+. Anal. Calcd for C17H10N2: C, 84.28; H, 4.16; N, 11.56; Found: C, 84.17;
with water (3 × 10 mL). The solvent was removed under reduced pressure, H, 4.15; N, 11.49.
and the residue was purified by a flash silica gel column chromatography Ethyl 3,3-dicyano-2-phenylcycloprop-1-enecarboxylate (5j): Yellow solid.
(EtOAc/petroleum ether = 1:10) to give 5a as colorless oil in a 94% yield.
m.p. 67-69 ºC. 1H NMR (500 MHz, CDCl3): δ = 1.45-1.47 (t, J = 7.0 Hz, 3H),
2-Phenylcycloprop-2-ene-1,1-dicarbonitrile (5a): Colorless oil. 1H NMR 4.47-4.49 (d, J = 7.0 Hz, 2H), 7.64-7.72 (m, 3H), 7.87-7.89 (d, J = 6.5 Hz,
(500 MHz, CDCl3): δ = 7.08 (s, 1H), 7.59-7.61 (t, J = 7.0 Hz, 3H), 7.72-7.74 2H). 13C NMR (CDCl3, 125 MHz): δ = 7.2, 14.1, 63.5, 95.5, 114.3, 117.9,
(t, J = 6.5 Hz, 2H). 13C NMR (CDCl3, 125 MHz): δ = 3.6, 92.5, 111.8, 116.1, 119.6, 129.9, 132.3, 134.7, 154.9. MS calcd m/z 238.07, found 239.07 [(M +
120.2, 129.6, 130.5, 132.8. MS calcd m/z 166.05, found 167.05 [(M + 1)]+. 1)]+. Anal. Calcd for C14H10N2O2: C, 70.58; H, 4.23; N, 11.76; Found: C,
Anal. Calcd for C11H6N2: C, 79.50; H, 3.64; N, 16.86; Found: C, 79.63; H, 70.69; H, 4.25; N, 11.86.
3.65; N, 16.94.
Ethyl 1-nitro-2-phenylcyclopropanecarboxylate (6a): Yellow oil. 1H NMR
2-(m-Tolyl)cycloprop-2-ene-1,1-dicarbonitrile (5b): Brown solid. m.p. 73- (500 MHz, CDCl3): δ = 1.37-1.39 (t, J = 7.0 Hz, 3H), 3.19-3.25 (m, 1H),
75 ºC. 1H NMR (500 MHz, CDCl3): δ = 2.51 (s, 3H), 7.03 (s, 1H), 7.42-7.43 3.62-3.68 (m, 1H), 4.35-4.39 (m, 2H), 5.77-5.81 (m, 1H), 7.32-7.40 (m, 5H).
(d, J = 8.0 Hz, 2H), 7.64-7.66 (d, J = 8.0 Hz, 2H). 13C NMR (CDCl3, 125 13C NMR (CDCl3, 125 MHz): δ = 14.1, 41.5, 62.2, 84.9, 125.9, 128.7, 128.9,
MHz): δ = 3.55, 21.8, 91.1, 111.7, 116.3, 117.4, 130.3, 130.5, 143.9. MS 139.6, 151.2, 160.6. MS calcd m/z 235.08, found 236.08 [(M + 1)]+. Anal.
calcd m/z 180.07, found 181.07 [(M + 1)]+. Anal. Calcd for C12H8N2: C, Calcd for C12H13NO4: C, 61.27; H, 5.57; N, 27.21; Found: C, 61.42; H, 5.59;
79.98; H, 4.47; N, 15.55; Found: C, 80.11; H, 4.48; N, 15.64.
N, 27.33.
2-(4-(tert-Butyl)phenyl)cycloprop-2-ene-1,1-dicarbonitrile (5c): Brown Ethyl 3-nitrotricyclo[3.2.1.02,4]octane-3-carboxylate (6b): Colorless oil. 1H
1
needle crystal. m.p. 75-77 ºC. H NMR (500 MHz, CDCl3): δ = 1.37 (s, 9H), NMR (500 MHz, CDCl3): δ = 1.18-1.21 (t, J = 8.5 Hz, 1H), 1.31-1.38 (m,
6.99 (s, 1H), 7.59-7.61 (d, J = 8.5 Hz, 2H), 7.65-7.67 (d, J = 8.0 Hz, 2H). 13
C
5H), 1.59-1.73 (m, 3H), 2.56-2.59 (t, J = 8.5 Hz, 2H), 3.47-3.49 (d, J = 8.5
NMR (CDCl3, 125 MHz): δ = 3.6, 31.0, 35.4, 91.3, 111.8, 116.4, 117.4, Hz, 1H), 4.27-4.36 (m, 2H), 4.59-4.60 (d, J = 8.0 Hz, 1H). 13C NMR (CDCl3,
126.7, 130.5, 157.0. MS calcd m/z 222.12, found 223.12 [(M + 1)]+. Anal. 125 MHz): δ = 13.9, 22.4, 26.9, 32.1, 40.1, 41.8, 52.2, 61.1, 80.8, 109.3,
Calcd for C15H14N2: C, 81.05; H, 6.35; N, 12.60; Found: C, 81.17; H, 6.37; N, 158.8. MS calcd m/z 225.10, found 226.10 [(M + 1)]+. Anal. Calcd for
12.69.
C11H15NO4: C, 58.66; H, 6.71; N, 6.22; Found: C, 58.55; H, 6.69; N, 6.14.
2-(3-chlorophenyl)cycloprop-2-ene-1,1-dicarbonitrile (5d): Brown solid. Ethyl 2-benzoyl-1-nitro-3-phenylcyclopropanecarboxylate (6c): Brown
1
m.p. 72-74 ºC. H NMR (500 MHz, CDCl3): δ = 7.19 (s, 1H), 7.54-7.63 (m, oil. 1H NMR (500 MHz, CDCl3): δ = 1.26-1.29 (t, J = 7.0 Hz, 3H), 4.26-4.31
3H), 7.71 (s, 1H). 13C NMR (CDCl3, 125 MHz): δ = 3.9, 94.4, 111.2, 115.8, (m, 2H), 5.32-5.34 (d, J = 8.0 Hz, 1H), 5.78-5.79 (d, J = 8.5 Hz, 1H), 7.28-
122.0, 128.6, 130.3, 131.0, 133.1, 135.9. MS calcd m/z 200.01, found 201.01 7.64 (m, 13H), 7.83-7.84 (d, J = 7.5 Hz, 2H), 7.98-8.00 (t, J = 7.5 Hz, 1H).
[(M + 1)]+. Anal. Calcd for C11H5ClN2: C, 65.85; H, 2.51; N, 13.96; Found: C, 13C NMR (CDCl3, 125 MHz): δ = 13.8, 13.9, 29.6, 54.1, 61.9, 62.1, 62.4,
65.72; H, 2.48; N, 13.88.
90.2, 91.2, 126.1, 127.7, 128.4, 128.6, 128.8, 128.9, 128.9, 129.2, 129.3,
2-(4-Fluorophenyl)cycloprop-2-ene-1,1-dicarbonitrile (5e): Brown solid. 129.4, 134.2, 134.3, 135.3, 137.2, 137.9, 150.4, 153.6, 159.3, 159.8, 191.8,
1
m.p. 63-65 ºC. H NMR (500 MHz, CDCl3): δ = 7.08 (s, 3H), 7.26-7.31 (m, 195.1. MS calcd m/z 339.11, found 340.11 [(M + 1)]+. Anal. Calcd for
2H), 7.73-7.76 (m, 2H). 13C NMR (CDCl3, 125 MHz): δ = 3.5, 91.9, 91.9, C19H17NO5: C, 67.25; H, 5.05; N, 4.13; Found: C, 67.37; H, 5.06; N, 4.17.
110.7, 115.7, 116.4, 116.4, 116.9, 117.1, 132.6, 132.7, 163.9, 165.9. MS Ethyl 1-nitro-2-phenylcycloprop-2-enecarboxylate (7): Yellow oil. 1H
calcd m/z 184.04, found 185.04 [(M + 1)]+. Anal. Calcd for C11H5FN2: C, NMR (500 MHz, CDCl3): δ= 1.43-1.46(m, 3H), 4.47-4.89 (d, J = 7.0 Hz, 2H),
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6.93 (s, 1H), 7.48-7.49 (m, 3H), 7.80-7.82 (m, 2H). MS calcd m/z 233.07,
found 234.07 [(M + 1)]+. Anal. Calcd for C12H11NO4: C, 61.08; H, 4.75; N,
6.01; Found: C, 61.21; H, 4.77; N, 6.06.
6
(a) M. S. Baird, In Houben-Weyl: Methods of Organic Chemistry, 4th
ed.; de Meijere, A., Ed.; Thieme: Stuggart, 1996; Vol. E17d; 2695–
2744; (b) Y. Lou, M. Horikawa, R. A. Kloster, N. A. Hawryluk and E.
J. Corey, J. Am. Chem. Soc., 2004, 126, 8916–8918; (c) H. M. L.
Notes and references
Davies and G. H. Lee, Org. Lett., 2004,
6, 1233–1236; (d) L. Liao, F.
Zhang, N. Yan, J. A. Golen and J. M. Fox, Tetrahedron., 2004, 60
,
1
(a) J. Salaun in Cyclopropane derivatives and their diverse biological
activities, Vol. 207 (Ed.: A. Meijere), Springer, Berlin, 2000. (b) J.
Pietruszka, Chem. Rev. 2003, 103, 1051–1170; (c) H.-U. Reissig and
R. Zimmer, Chem. Rev., 2003, 103, 1151–1196; (d) M. Rubin, M.
Rubina and V. Gevorgyan, Chem. Rev., 2007, 107, 3117–3179; (e) C.
A. Carson and M. A. Kerr, Chem. Soc. Rev., 2009, 38, 3051–3060; (f)
M. Shi, L.-X. Shao, J.-M. Lu, Y. Wei, K. Mizuno and H. Maeda,
Chem. Rev., 2010, 110, 5883–5913; (g) D. Y.-K. Chen, R. H. Pouwer
and J.-A. Richard, Chem. Soc. Rev., 2012, 41, 4631–4642.
1803–1816; (e) D. T. Nowlan III and D. A. Singleton, J. Am. Chem.
Soc., 2005, 127, 6190–6191; (f) Y. Lou, T. P. Remarchuk and E. J.
Corey, J. Am. Chem. Soc., 2005, 127
,
14223–14230; (g) S.
, 4463–4466; (h) J.
Chuprakov and V. Gevorgyan, Org. Lett., 2007,
9
F. Briones, J. Hansen, K. I. Hardcastle, J. Autschbach and H. M. L.
Davies, J. Am. Chem. Soc., 2010, 132, 17211–17215; (i) ref 3f; (j) M.
Uehara, H. Suematsu, Y. Yasutomi and T. Katsuki, J. Am. Chem.
Soc., 2011, 133, 170–171; (k) X. Cui, X. Xu, H. Lu, S. Zhu, L.
Wojtas and X. P. Zhang, J. Am. Chem. Soc., 2011, 133, 3304–3307;
(l) X. Cui, X. Xu, L. Wojtas, M. M. Kim and X. P. Zhang, J. Am.
Chem. Soc., 2012, 134, 19981–19984; (m) J. F. Briones and H. M. L.
Davies, Org. Lett., 2011, 13, 3984–3987; (n) J. F. Briones and H. M.
L. Davies, J. Am. Chem. Soc., 2012, 134, 11916–11919.
2
3
(a) M. Nakamura, A. Hirai and E. Nakamura, J. Am. Chem. Soc.,
2003, 125, 2341–2350; (b) J. Long, Y. Yuan and Y. Shi, J. Am. Chem.
Soc., 2003, 125, 13632–13633; (c) S. R. Goudreau and A. B. Charette,
J. Am. Chem. Soc., 2009, 131, 15633–15635; (d) T. Wang, Y. Liang
and Z.-X. Yu, J. Am. Chem. Soc., 2011, 133, 9343–9353; (e) H. Y.
Kim and P. J. Walsh, Acc. Chem. Res., 2012, 45, 1533–1547.
7
(a) M. S. Baird, In Houben-Weyl: Methods of Organic Chemistry, 4th
ed.; de Meijere, A., Ed.; Thieme: Stuttgart, 1996; Vol. E17d, 2747–
2759; (b) H. Hopf, In Houben-Weyl: Methods of Organic Chemistry,
4th ed.; de Meijere, A., Ed.; Thieme: Stuttgart, 1996; Vol. E17d,
2745–2746.
(a) M. P. Doyle, M. A. McKervey and T. Ye, Modern Catalytic
Methods for Organic Synthesis with Diazo Compounds: From
Cyclopropanes to Ylides, Wiley, New York, 1998; (b) B. Moreau and
A. B. Charette, J. Am. Chem. Soc., 2005, 127, 18014–18015; (c) D.
Marcoux, S. R. Goudreau and A. B. Charette, J. Org. Chem., 2009,
74, 8939–8955; (d) R. R. Nani and S. E. Reisman, J. Am. Chem. Soc.,
2013, 135, 7304–7311; (e) V. N. G. Lindsay, D. Fiset, P. J. Gritsch, S.
Azzi and A. B. Charette, J. Am. Chem. Soc., 2013, 135, 1463–1470;
8
9
S. Lin, Y. Wei and F. Liang, Chem. Commun., 2012, 48, 9879–9881.
In the past decade, the application of hypervalent iodine reagents in
organic synthesis has attracted intense interest, due to the intriguing
oxidizing properties, low toxicity, high reactivity, easy handling and
ready availability. Books: (a) A. Varvoglis, The Organic Chemistry
of Polycoordinated Iodine; VCH Publishers, Inc.: New York, 1992;
(f) B. Moreau and A. B. Charette, J. Am. Chem. Soc., 2005, 127
,
18014–18015; (g) S. R. Goudreau, D. Marcoux and A. B. Charette, J.
Org. Chem., 2009, 74, 470–473; (h) C. Deng, L. Wang, J. Zhu and Y.
Tang, Angew. Chem. Int. Ed., 2012, 51, 11620–11623.
(b
)
T. Wirth, Ed. Hypervalent Iodine Chemistry: Modern
Developments in Organic Synthesis; Topics in Current Chemistry
Series 224; Springer: Berlin-Tokyo, 2003; (c) R. M. Moriarty, O.
Prakash, Hypervalent Iodine in Organic Chemistry: Chemical
Transformations; Wiley-Interscience: 2008; Reviews: (d) V. V.
Zhdankin and P. J. Stang, Chem. Rev., 2002, 102, 2523–2584; (e) T.
Wirth, In Organic Synthesis Highlights V, (Eds.: Schmalz, H.-G.;
Wirth, T.), Wiley-VCH, Weinheim, 2003, 144–150; (f) H. Tohma
and Y. Kita, Adv. Synth. Catal., 2004, 346, 111–124; (g) T. Wirth,
Angew. Chem., Int. Ed., 2005, 44, 3656–3665; (h) R. M. Moriarty, J.
Org. Chem., 2005, 70, 2893–2903; (i) V. V. Zhdankin and P. J. Stang,
Chem. Rev., 2008, 108, 5299–5358; (j) M. Ochiai and K. Miyamoto,
Eur. J. Org. Chem., 2008, 44, 4229–4239; (k) T. Dohi and Y. Kita,
Chem. Commun., 2009, 45, 2073–2085; (l) M. Uyanik and K.
Ishihara, Chem. Commun., 2009, 45, 2086–2099; (m) V. V. Zhdankin,
J. Org. Chem., 2011, 76, 1185–1197.
4
(a) V. K. Aggarwal, E. Alsono, G. Fang, M. Ferrara and G. Hynd, M.
Porcelloni, Angew. Chem. Int. Ed., 2001, 40, 1433–1436; (b) C. D.
Papageorgiou, S. V. Ley and M. J. Gaunt, Angew. Chem. Int. Ed.,
2003, 42, 828–831; (c) N. Bremeyer, S. C. Smith, S. V. Ley and M. J.
Gaunt, Angew. Chem. Int. Ed., 2004, 43, 2681–2684; (d) C. D.
Papageorgiou, M. A. Cubillo de Dios, S. V. Ley and M. J. Gaunt,
Angew. Chem. Int. Ed., 2004, 43, 4641–4644; (e) R. K. Kunz and D.
W. C. MacMillan, J. Am. Chem. Soc., 2005, 127, 3240–3241; (f) M. J.
Gaunt and C. C. C. Johansson, Chem. Rev., 2007, 107, 5596–5605; (g)
X. L. Sun and Y. Tang, Acc. Chem. Res., 2008, 41, 937–948; (h) M.
Rueping, H. Sundén, L. Hubener and E. Sugiono, Chem. Commun.,
2012, 48, 2201–2203; (i) A. Biswas, S. D. Sarkar, L. Tebben and A.
Studer, Chem. Commun., 2012, 48, 5190–5192.
5
(a) M. S. Baird, Chem. Rev., 2003, 103, 1271–1294; (b) W. R. Dolbier
and M. A. Battiste, Chem. Rev., 2003, 103, 1071–1098; (c) R. Walsh,
10 Diamination without metal catalysts, see: (a) C. Röben, J. A. Souto,
Y. González, A. Lishchynskyi and , Angew. Chem. Int. Ed.,
2011, 50, 9478–9482; (b) J. A. Souto, C. Martnez, I. Velilla and
, Angew. Chem. Int. Ed., 2013, 52, 1324–1328; (c) C. Röben, J.
Chem. Soc. Rev., 2005, 34, 714–732; (d) M. Rubin, M. Rubina and V.
Gevorgyan, Chem. Rev., 2007, 107, 3117–3179; (e) I.; Marek, S.
Simaan andA. Masarwa, Angew. Chem., 2007, 119, 7508–7520;
Angew. Chem. Int. Ed., 2007, 46, 7364–7376; (f) F. Miege, C. Meyer
and J. Cossy, Angew. Chem. Int. Ed., 2011, 50, 5932–5937; (g) M. R.
Wilson and R. E. Taylor, Angew. Chem. Int. Ed., 2013, 52, 4078–
4087.
A. Souto, E. C. Escudero-Adan and , Org. Lett., 2013, 15
,
1008–1011; With hypervalent iodine reagent and metal catalysts: (d)
J. Streuff, C. H. Hövelmann, M. Nieger and , J. Am. Chem.
Soc., 2005, 127, 14586–14587; (e) K. , J. Streuff, C. H.
Hvelmann and A. Núñez, Angew. Chem. Int. Ed., 2007, 46, 7125–
7127; ( , J. Am. Chem. Soc., 2007, 129, 14542–14543; (
8 | Org. Biomol. Chem., 2013, 00, 1-9
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ARTICLE
, C. H. Hövelmann and J. Streuff, J. Am. Chem. Soc., 2008,
130, 763–773; (h) L. Iglesias, E. G. Prez and , Angew.
Chem. Int. Ed., 2010, 49, 8109–8111; (i) C. Martnez and ,
Angew. Chem. Int. Ed., 2012, 51, 7031–7034; Alkyne amination: (j) J.
A. Souto, P. Becker, Á. Iglesias and , J. Am. Chem. Soc.,
2012, 134, 15505–15511.
54, 2605–2608; (e) V. V. Grushin, Chem. Soc. Rev., 2000, 29, 315–
324.
11 Dioxygenation: (a) Y. Li, D. Song and V. M. Dong, J. Am. Chem.
Soc., 2008, 130, 2962–2964; (b) M. Fujita, Y. Yoshida, K. Miyata, A.
Wakisaka and T. Sugimura, Angew. Chem. Int. Ed., 2010, 49, 7068–
7071; (c) Y.-B. Kang and L. H. Gade, J. Am. Chem. Soc., 2011, 133
,
3658–3667; (d) W. Zhong, J. Yang, X. Meng and Z. Li, J. Org.
Chem., 2011, 76, 9997–10004; (e) M. Fujita, M. Wakita and T.
Sugimura, Chem. Commun., 2011, 47, 3983–3985; (f) S. R. Neufeldt
and M. S. Sanford, Org. Lett., 2013, 15, 46–49.
12 A. S. Biland, S. Altermann and T. Wirth, ARKIVOC 2003, (vi) 164–
169.
13 CCDC 948734 (2a) and 948733 (2n) contain the supplementary
crystallographic data for this paper. The data can be obtained free of
charge from The Cambridge Crystallographic Data Centre via
www.ccdc.cam.ac.uk/data_request/cif.
14 We think that cis-1,2-disubstituted cycloalkanes are generated due to
the double backside nucleophilic substitution.
15 Electronic factors might be responsible for the different outcome as for
parent cycloalkenes (dialkylation, Scheme 3) and substituted
cycloalkenes (cyclopropanation, entries 15-19, Table 2).
16 Two examples for the cyclopropenation of internal alkynes with Ag(I)
catalyst were presented, see: refs 6m and 6n. No report on the
cyclopropenation of electron deficient alkynes was found.
17 In our work, excess alkene or alkyne is not required in all cases,
contrary to the observation in selected papers. Please refer to: (a) P.
Müller and A. Ghanem, Org. Lett., 2004, 6, 4347–4350. (b) ref 3b. (c)
S. R. Goudreau, D. Marcoux and A. B. Charette, J. Org. Chem., 2009,
74, 470–473.
18 Other active methylene compounds including diethyl malonate and
bis(phenylsulfonyl)methane were also examined, but proved to be
inefficient at the moment.
19 For cis-alkene substrates, the possible cyclopropanation mechansim
was proposed as follow.
20 (a) K. Niedermann, N. Früh, E. Inogradova, V M. S. Wiehn, A.
Moreno and A. Togni, Angew. Chem. Int. Ed., 2011. 50, 1059–1063;
(b) D. Lubriks, I. Sokolovs and E. Suna J. Am. Chem. Soc. 2012, 134
15436–15442; (c) V. V. Zhdankin, R. Tykwinski, R. Caple, B.
Berglund, A. S. Kozmin, N. S. Zefirov, Tetrahedron Lett. 1988, 29
,
,
3703–3704; (d) V. V. Zhdankin, M. Mullikin, R. Tykwinski, B.
Berglund, R. Caple, N. S. Zefirov, A. S. Kozmin, J. Org. Chem. 1989,
This journal is © The Royal Society of Chemistry 2013
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