N-Iodosuccinimide-Initiated Spirocyclopropanation of Styrenes with 1,3-Dicarbonyl Compound for the Synthesis of Spirocyclopropanes

Article abstract of DOI:10.1021/acs.joc.6b01163

Herein is reported an N-iodosuccinimide-initiated spirocyclopropanation reaction of styrenes with 1,3-dicarbonyl compounds in the presence of white LED light. The reaction proceeds via two C-H and two C-I bond cleavage event, along with two C-C bond forma

Full text of DOI:10.1021/acs.joc.6b01163

Article
pubs.acs.org/joc
N‑Iodosuccinimide-Initiated Spirocyclopropanation of Styrenes with
1,3-Dicarbonyl Compound for the Synthesis of Spirocyclopropanes
Ping Qian,† Bingnan Du,† Ruichun Song,† Xiaodong Wu,‡ Haibo Mei,† Jianlin Han,*,† and Yi Pan†
†School of Chemistry and Chemical Engineering, State Key Laboratory of Coordination Chemistry, Nanjing University, Nanjing
210093, China
‡MaAnShan High-Tech Research Institute of Nanjing University, MaAnShan 238200, China
S
* Supporting Information
ABSTRACT: Herein is reported an N-iodosuccinimide-initiated spirocyclopropanation reaction of styrenes with 1,3-dicarbonyl
compounds in the presence of white LED light. The reaction proceeds via two C−H and two C−I bond cleavage event, along
with two C−C bond formation event, and formation of quaternary centers. These reactions could be carried out at room
temperature and tolerated a wide range of substrates, resulting in good to excellent chemical yields. This developed radical
reaction provides easy and practical access to spiro[2.4]heptane-4,7-dione derivatives.
catalyzed cyclopropanation reaction of 2-diazo-1-indanone with
various substituted styrenes was developed for the construction
of spiro[2.4]heptane-4,7-dione derivatives (Scheme 1a).6 The
Barba group reported an electrochemical reduction synthetic
method by using 2,2-dibromo-1,3-indandione and styrene as
substrates (Scheme 1a).7 The Bavantula group reported a one-
pot two-step tandem reaction starting from pyridine, 4-chloro
phenacyl bromide, 1,3-indandione, and aromatic aldehydes
using triethylamine as catalyst for the synthesis of polysub-
stituted spirocyclopropane derivatives (Scheme 1b).5 Recently,
the Yakura group also reported a synthetic method for
cyclopentane-1,3-dione-2-spirocyclopropanes from 1H-indene-
1,3(2H)-dione and (1-aryl-2-bromoethyl)dimethylsulfonium
bromides in the presence of K2CO3 (Scheme 1b).8 In 2009,
the Wang group reported the oxidative addition reaction of
various aldehydes with 5,5-dimethylcyclohexane-1,3-dione and
1,3-indanedione to selectively afford spirocyclopropane deriv-
atives, promoted by molecular iodine and dimethylaminopyr-
idine under mechanical milling conditions (Scheme 1b).9 Such
spirocyclopropane also could be prepared from 2-arylmethyli-
deneindan-1,3-diones with α-monohalogenated active methyl-
ene compounds via a base-promoted MIRC (Michael-induced
ring closure) approach10 or bromine-containing zinc enolates
intermediate11 (Scheme 1c). However, these methods generally
require the pregeneration of reagents or harsh reaction
conditions, which lowers the synthetic efficiency and limits
the practical application. Thus, developing an efficient method
for the preparation of spiro[2.4]heptane-4,7-dione derivatives
INTRODUCTION
■
The spirocyclopropanes represent an important class of organic
compounds in the field of organic chemistry, which show a
diverse range of biological activities, such as anti-inflammatory,
antibiotic, analgesic, anticancer, and cytotoxic activity.1 This
spirocyclopropane functionality is also a unique structure
occurring in a number of natural products (Figure 1).2
Figure 1. Natural products containing spirocyclopropane unit.
Furthermore, the spirocyclopropanes could be used as versatile
tools for the preparation of natural and other organic
compounds.3 For example, the Carreira group reported the
total synthesis of Gelsemoxonine by using the spirocyclopro-
pane isoxazolidine ring contraction as a key step.4 Among the
various types of spirocyclopropanes skeletons, the spiro[2.4]-
heptane-4,7-dione derivatives play an important role and have
been demostrated to show antimicrobial and nematicidal
activities.5 Thus, there is a compelling interest in the
development of efficient synthetic methodologies to access
such a privileged structure. However, there have been only a
few examples reported for the synthesis of spiro[2.4]heptane-
4,7-dione derivatives until now.5 In 2000, a rhodium acetate-
Received: May 18, 2016
© XXXX American Chemical Society
A
DOI: 10.1021/acs.joc.6b01163
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Scheme 1. Preparation of Spiro[2.4]heptane-4,7-dione Derivatives and Light-Driven Cyclopropanation
from simple and available starting materials under convenient
condition still remains desirable.
has never been explored. Herein, we report an efficient pathway
for the synthesis of spiro[2.4]heptane-4,7-dione derivatives via
NIS-initiated spirocyclopropanation reaction of styrenes with
1,3-dicarbonyl compound in the presence of white LED light.
This reaction could be carried out under simple conditions with
readily available NIS as promoter. Furthermore, this process
demonstrates a multistep radical reaction for functionalization
of 1,3-dicarbonyl compounds and also represents easy access to
spirocyclopropane.
Very recently, the Itoh group developed a light-driven
intermolecular cyclopropanation of aromatic olefins with
activated methylene compounds using molecular iodine,
which provides cyclopropanes as products in good chemical
yields (Scheme 1d).12 Taking advantage of this work12 and
recent works in C−H functionalization,13 direct sp3 C−H
functionalization of simple 1,3-dicarbonyl compound, subse-
quent coupling with styrene, and following cyclization under
mild condition would be an ideal pathway for synthesis of
spiro[2.4]heptane-4,7-dione derivatives. Notably, Sutherland
and other groups have reported elegant works on iodination
with NIS (N-iodosuccinimide) as precursor.14 Also, several
groups developed relevant cyclopropanation methodologies to
give substituted cyclopropanes with the use of molecular iodine
in recent years.15 However, to the best of our knowledge, NIS-
promoted spirocyclopropanes of 1,3-dicarbonyl compounds
with styrenes via C−H bond cleavage, iodination, and
intramolecular spirocyclization to assemble spiro[2.4]heptane
RESULTS AND DISCUSSION
■
Initial examination of reactivity between 2H-indene-1,3-dione
2a and styrenes 1a was conducted at room temperature using
ethyl acetate as a solvent (Table 1).16 As shown in entries 1−5,
the corresponding spiro[2.4]heptane-4,7-dione 3aa was gen-
erated in up to 56% yield with the use of inorganic bases.
Application of different organic bases (entries 6−8) was also
examined in this reaction, and the best results were obtained in
the case of sterically bulky base TBD (1,5,7-
triazabicyclo[4.4.0]dec-5-ene), allowing preparation of 3aa
B
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a
efficiently coupled with 2H-indene-1,3-dione 2a under standard
reaction conditions to produce the corresponding spirocyclo-
propanes 3 in good yields. The presence of a substituent on the
phenyl ring of styrenes 1 had almost no effect on chemical
yields. The substituents, including alkyl (1b, 1c, and 1f),
methoxyl (1d), and halo (1g−i, 1m) groups, were well
tolerated and successfully cyclized, even for the strong
electron-withdrawing groups (nitro 1j, cyano 1k). Very
interestingly, the substrates with naphthyl (1n) or pyridinyl
substituent (1o) could also work well, and the products 3na
and 3oa were isolated in excellent yields (87% and 80%,
respectively). Notably, allylbenzene (1p) also was tried as
substrate in this reaction, which was transformed into benzyl-
substituted product in a low yield (15%, 3pa). Finally,
substrates with substituents on the C−C double bond of
styrenes were tried to investigate the steric effect, and the
results indicate that steric hindrance had almost no effect on
this reaction. For example, the reaction with methyl- or phenyl-
substituted olefins could work well, affording products with
yields of 70% (3sa) and 71% (3ta), respectively. However, the
electronegativity of the substituents showed a significant effect
on this reaction, and iodo- (1q) and bromo- (1r) substituted
styrenes gave obviously lower chemical yields of corresponding
products along with a complex mixture.
As the next goal of the substrate study on cyclopropanation
reaction, several other types of 1,3-dicarbonyl compounds were
selected as substrates for this reaction (Scheme 3). First, several
Meldrum’s acid derivatives (2b−d) were chosen to react with
styrenes 1a. As shown in Scheme 3, the reactions with
Meldrum’s acid and its analogs (1,5-dioxaspiro[5.5]undecane-
2,4-dione 2c and 6,10-dioxaspiro[4.5]decane-7,9-dione 2d)
could proceed very well under the standard condition, affording
the corresponding product with 84−89% yields (3ab−ad).
Then several barbituric acid derivatives were examined. For
example, 1,3-dimethylbarbituric acid 2e and 1,3-dicyclohex-
ylbarbituric acid 2f could be smoothly transferred into the
desired product with good yield (3ae and 3af). Finally, the
substrate with a variation to the sulfur atom, 1,3-dibutyl-2-
thiobarbituric acid 2g, was used in this reaction. Unfortunately,
almost no desired product 3ag was observed under the
standard condition.
To investigate the details of the mechanism for this
spirocyclization reaction, several control experiments were
carried out (Scheme 4). First, 2,2-diiodo-1H-indene-1,3(2H)-
dione 4a, instead of 2H-indene-1,3-dione 2a, was used to react
with styrene 1a under the standard condition. No desired
product 3aa was obtained, which indicates that 2-iodo-1H-
indene-1,3(2H)-dione radical generated from the light-
promoted C−I bond cleavage is not the reaction intermediate
(Scheme 4a). The reaction does not happen at all without
addition of base TBD (Scheme 4b). Also, it is found that in the
absence of NIS, the reaction gives no desired product 3aa
(Scheme 4c). A reaction of 1a and 2a with the addition of
radical-trapping reagent 2,2,6,6-tetramethyl-1-piperidinyloxy
(TEMPO) or butylated hydroxytoluene (BHT) under the
standard condition was performed, and the formation of
desired product 3aa was suppressed, which suggests the radical
nature of the mechanism.
Table 1. Optimization of Reaction Conditions
b
entry additive (equiv)
base
time (h)
solvent
yield (%)
c
1
NIS (2)
NIS (2)
NIS (2)
NIS (2)
NIS (2)
NIS (2)
NIS (2)
NIS (2)
NIS (2)
NIS (2)
NIS (2)
NIS (2)
NIS (2)
NIS (2)
NIS (2)
NIS (1)
NIS (2)
NIS (2)
NBS (2)
I2 (2)
K2CO3
KOH
CH3ONa
t-BuONa
DABCO
TEA
10
10
10
10
10
10
10
10
10
10
10
10
10
10
2
EA
0
2
EA
20
48
56
6
3
EA
4
EA
5
EA
6
EA
23
61
87
87
80
62
91
88
95
98
41
7
DBU
TBD
EA
8
EA
9
TBD
DMF
DMSO
THF
CH3CN
CHCl3
DCM
DCM
DCM
DCM
DCM
DCM
DCM
DCM
DCM
10
11
12
13
14
15
16
17
18
19
20
21
22
TBD
TBD
TBD
TBD
TBD
TBD
TBD
2
d
TBD
2
91
e
TBD
2
68
TBD
10
10
2
21
10
TBD
f
NIS (2)
NIS (2)
TBD
84
g
TBD
2
88
a
Reaction conditions: 1a (0.9 mmol), 2a (0.3 mmol), additive, base (1
equiv), white LED lamp, solvent (3 mL), rt, under argon atmosphere.
Ethyl acetate. Isolated yield. 2 equiv of 1a. Reaction was carried
b
c
d
e
f
g
out in the dark. Yellow LED lamp was used. Blue LED lamp was
used.
with 87% yield (entry 8). The reaction media was found to
have a significant effect on the reaction efficiency. The
cyclopropanation reactions performed in DMF (entry 9),
DMSO (entry 10), and CHCl3 (entry 13) gave the product 3aa
with a similar yield to that observed in ethyl acetate (entry 8).
An excellent yield of 3aa was obtained when the reaction was
carried out in acetonitrile (entry 12). CH2Cl2 was the best
choice, resulting in an increased yield of 95% (entry 14). It is
desireable that the reaction could be completed within 2 h, with
an almost quantitative yield of 3aa (98%, entry 15). Further
scan showed that decreasing the loading amount of NIS to 1
equiv led to a dramatically lower yield (41%, entry 16). On the
other hand, decreasing the use of 1a to 2 equiv gave a slightly
lower yield of product 3aa (entry 17). It should be mentioned
that the reaction performed in the dark also could proceed,
however, with significantly less efficiency (68% yield, entry 18).
Other additives, such as NBS (entry 19) and iodine (entry 20),
were tried for this reaction instead of NIS, and the results
clearly suggested that NIS might be considered as the best
choice. Finally, the reactions in the presence of a yellow LED
lamp (entry 21) and blue LED lamp (entry 22) were examined,
and the reactions could also proceed smoothly with 84% and
88% yield, respectively.
On the basis of the control experiments and the previous
reports,12 a possible mechanism was proposed in Scheme 5.
Initially, 2H-indene-1,3-dione 2a in the presence of TBD
undergoes deprotonation and is converted into anion A.
Subsequently, anion A reacts with NIS to form the 2-iodo-1H-
Then examination of the substrate scope for this NIS-
initiated spirocyclopropanation reaction of styrenes was
performed. As shown in Scheme 2, a variety of styrenes
C
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a b
,
Scheme 2. Substrate Study with Variation of Styrenes
a
Reaction conditions: 1 (0.9 mmol), 2a (0.3 mmol), NIS (2 equiv) based on 2a, TBD (1 equiv), white LED lamp 2 h, rt, under argon atmosphere.
Isolated yield.
b
indene-1,3(2H)-dione B along with regeneration of TBD by
standard reaction condition, the reaction between 1u and 2a
proceeds smoothly to produce the corresponding product 3ua
in excellent yield (91%) (Scheme 6). Such spiro[2.5]octa-4,7-
dien-6-one core is a privileged structure found in many natural
products.17 However, the previous literature method has to use
2-halo 1,3-dicarbonyl compound as starting material.18 Thus,
this developed reaction represents a straightforward method to
prepare valuable spiro[2.5]octa-4,7-dien-6-one compounds
from the readily available 2H-indene-1,3-dione.
succinimide anion. The intermediate B proceeds through C−I
bond cleavage with irradiation of light to generate intermediate
C. Then C couples with styrene 1a, affording the intermediate
D, which undergoes the second C−I bond formation with
another equivalent of NIS. This is accounting for the necessity
of 2 equiv of NIS. The second deprotonation happens on the
intermediate E with the aid of base TBD, giving the
intermediate F. Finally, intramolecular nucleophilic attack of
F happens via the second C−I bond cleavage to give the
corresponding product 3aa.
CONCLUSION
■
The synthetic value of this new reaction was further
demonstrated by the successful spirocyclopropanation of p-
quinone methide 1u with 2H-indene-1,3-dione 2a. Under the
In summary, we developed an efficient cascade spirocyclopro-
panation reaction between 1,3-dicarbonyl compounds and
styrenes, which proceeded through cleavage of a sp3 C−H bond
D
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a b
,
Scheme 3. Substrate Study with Variation of 1,3-Dicarbonyl Compounds
a
Reaction conditions: 1a (0.9 mmol), 2 (0.3 mmol), NIS (2 equiv) based on 2, TBD (1 equiv), white LED lamp 2 h, rt, under argon atmosphere.
Isolated yield.
b
Scheme 4. Investigation of the Mechanism Conditions
of 2H-indene-1,3-dione, iodination, coupling with styrene,
second iodination, and intramolecular cyclization. These
reactions could be carried out at room temperature and
tolerated a wide range of substrates, resulting in good to
excellent chemical yields. This process demonstrates a
multistep radical reaction for functionalization of 1,3-dicarbonyl
compounds and also represents a new strategy for preparation
of spirocyclopropane. Further studies directly toward the
development of new coupling partners for the construction of
spirocyclobutane are currently underway in our lab.
EXPERIMENTAL SECTION
■
General Procedure for the Synthesis of Spirocyclopropanes
between Styrenes with 1,3-Dicarbonyl Compounds. Into an
oven-dried reaction vial flushed with argon was added 1H-indene-
1,3(2H)-dione (2a) (0.3 mmol), styrene (1a, 0.9 mmol), NIS (0.6
mmol), TBD (0.3 mmol), and DCM (3 mL). Then the reaction
mixture was stirred for 2 h at room temperature under argon
E
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2-(4-Methoxyphenyl)spiro[cyclopropane-1,2′-indene]-1′,3′-
Scheme 5. Proposed Mechanism
1
dione(3da). White solid (75.1 mg, 90% yield), mp 148−150 °C. H
NMR (400 MHz, CDCl3) δ 7.94 (t, J = 7.1 Hz, 1H), 7.82−7.69 (m,
3H), 7.22 (d, J = 8.6 Hz, 2H), 6.82 (d, J = 8.7 Hz, 2H), 3.77 (s, 3H),
3.41 (t, J = 8.9 Hz, 1H), 2.45 (dd, J = 8.8, 4.3 Hz, 1H), 2.29 (dd, J =
9.0, 4.3 Hz, 1H). 13C NMR (101 MHz, CDCl3) δ 198.3, 196.0, 159.2,
142.7, 141.6, 134.8, 134.6, 130.4, 125.5, 122.4, 122.4, 113.6, 55.3, 55.2,
43.1, 41.4, 22.4. IR (attenuated total reflection, cm−1): ν 1697, 1520,
1333, 1256, 1224, 1187, 1150, 1045, 1024, 1008, 841, 756, 686. HRMS
+
(TOF MS ESI): calcd for C18H15O3 [M + H]+ 279.1021, found
279.1015.
2-([1,1′-Biphenyl]-4-yl)spiro[cyclopropane-1,2′-indene]-1′,3′-
dione(3ea). Light yellow solid (94.31 mg, 97% yield), mp 169−170
1
°C. H NMR (400 MHz, CDCl3) δ 7.81−7.79 (m, 1H), 7.65−7.63
(m, 1H), 7.56−7.51 (m, 2H), 7.42−7.37 (m, 4H), 7.26−7.21 (m, 4H),
7.17−7.13 (m, 1H), 3.33 (t, J = 8.9 Hz, 1H), 2.35 (dd, J = 8.8, 4.3 Hz,
1H), 2.17 (dd, J = 9.0, 4.3 Hz, 1H). 13C NMR (101 MHz, CDCl3) δ
198.2, 196.0, 142.8, 141.7, 140.8, 140.7, 135.0, 134.8, 132.8, 129.7,
128.8, 127.4, 127.2, 127.0, 122.6, 122.6, 43.0, 41.2, 22.5. IR (attenuated
total reflection, cm−1): ν 1700, 1601, 1380, 1334, 1311, 1225, 1194,
1064, 1044, 1007, 843, 768, 729. HRMS (TOF MS ESI): calcd for
atmosphere in the presence of white LED light. After the reaction was
complete, the mixture was poured into H2O (20 mL) and extracted
with DCM three times. The combined organic layer was dried with
anhydrous Na2SO4 and evaporated under vacuum. The crude mixture
was charged onto silica gel and purified by flash chromatography
(petroleum ether:ethyl acetate = 6:1) to furnish the corresponding
product 3aa. Other compounds 3 were obtained with similar reaction
conditions.
+
C23H17O2 [M + H]+ 325.1229, found 325.1219.
2-(2,5-Dimethylphenyl)spiro[cyclopropane-1,2′-indene]-1′,3′-
1
dione (3fa). White solid (76.2 mg, 92% yield), mp 128−129 °C. H
NMR (400 MHz, CDCl3) δ 8.02−7.93 (m, 1H), 7.85−7.71 (m, 3H),
7.16 (s, 1H), 7.01 (d, J = 8.0 Hz, 1H), 6.96 (d, J = 7.7 Hz, 1H), 3.29 (t,
J = 8.8 Hz, 1H), 2.47 (dd, J = 8.8, 4.0 Hz, 1H), 2.36 (s, 3H), 2.28 (dd,
J = 8.8, 4.0 Hz, 1H), 1.87 (s, 3H). 13C NMR (101 MHz, CDCl3) δ
198.6, 195.6, 142.3, 141.4, 135.1, 134.9, 134.8, 134.7, 132.4, 129.7,
129.6, 128.8, 122.5, 122.4, 42.0, 39.7, 22.5, 21.2, 19.1. IR (attenuated
total reflection, cm−1): ν 1700, 1375, 1330, 1311, 1285, 1196, 1042,
820, 561, 556. HRMS (TOF MS ESI): calcd for C19H17O2+ [M + H]+
277.1229, found 277.1223.
2-Phenylspiro[cyclopropane-1,2′-indene]-1′,3′-dione (3aa). Light
1
yellow solid (72.9 mg, 98% yield), mp 126−128 °C. H NMR (400
MHz, CDCl3) δ 7.93−7.88 (m, 1H), 7.75−7.64 (m, 3H), 7.24−7.16
(m, 5H), 3.38 (t, J = 8.9 Hz, 1H), 2.41 (dd, J = 8.8, 4.3 Hz, 1H), 2.23
(dd, J = 9.0, 4.3 Hz, 1H). 13C NMR (101 MHz, CDCl3) δ 198.3,
196.0, 142.8, 141.7, 135.0, 134.7, 133.7, 129.3, 128.2, 127.9, 122.6,
122.6, 42.8, 41.3, 22.3. IR (attenuated total reflection, cm−1): ν 1967,
1381, 1330, 1320, 1310, 1287, 1216, 1061, 1040, 1027, 998, 942, 745,
2-(4-Fluorophenyl)spiro[cyclopropane-1,2′-indene]-1′,3′-dione
1
(3ga). Light yellow solid (63.1 mg, 79% yield), mp 150−151 °C. H
NMR (400 MHz, CDCl3) δ 7.88 (dd, J = 6.2, 1.3 Hz, 1H), 7.75−7.62
(m, 3H), 7.21−7.13 (m, 2H), 6.92−6.86 (m, 2H), 3.32 (t, J = 8.9 Hz,
1H), 2.33 (dd, J = 8.7, 4.3 Hz, 1H), 2.21 (dd, J = 9.1, 4.3 Hz, 1H). 13C
NMR (101 MHz, CDCl3) δ 198.0, 195.9, 163.6 (1JC−F = 248.5 Hz),
142.7, 141.7, 135.0, 134.8, 130.9, 130.9, 129.4, 129.4, 122.6, 122.6,
115.3 (2JC−F = 22.2 Hz), 42.6, 40.2, 22.4. IR (attenuated total
reflection, cm−1): ν 1700, 1513, 1334, 1306, 1287, 1219, 1191, 1161,
1152, 1037, 1109, 844, 762, 726. HRMS (TOF MS ESI): calcd for
C17H11FO2Na+ [M + Na]+ 289.0641, found 289.0635.
+
706, 593. HRMS (TOF MS ESI): calcd for C17H13O2 [M + H]+
249.0916, found 249.0911.
2-(p-Tolyl)spiro[cyclopropane-1,2′-indene]-1′,3′-dione (3ba).
1
Light yellow solid (70.0 mg, 89% yield), mp 90−92 °C. H NMR
(400 MHz, CDCl3) δ 7.86 (dd, J = 6.4, 1.3 Hz, 1H), 7.72−7.60 (m,
3H), 7.04 (d, J = 8.1 Hz, 2H), 6.99 (d, J = 8.0 Hz, 2H), 3.33 (t, J = 8.9
Hz, 1H), 2.37 (dd, J = 8.8, 4.2 Hz, 1H), 2.21(s, 3H), 2.22−2.18 (m,
1H). 13C NMR (101 MHz, CDCl3) δ 198.3, 196.0, 142.7, 141.6, 137.6,
134.8, 134.6, 130.6, 129.6, 129.1, 128.9, 122.5, 122.4, 42.9, 41.4, 22.3,
21.3, 21.1. IR (attenuated total reflection, cm−1): ν 1696, 1350, 1334,
1309, 1289, 1223, 1162, 1045, 816, 757, 721. HRMS (TOF MS ESI):
2-(4-Chlorophenyl)spiro[cyclopropane-1,2′-indene]-1′,3′-dione-
1
(3ha). Light yellow solid (77.8 mg, 92% yield), mp 165−166 °C. H
NMR (400 MHz, CDCl3) δ 7.96 (dt, J = 8.6, 4.2 Hz, 1H), 7.83−7.73
(m, 3H), 7.29−7.20 (m, 4H), 3.39 (t, J = 8.9 Hz, 1H), 2.42 (dd, J =
8.7, 4.3 Hz, 1H), 2.29 (dd, J = 9.0, 4.3 Hz, 1H). 13C NMR (101 MHz,
CDCl3) δ 197.9, 195.8, 142.6, 141.6, 135.0, 134.9, 133.7, 132.2, 130.6,
128.4, 122.6, 122.6, 42.5, 40.1, 22.3. IR (attenuated total reflection,
cm−1): ν 1700, 1594, 1363, 1344, 1336, 1310, 1198, 1091, 768, 727.
+
calcd for C18H15O2 [M + H]+ 263.1072, found 263.1066.
2-(4-(tert-Butyl)phenyl)spiro[cyclopropane-1,2′-indene]-1′,3′-
1
dione (3ca). White solid (83.0 mg, 91% yield), mp 85−87 °C. H
NMR (400 MHz, CDCl3) δ 7.86 (dd, J = 6.3, 1.4 Hz, 1H), 7.73−7.60
(m, 3H), 7.24−7.14 (m, 4H), 3.32 (t, J = 9.0 Hz, 1H), 2.38 (dd, J =
8.9, 4.2 Hz, 1H), 2.20 (dd, J = 9.1, 4.2 Hz, 1H), 1.20 (s, 9H). 13C
NMR (101 MHz, CDCl3) δ 198.3, 196.0, 150.7, 142.8, 141.6, 134.8,
134.6, 130.6, 128.9, 125.1, 122.5, 122.5, 43.0, 41.4, 34.6, 31.4, 22.6. IR
(attenuated total reflection, cm−1): ν 1700, 1381, 1354, 1334, 1310,
1289, 1225, 1064, 1040, 1009, 824, 760, 744. HRMS (TOF MS ESI):
+
HRMS (TOF MS ESI): calcd for C17H12ClO2 [M + H]+ 283.0526,
found 283.0521.
2-(4-Bromophenyl)spiro[cyclopropane-1,2′-indene]-1′,3′-dione
1
(3ia). White solid (82.1 mg, 84% yield), mp 179−180 °C. H NMR
(400 MHz, CDCl3) δ 7.88 (dt, J = 7.9, 3.8 Hz, 1H), 7.76−7.64 (m,
3H), 7.36−7.30 (m, 2H), 7.08 (d, J = 8.4 Hz, 2H), 3.29 (t, J = 8.9 Hz,
+
calcd for C21H21O2 [M + H]+ 305.1542, found 305.1538.
Scheme 6. Spirocyclopropanation Reaction of p-Quinone Methide
F
DOI: 10.1021/acs.joc.6b01163
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The Journal of Organic Chemistry
Article
1H), 2.33 (dd, J = 8.7, 4.4 Hz, 1H), 2.21 (dd, J = 9.0, 4.3 Hz, 1H). 13
C
2-Benzylspiro[cyclopropane-1,2′-indene]-1′,3′-dione (3pa). Light
yellow oil (11.8 mg, 15% yield). 1H NMR (400 MHz, CDCl3) δ 7.95−
7.90 (m, 2H), 7.80−7.75 (m, 2H), 7.25−7.18 (m, 2H), 7.18−7.07 (m,
3H), 3.18−3.07 (m, 2H), 2.55−2.47 (m, 1H), 2.05 (dd, J = 8.7, 3.6
Hz, 1H), 1.92 (dd, J = 8.3, 3.6 Hz, 1H). 13C NMR (101 MHz, CDCl3)
δ 199.1, 198.7, 142.7, 141.6, 140.1, 134.9, 134.8, 128.6, 128.4, 126.4,
122.6, 122.4, 40.0, 38.2, 32.6, 26.2. IR (attenuated total reflection,
cm−1): ν 1702, 1597, 1454, 1387, 1335, 1314, 1285, 1205, 1157, 1098,
1021, 743, 721, 697. HRMS (TOF MS ESI): calcd for C18H15O2+ [M
+ H]+ 263.1072, found 263.1063.
NMR (101 MHz, CDCl3) δ 197.9, 195.8, 142.6, 141.6, 135.1, 134.9,
132.7, 131.3, 130.9, 122.6, 122.6, 121.9, 42.5, 40.1, 22.2. IR (attenuated
total reflection, cm−1): ν 1697, 1334, 1314, 1289, 1260, 1219, 1091,
1076, 1067, 1008, 750, 721, 691. HRMS (TOF MS ESI): calcd for
C17H11BrO2Na+ [M + Na]+ 348.9840, found 348.9834.
2-(4-Nitrophenyl)spiro[cyclopropane-1,2′-indene]-1′,3′-dione
1
(3ja). Light yellow solid (80.0 mg, 91% yield), mp 169−170 °C. H
NMR (400 MHz, CDCl3) δ 8.08 (d, J = 8.7, 2H), 7.91 (dd, J = 12.2,
5.6 Hz, 1H), 7.78−7.68 (m, 3H), 7.40 (d, J = 8.7 Hz, 2H), 3.38 (t, J =
8.8 Hz, 1H), 2.40 (dd, J = 8.6, 4.5 Hz, 1H), 2.28 (dd, J = 8.9, 4.5 Hz,
1H). 13C NMR (101 MHz, CDCl3) δ 197.3, 195.6, 147.4, 142.5, 141.6,
141.4, 135.4, 135.2, 130.2, 123.4, 122.9, 122.8, 42.4, 39.0, 22.2. IR
(attenuated total reflection, cm−1): ν 1698, 1507, 1314, 1289, 1226,
1041, 1009, 871, 766, 689. HRMS (TOF MS ESI): calcd for
C17H11NO4Na+ [M + Na]+ 316.0586, found 316.0581.
2-Iodo-2-phenylspiro[cyclopropane-1,2′-indene]-1′,3′-dione
1
(3qa). White solid (39.3 mg, 35% yield), mp 65−67 °C. H NMR
(400 MHz, CDCl3) δ 8.05−7.97 (m, 1H), 7.82−7.70 (m, 3H), 7.25−
7.11 (m, 5H), 2.71 (d, J = 5.7 Hz, 1H), 2.35 (d, J = 5.7 Hz, 1H). 13C
NMR (101 MHz, CDCl3) δ 194.4, 193.6, 142.4, 142.4, 142.3, 135.4,
128.6, 128.6, 123.3, 122.9, 42.8, 32.2, 16.3. IR (attenuated total
reflection, cm−1): ν 1707, 1353, 1254, 1165, 1064, 1051, 1039, 1020,
1010, 936, 853, 751. HRMS (TOF MS ESI): calcd for C17H12IO2+ [M
+ H]+ 374.9882, found 374.9888.
4-(1′,3′-Dioxo-1′,3′-dihydrospiro[cyclopropane-1,2′-inden]-2-yl)-
benzonitrile (3ka). Light yellow solid (61.4 mg, 75% yield), mp 206−
1
208 °C. H NMR (400 MHz, CDCl3) δ 8.01−7.98 (m, 1H), 7.85−
2-Bromo-2-phenylspiro[cyclopropane-1,2′-indene]-1′,3′-dione
(3ra). White solid (46.9 mg, 48% yield), mp 95−96 °C. 1H NMR (400
MHz, CDCl3) δ 8.12−8.04 (m, 1H), 7.88−7.76 (m, 3H), 7.36−7.25
(m, 5H), 2.80 (d, J = 6.0 Hz, 1H), 2.60 (d, J = 6.0 Hz, 1H). 13C NMR
(101 MHz, CDCl3) δ 193.8, 193.6, 142.8, 142.3, 138.7, 135.4, 135.2,
129.1, 129.0, 128.7, 123.3, 123.0, 46.6, 44.3, 29.1. IR (attenuated total
reflection, cm−1): ν 1709, 1354, 1256, 1066, 1057, 752, 716, 607.
7.76 (m, 3H), 7.63−7.58 (m, 2H), 7.42 (d, J = 8.1 Hz, 2H), 3.42 (t, J =
8.8 Hz, 1H), 2.45 (dd, J = 8.7, 4.5 Hz, 1H), 2.33 (dd, J = 9.0, 4.5 Hz,
1H). 13C NMR (101 MHz, CDCl3) δ 197.5, 195.7, 142.6, 141.7, 139.3,
135.4, 135.2, 132.0, 130.1, 122.9, 122.8, 118.8, 111.7, 42.4, 39.5, 22.1.
IR (attenuated total reflection, cm−1): ν 2227, 1700, 1593, 1333, 1286,
1218, 1093, 1063, 1009, 853, 763, 736. HRMS (TOF MS ESI): calcd
+
for C18H12NO2 [M + H]+ 274.0868, found 274.0872.
+
HRMS (TOF MS ESI): calcd for C17H12BrO2 [M + H]+ 327.0021,
Methyl 4-(1′,3′-Dioxo-1′,3′-dihydrospiro[cyclopropane-1,2′-
found 327.0021.
inden]-2-yl)benzoate (3la). White solid (41.3 mg, 45% yield), mp
1
2-Methyl-2-phenylspiro[cyclopropane-1,2′-indene]-1′,3′-dione
205−207 °C. H NMR (400 MHz, CDCl3) δ 7.94−7.86 (m, 3H),
1
(3sa). Light yellow oil (55.0 mg, 70% yield). H NMR (400 MHz,
7.76−7.65 (m, 3H), 7.30 (d, J = 8.2 Hz, 2H), 3.86−3.78 (s, 3H), 3.37
(dd, J = 10.9, 6.8 Hz, 1H), 2.41 (dd, J = 8.7, 4.4 Hz, 1H), 2.25 (dd, J =
9.0, 4.4 Hz, 1H). 13C NMR (101 MHz, CDCl3) δ 197.9, 195.7, 166.9,
142.7, 141.7, 139.0, 135.2, 135.0, 129.6, 129.5, 129.4, 122.7, 122.7,
52.2, 42.6, 40.2, 22.2. IR (attenuated total reflection, cm−1): ν 1715,
1700, 1430, 1278, 1260, 1220, 1177, 1108, 1041, 1020, 800, 776.
CDCl3) δ 7.99−7.94 (m, 1H), 7.80−7.71 (m, 3H), 7.33−7.24 (m,
3H), 7.20−7.12 (m, 2H), 2.53 (d, J = 4.2 Hz, 1H), 2.18 (d, J = 4.2 Hz,
1H), 1.76 (s, 3H). 13C NMR (101 MHz, CDCl3) δ 197.8, 196.1,
142.6, 142.4, 140.6, 134.7, 134.6, 128.6, 128.5, 127.5, 122.4, 122.3,
49.3, 46.1, 29.0, 22.0. IR (attenuated total reflection, cm−1): ν 1702,
1597, 1350, 1249, 1220, 1158, 1132, 1069, 1027, 758, 698. HRMS
(TOF MS ESI): calcd for C18H14O2Na+ [M + Na]+ 285.0891, found
285.0894.
+
HRMS (TOF MS ESI): calcd for C19H15O4 [M + H]+ 307.0970,
found 307.0965.
2-(2-Chlorophenyl)spiro[cyclopropane-1,2′-indene]-1′,3′-dione
2,2-Diphenylspiro[cyclopropane-1,2′-indene]-1′,3′-dione (3ta).
1
(3ma). White solid (70.2 mg, 83% yield), mp 176−177 °C. H NMR
1
White solid (69.0 mg, 71% yield), mp 176−178 °C. H NMR (400
(400 MHz, CDCl3) δ 7.90−7.89 (m, 1H), 7.75−7.62 (m, 3H), 7.35
(d, J = 7.6 Hz, 1H), 7.25−7.10 (m, 3H), 3.27 (t, J = 8.7 Hz, 1H), 2.29
(dd, J = 8.7, 4.2 Hz, 1H), 2.21 (dd, J = 8.8, 4.2 Hz, 1H). 13C NMR
(101 MHz, CDCl3) δ 198.2, 195.7, 142.4, 141.6, 136.0, 134.9, 134.7,
132.7, 130.7, 129.2, 129.0, 126.7, 122.5, 122.5, 41.4, 38.1, 22.0. IR
(attenuated total reflection, cm−1): ν 1700, 1594, 1377, 1336, 1313,
1287, 1219, 1039, 1009, 770, 749, 734. HRMS (TOF MS ESI): calcd
MHz, CDCl3) δ 7.92−7.89 (m, 2H), 7.80−7.77 (m, 2H), 7.31−7.29
(m, 5H), 7.27−7.24 (m, 3H), 7.22−7.18 (m, 2H), 2.71 (s, 2H). 13C
NMR (101 MHz, CDCl3) δ 196.4, 142.6, 139.7, 134.9, 129.2, 128.7,
127.6, 122.8, 56.2, 46.2, 27.5. IR (attenuated total reflection, cm−1): ν
1740, 1706, 1490, 1446, 1358, 1238, 1156, 1061, 819, 773. HRMS
+
(TOF MS ESI): calcd for C23H17O2 [M + H]+ 325.1229, found
325.1223.
+
for C17H12ClO2 [M + H]+ 283.0526, found 283.0520.
6,6-Dimethyl-1-phenyl-5,7-dioxaspiro[2.5]octane-4,8-dione
1
2-(Naphthalen-1-yl)spiro[cyclopropane-1,2′-indene]-1′,3′-dione
(3ab). Light yellow solid (65.7 mg, 89% yield), mp 130−131 °C. H
1
(3na). Light yellow solid (77.8 mg, 87% yield), mp 155−156 °C. H
NMR (400 MHz, CDCl3) δ 7.38−7.29 (m, 5H), 3.45 (t, J = 9.4 Hz,
1H), 2.69 (dd, J = 9.3, 4.8 Hz, 1H), 2.55 (dd, J = 9.5, 4.8 Hz, 1H), 1.73
(d, J = 1.8 Hz, 6H). 13C NMR (101 MHz, CDCl3) δ 167.9, 163.6,
131.2, 129.6, 128.8, 128.5, 105.0, 44.7, 33.2, 28.1, 27.8, 23.0. IR
(attenuated total reflection, cm−1): ν 1731, 1331, 1287, 1175, 1035,
959, 718, 658. HRMS (TOF MS ESI): calcd for C14H14O4Na+ [M +
Na]+ 269.0790, found 269.0782.
NMR (400 MHz, CDCl3) δ 8.03−8.02 (d, J = 7.6 Hz, 1H), 7.79−7.72
(m, 3H), 7.66−7.59 (m, 2H), 7.56−7.55 (m, 2H), 7.48 (t, J = 7.6 Hz,
1H), 7.33 (t, J = 7.4 Hz, 1H), 7.20 (t, J = 7.6 Hz, 1H), 3.78 (t, J = 8.7
Hz, 1H), 2.61 (dd, J = 8.6, 4.0 Hz, 1H), 2.41 (dd, J = 8.7, 4.0 Hz, 1H).
13C NMR (101 MHz, CDCl3) δ 198.9, 195.4, 142.5, 141.6, 135.1,
134.7, 133.5, 132.9, 130.2, 129.0, 128.8, 127.0, 126.5, 125.8, 125.3,
122.8, 122.6, 122.6, 42.3, 38.4, 22.4. IR (attenuated total reflection,
cm−1): ν 1700, 1593, 1362, 1344, 1335, 1309, 1291, 1198, 1148, 1091,
1045, 999, 768, 727. HRMS (TOF MS ESI): calcd for C21H15O2+ [M
+ H]+ 299.1072, found 299.1067.
1-Phenyl-5,12-dioxadispiro[2.2.56.23]tridecane-4,13-dione (3ac).
1
White solid (73.0 mg, 85% yield), mp 146−148 °C. H NMR (400
MHz, CDCl3) δ 7.40−7.27 (m, 5H), 3.43 (t, J = 9.4 Hz, 1H), 2.67
(dd, J = 9.3, 4.7 Hz, 1H), 2.52 (dd, J = 9.5, 4.7 Hz, 1H), 2.08−1.86 (m,
4H), 1.82−1.33 (m, 6H). 13C NMR (101 MHz, CDCl3) δ 167.9,
163.6, 131.4, 129.5, 128.7, 128.4, 105.8, 44.3, 37.2, 36.2, 33.3, 24.1,
23.0, 22.3, 21.8. IR (attenuated total reflection, cm−1): ν 1735, 1366,
1340, 1298, 1268, 1252, 1221, 1180, 1108, 1058, 971, 836, 697. HRMS
(TOF MS ESI): calcd for C17H18O4Na+ [M + Na]+ 309.1103, found
309.1101.
2-(Pyridin-2-yl)spiro[cyclopropane-1,2′-indene]-1′,3′-dione
1
(3oa). Light yellow oil (59.8 mg, 80% yield), H NMR (400 MHz,
CDCl3) δ 8.52−8.51 (m, 1H), 7.99−7.96 (m, 1H), 7.86−7.62 (m,
4H), 7.37 (d, J = 7.9 Hz, 1H), 7.18 (m, 1H), 3.59 (t, J = 8.8 Hz, 1H),
2.59 (dd, J = 8.6, 4.2 Hz, 1H), 2.31 (dd, J = 9.0, 4.2 Hz, 1H). 13C
NMR (101 MHz, CDCl3) δ 197.7, 196.2, 153.8, 149.3, 142.6, 141.8,
136.2, 135.0, 134.9, 123.7, 122.7, 122.6, 122.5, 41.8, 41.2, 21.8. IR
(attenuated total reflection, cm−1): ν 1696, 1591, 1433, 1333, 1311,
1289, 1222, 1039, 787, 748, 704. HRMS (TOF MS ESI): calcd for
1-Phenyl-5,11-dioxadispiro[2.2.46.23]dodecane-4,12-dione (3ad).
1
White solid (68.6 mg, 84% yield), mp 137−138 °C. H NMR (400
MHz, CDCl3) δ 7.40−7.28 (m, 5H), 3.40 (t, J = 9.4 Hz, 1H), 2.67
(dd, J = 9.3, 4.9 Hz, 1H), 2.53 (dd, J = 9.5, 4.9 Hz, 1H), 2.28−2.10 (m,
+
C16H12NO2 [M + H]+ 250.0868, found 250.0866.
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DOI: 10.1021/acs.joc.6b01163
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3H), 1.94−1.71 (m, 5H). 13C NMR (101 MHz, CDCl3) δ 168.2,
164.1, 131.2, 129.5, 128.8, 128.4, 114.2, 44.6, 39.8, 38.4, 33.9, 24.3,
22.8, 22.5. IR (attenuated total reflection, cm−1): ν 1739, 1700, 1338,
1216, 977, 698, 650. HRMS (TOF MS ESI): calcd for C16H16O4Na+
[M + Na]+ 295.0946, found 295.0956.
Bednarski, P. J.; Lalk, M.; Langer, P. Bioorg. Med. Chem. 2006, 14,
4694−4703.
(2) (a) Kakiuchi, K.; Tadaki, T.; Tobe, Y.; Odaira, Y. Chem. Lett.
1985, 1565−1568. (b) Richter, R.; von Reuß, S. H.; Konig, W. A.
̈
Phytochemistry 2010, 71, 1371−1374.
5,7-Dimethyl-1-phenyl-5,7-diazaspiro[2.5]octane-4,6,8-trione
(3) (a) Lerchner, A.; Carreira, E. M. J. Am. Chem. Soc. 2002, 124,
14826−14827. (b) Sedenkova, K. N.; Averina, E. B.; Grishin, Y. K.;
Andriasov, K. S.; Stepanova, S. A.; Roznyatovsky, V. A.; Kutateladze, A.
G.; Rybakov, V. B.; Albov, D. V.; Kuznetsova, T. S.; Zefirov, N. S.
Chem. - Eur. J. 2016, 22, 3996−3999. (c) Diethelm, S.; Carreira, E. M.
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Janssen, A.; Es-Sayed, M.; Magull, J.; De Meijere, A. Eur. J. Org. Chem.
2005, 2005, 610−617.
1
(3ae). Light yellow solid (65.0 mg, 84% yield), mp 87−88 °C. H
NMR (400 MHz, CDCl3) δ 7.34−7.24 (m, 5H), 3.52 (t, J = 9.3 Hz,
1H), 3.37 (s, 3H), 3.12 (s, 3H), 2.59 (dd, J = 9.2, 4.0 Hz, 1H), 2.45
(dd, J = 9.4, 4.0 Hz, 1H). 13C NMR (101 MHz, CDCl3) δ 168.4,
165.0, 152.0, 132.6, 129.8, 128.3, 128.2, 46.4, 36.0, 28.9, 28.6, 24.7. IR
(attenuated total reflection, cm−1): ν 1672, 1413, 1368, 1283, 1127,
+
1057, 787, 749, 691. HRMS (TOF MS ESI): calcd for C14H15N2O3
[M + H]+ 259.1083, found 259.1079.
(4) Diethelm, S.; Carreira, E. M. J. Am. Chem. Soc. 2015, 137, 6084−
6096.
(5) Banothu, J.; Basavoju, S.; Bavantula, R. J. Heterocyclic Chem. 2015,
5,7-Dicyclohexyl-1-phenyl-5,7-diazaspiro[2.5]octane-4,6,8-trione
(3af). White solid (94.6 mg, 80%), 144−146 °C. 1H NMR (400 MHz,
CDCl3) δ 7.33−7.25 (m, 3H), 7.24−7.17 (m, 2H), 4.70−4.63 (m,
1H), 4.41−4.33 (m, 1H), 3.37 (t, J = 9.1 Hz, 1H), 2.54 (dd, J = 9.0, 4.1
Hz, 1H), 2.38 (dd, J = 9.3, 4.1 Hz, 1H), 2.37−2.23 (m, 2H), 2.17−
2.06 (m, 1H), 1.91−1.78 (m, 3H), 1.72−1.66 (m, 5H), 1.55−1.52 (m,
1H), 1.45−1.32 (m, 3H), 1.27−1.02 (m, 5H). 13C NMR (101 MHz,
CDCl3) δ 168.5, 165.1, 151.4, 133.0, 129.7, 128.2, 128.1, 55.7, 55.5,
46.0, 36.8, 29.6, 29.5, 29.1, 28.4, 26.6, 26.5, 26.4, 26.3, 25.4, 25.1, 22.8.
IR (attenuated total reflection, cm−1): ν 1681, 1663, 1404, 1364, 1428,
1264, 894, 821, 754. HRMS (TOF MS ESI): calcd for C24H31N2O3
[M + H]+ 395.2335, found 395.2331.
52, 853−860.
(6) (a) Bauta, W.; Dodd, J.; Bullington, J.; Gauthier, D.; Leo, G.;
McDonnell, P. Tetrahedron Lett. 2000, 41, 1491−1494. (b) Rosenfeld,
M. J.; Shankar, B. K. R.; Shechter, H. J. Org. Chem. 1988, 53, 2699−
2705.
(7) (a) Horcajada, R.; Batanero, B.; Barba, F.; Martín, A. Tetrahedron
Lett. 2007, 48, 6437−6441. (b) Yoshida, J.; Yamamoto, M.; Kawabata,
N. Tetrahedron Lett. 1985, 26, 6217−6220.
(8) Nambu, H.; Fukumoto, M.; Hirota, W.; Ono, N.; Yakura, T.
Tetrahedron Lett. 2015, 56, 4312−4315.
(9) Wang, G. W.; Gao, J. Org. Lett. 2009, 11, 2385−2388.
(10) Russo, A.; Meninno, S.; Tedesco, C.; Lattanzi, A. Eur. J. Org.
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A.; Kodess, M. I. Russ. J. Org. Chem. 2010, 46, 499−502.
(12) Usami, K.; Nagasawa, Y.; Yamaguchi, E.; Tada, N.; Itoh, A. Org.
Lett. 2016, 18, 8−11.
3ua. Light yellow solid (119.7 mg, 91% yield), mp 208−210 °C. 1H
NMR (400 MHz, CDCl3) δ 8.02 (m, 1H), 7.96−7.89 (m, 1H), 7.88−
7.77 (m, 2H), 7.39−7.29 (m, 3H), 7.23 (d, J = 2.7 Hz, 1H), 7.18 (d, J
= 2.7 Hz, 1H), 7.12−7.03 (m, 2H), 4.30 (s, 1H), 1.29 (s, 9H), 1.19 (s,
9H). 13C NMR (101 MHz, CDCl3) δ 195.6, 193.2, 186.2, 150.2, 150.0,
143.0, 141.5, 135.7, 135.6, 135.4, 133.7, 131.6, 130.3, 128.4, 128.2,
123.1, 123.1, 51.9, 49.2, 46.9, 35.9, 35.6, 29.5, 29.4. IR (attenuated
total reflection, cm−1): ν 2920, 2160, 2031, 1710, 1610, 1610, 1380,
1255, 1220, 1148, 1005, 914, 743, 534. HRMS (TOF MS ESI): calcd
(13) For selected recent reviews on C(sp3)−H bond functionaliza-
tion, see: (a) Davies, H. M. L.; Morton, D. Chem. Soc. Rev. 2011, 40,
1857−1869. (b) Engle, K. M.; Mei, T. S.; Wasa, M.; Yu, J. Q. Acc.
Chem. Res. 2012, 45, 788−802. (c) Liu, C.; Zhang, H.; Shi, W.; Lei, A.
Chem. Rev. 2011, 111, 1780−1824. (d) Newhouse, T.; Baran, P. S.
Angew. Chem., Int. Ed. 2011, 50, 3362−3374. (e) Zhang, S. Y.; Zhang,
F. M.; Tu, Y. Q. Chem. Soc. Rev. 2011, 40, 1937−1949. (f) Rouquet,
G.; Chatani, N. Angew. Chem., Int. Ed. 2013, 52, 11726−11743.
(g) Girard, S. A.; Knauber, T.; Li, C. J. Angew. Chem., Int. Ed. 2014, 53,
74−100.
+
for C30H31O3 [M + H]+ 439.2273, found 439.2270.
ASSOCIATED CONTENT
■
S
* Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.joc.6b01163.
1H NMR and 13C NMR spectra for compounds 3 (PDF)
(14) For selected examples on iodination with NIS as precursor, see:
(a) Racys, D. T.; Sharif, S. A. I.; Pimlott, S. L.; Sutherland, A. J. Org.
Chem. 2016, 81, 772−780. (b) Racys, D. T.; Warrilow, C. E.; Pimlott,
S. L.; Sutherland, A. Org. Lett. 2015, 17, 4782−4785. (c) Zhu, L.; Xu,
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AUTHOR INFORMATION
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Corresponding Author
*E-mail: hanjl@nju.edu.cn.
Notes
́
́
Lett. 2016, 18, 712−715. (e) Testa, C.; Gigot, E.; Genc, S.; Decreau,
The authors declare no competing financial interest.
R.; Roger, J.; Hierso, J. Angew. Chem., Int. Ed. 2016, 55, 5555−5559.
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Org. Chem. 2011, 76, 9809−9816. (b) Kamimura, A.; Takeuchi, R.;
Ikeda, K.; Moriyama, T.; Sumimoto, M. J. Org. Chem. 2012, 77, 2236−
2245. (c) Yavari, I.; Hosseinpour, R.; Skoulika, S. Synlett 2015, 26,
380−384.
ACKNOWLEDGMENTS
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We gratefully acknowledge the financial support from the
National Natural Science Foundation of China (Nos. 21102071
and 21472082), the Jiangsu 333 program (Y.P.), and
Changzhou Jin-Feng-Huang program (J.H.).
(16) (a) Alegret, N.; Rodrguez-Fortea, A.; Poblet, J. M. Chem. - Eur. J.
2013, 19, 5061−5069. (b) Garcia-Borras
Izquierdo, M.; Luis, J. M.; Echegoyen, L.; Sola,
Ed. 2016, 55, 2374−2377.
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, M.; Ceron
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, M. R.; Osuna, S.;
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