Hypervalent iodine compounds for anti-markovnikov-type iodo-oxyimidation of vinylarenes

Article abstract of DOI:10.3762/bjoc.14.188

The iodo-oxyimidation of styrenes with the N-hydroxyimide/I₂/hypervalent iodine oxidant system was proposed. Among the examined hypervalent iodine oxidants (PIDA, PIFA, IBX, DMP) PhI(OAc)₂ proved to be the most effective; yields of iodo-oxyimides are 34–91%. A plausible reaction pathway includes the addition of an imide-N-oxyl radical to the double C=C bond and trapping of the resultant benzylic radical by iodine. It was shown that the iodine atom in the prepared iodo-oxyimides can be substituted by various nucleophiles.

Full text of DOI:10.3762/bjoc.14.188

Hypervalent iodine compounds for anti-Markovnikov-type
iodo-oxyimidation of vinylarenes
Igor B. Krylov1,2, Stanislav A. Paveliev1, Mikhail A. Syroeshkin1,
Alexander A. Korlyukov3,4, Pavel V. Dorovatovskii5, Yan V. Zubavichus5,
Gennady I. Nikishin1 and Alexander O. Terent’ev*1,2
Full Research Paper
Open Access
Address:
Beilstein J. Org. Chem. 2018, 14, 2146–2155.
1N. D. Zelinsky Institute of Organic Chemistry of the Russian
doi:10.3762/bjoc.14.188
Academy of Sciences, 47 Leninsky prosp., 119991 Moscow, Russian
Federation, 2All-Russian Research Institute for Phytopathology,
Received: 27 May 2018
Accepted: 31 July 2018
Published: 16 August 2018
143050 B. Vyazyomy, Moscow Region, Russian Federation,
3Nesmeyanov Institute of Organoelement Compounds, Russian
Academy of Sciences, Vavilov str., 28, 119991 Moscow, Russian
Federation, 4Pirogov Russian National Research Medical University,
Ostrovitianov str., 1, 117997 Moscow, Russian Federation and
This article is part of the Thematic Series "Hypervalent iodine chemistry in
organic synthesis".
5National Research Center “Kurchatov Institute”, Akademika
Kurchatova pl., 1, 123182 Moscow, Russian Federation
Guest Editor: T. Wirth
Email:
© 2018 Krylov et al.; licensee Beilstein-Institut.
License and terms: see end of document.
Alexander O. Terent’ev* - terentev@ioc.ac.ru
*
Corresponding author
Keywords:
free radicals; hypervalent iodine; imide-N-oxyl radicals; iodination;
N-hydroxyimides; oxidative functionalization
Abstract
The iodo-oxyimidation of styrenes with the N-hydroxyimide/I2/hypervalent iodine oxidant system was proposed. Among the exam-
ined hypervalent iodine oxidants (PIDA, PIFA, IBX, DMP) PhI(OAc)2 proved to be the most effective; yields of iodo-oxyimides
are 34–91%. A plausible reaction pathway includes the addition of an imide-N-oxyl radical to the double C=C bond and trapping of
the resultant benzylic radical by iodine. It was shown that the iodine atom in the prepared iodo-oxyimides can be substituted by
various nucleophiles.
Introduction
The presented work opens a new chapter in the chemistry of It is important to note, that nitroxyl radicals are widely used in
N-hydroxyimides in combination with hypervalent iodine com- organic and biological chemistry, and in material design [1-3].
pounds with formation of imide-N-oxyl radicals. These radicals These radicals are applied in the development of monomolec-
were used as reagents for the addition to a terminal position of ular magnets [4,5], spintronics [2,6], magneto-LC effect
the double bond of styrenes with subsequent iodination of the studies [7,8], organic voltaic cells [9], electrodes for electro-
resulting benzylic radical.
chemical synthesis [2], and as mediators of living polymeriza-
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tion [10,11]. In organic synthesis more stable types of N-oxyl tion of stabilized benzyl radicals, which undergo the
radicals can be used as carbon-centered radical scavengers [12], subsequent functionalization. In the presence of oxygen or tert-
oxidation catalysts, mainly for conversion of alcohols to car- butyl hydroperoxide, oxidation proceeds to form the C–O
bonyl compounds [11,13-17]. Less stable imide-N-oxyl [46-51] or the C=O [52-55] moiety. More complex reagents and
radicals are used as effective mediators for CH-functionaliza- reaction systems allows to form C–C [56,57] and C–N [58,59]
tion with formation of C–C, C–O, C–S, and C–N bonds bonds.
[
11,16,18-42].
Among the above-mentioned methods, there are no examples of
Phthalimide-N-oxyl (PINO) is one of the most known imide-N- C–Hal bond formation despite the wide usage of organohalides
oxyl radicals that is generated from an inexpensive N-hydroxy- in chemical syntheses. In the row of organohalides, iodides are
phthalimide (NHPI). This radical was used in various aerobic the most reactive and versatile reagents for the following trans-
oxidations of bulk chemicals [18,19,43,44].
formations [60].
In the present work imide-N-oxyl radicals were used for the ad- One of the purposes of our work was to introduce iodine in the
dition to the C=C bonds of styrenes with subsequent functional- process of difunctionalization of styrenes with imide-N-oxyl
ization of the resulting benzylic radicals.
radicals. Iodine atom in the product can act as a versatile
leaving group for further transformations. The involvement of
Recently, the precursors of N-oxyl radicals, such as N-hydroxy- the iodine in the radical reactions of styrenes is complicated by
phthalimide (NHPI), N-hydroxysuccinimide (NHSI), the fact that unsaturated compounds readily undergo electro-
N-hydroxybenzotriazole (HOBt) and hydroxamic acids, have philic iodination with the addition of an external nucleophile
been used in the reactions of radical oxygenation of styrenes [61,62]. The oxidants used for the preparation of imide-N-oxyl
[
45]. Growth of interest is observed concerning the reactions of radicals, in particular the hypervalent iodine compounds and
styrenes with imide-N-oxyl radicals, in which the latter add to peroxides [63-73], also generate electrophilic iodinating inter-
the terminal position of the double C=C bond with the forma- mediates (Scheme 1).
Scheme 1: Difunctionalization of double C=C bond with the formation of C–O and C–I bonds.
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For several decades, a number of papers on the electrophilic showed less efficacy in this process. Peroxide oxidants, such as
iodination of C=C bonds by iodine-containing oxidative TBHP, TBAI/TBHP system [74], (NH4)2S2O8, and DDQ were
systems with the addition of various nucleophiles have been ineffective in the studied process (Table 1, entries 17–22). A
published, all of these processes have common mechanism and satisfactory yield of 3aa (44%) was achieved using Oxone as
the same regioselectivity. The free-radical approach developed the oxidant (Table 1, entry 15). The addition of a catalytic
in the present work affords the opposite (anti-Markovnikov) amount of 2-iodobenzoic acid, which forms hypervalent iodine
regioselectivity of the addition to the double bond.
compounds in the presence of Oxone [75], did not lead to an in-
creased yield of 3aa (Table 1, entry 16).
Results and Discussion
In the present work, the reaction of styrenes 1a–k and Dichloromethane proved to be the best solvent for the reaction,
N-hydroxyimides 2a,b with the formation of iodo-oxyimidated as carrying out the reaction in other solvents led to a decrease in
products 3aa–ka, 3ab–db, 3fb, 3hb and 3kb was carried out the yield of 3aa (Table 1, entries 5–7). Increasing the amount of
(
Scheme 2).
PhI(OAc)2 from 0.6 mmol to 1.5 mmol (Table 1, entry 4) leads
to a decrease in the yield of 3aa presumably due to the
The key feature of the developed process is the non-standard enhancing the role of side oxidation processes. The optimal
regioselectivity of the formation of C–I and C–O bonds, which reaction time was 10 min, a reaction of 5 min resulted in a sig-
implies the radical pathway of the reaction.
nificant decrease in the yield of the desired product (Table 1,
entry 1). Prolongation of the reaction time to 24 h led to a slight
The iodo-oxyimidation of styrenes was studied in the model decrease in the yield of 3aa (Table 1, entry 3) due to its insta-
reaction of styrene (1a) with N-hydroxyphthalimide (2a). bility under the reaction conditions.
During the optimization, the oxidant and the iodine source, as
well as the nature of the solvent and the reaction time were The possibility of using iodide salts (NaI and TBAI) was shown
varied (Table 1).
in Entries 8 and 9, however, the yield of 3aa in that cases is
lower than in the case of molecular iodine.
In general, the iodo-oxyimidation reaction is characterized by
the following: The product 3aa is formed regardless what kind In the optimized reaction conditions (Table 1, entry 2) iodo-
of hypervalent iodine compound is used (Table 1, entries 1-14) oxyimidation of various vinylarenes were performed in order to
and Oxone (Table 1, entries 15 and 16) as the oxidant. The best study the scope of the developed method (Figure 1).
yield of 3aa (90%) was obtained using PhI(OAc)2 (Table 1,
entry 2). Other iodine-based oxidants, such as PhI(OCOCF3)2 The iodo-oxyimidation successfully proceeded using styrenes
(
Table 1, entry 10, yield 31%), IBX (Table 1, entries 11 and 12, having both electron-withdrawing (Cl, F, Br) substituents
yield 32–54%), DMP (Table 1, entries 13–14, yield 52%), in the aromatic ring (products 3ca, 3da, 3fa, 3ha, 3cb–hb,
Scheme 2: Iodo-oxyimidation of styrenes 1a–k with preparation of products 3aa–ka, 3ab–db, 3fb, 3hb, and 3kb.
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Table 1: Optimization of the synthesis of iodo-oxyimidation product 3a from styrene 1a and N-hydroxyimide 2a a.
entry
oxidant (molar ratio: mol/mol of 1a)
solvent
time
yield of 3aab (%)
1
2
3
4
5
6
7
PhI(OAc)2 (0.6)
PhI(OAc)2 (0.6)
PhI(OAc)2 (0.6)
PhI(OAc)2 (1.5)
PhI(OAc)2 (0.6)
PhI(OAc)2 (0.6)
PhI(OAc)2 (0.6)
PhI(OAc)2 (2)
DCM
DCM
5 min
10 min
24 h
63
90
84
73
73
65
84
7
DCM
DCM
10 min
10 min
10 min
10 min
10 min
10 min
10 min
24 h
MeCN
AcOH
PhMe
8c
DCM
9d
PhI(OAc)2 (2)
DCM
52
31
54
32
52
52
44
44
ND
ND
ND
ND
5
10
11
12
13
14
15
16
17
18
19
20
21
22
PhI(OCOCF3)2 (0.6)
IBX (1.0)
DCM
DCM
IBX (0.3)
DCM
24 h
DMP (0.6)
DCM
30 min
30 min
4 h
DMP (0.3)
DCM
Oxone (2)
DCM/H2O (2:1)
DCM/H2O (2:1)
DCM
2-iodobenzoic acid (0.1), Oxone (2)
TBHP (70% aq) (2)
TBHP (70% aq) (2)
TBHP (70% aq) (2)
TBAI (0.1), TBHP (70% aq) (2)
(NH4)2S2O8 (1.5)
DDQ (2)
4 h
12 h
MeCN
12 h
AcOH
12 h
MeCN
12 h
DCM/H2O (2:1)
MeCN
12 h
30 min
5
aReaction conditions: 1a (1 mmol), 2a (1 mmol), I2 (0.5 mmol), oxidant (0.3–2 mmol), solvent (6.0 mL), 20–25 °C, 5 min–24 h, under air. For entries
where a mixture of solvents was used, the v/v ratio is given in parentheses. bIsolated yield. ND = not detected. cNaI·2H2O (1 mmol) was employed
instead of I2. dTBAI (1 mmol) was employed instead of I2.
yield 34–91%), and an electron-donating methyl group (prod- Structures of the iodo-oxyimides 3aa–ka, 3ab–db, 3fb, 3hb
ucts 3ba, 3ea, 3ga, 3bb, yield 39–85%). Good yields (60–79%) and 3kb were confirmed by 1D and 2D NMR spectroscopy,
were achieved with a cyclic analogue of styrene – indene (1k, IR spectroscopy, high-resolution mass spectrometry and
compounds 3ka, 3kb). β-Substituted styrenes (β-methyl styrene elemental analysis. An additional confirmation of the structure
(
1i) and (E)-stilbene (1j) also underwent the studied transfor- of 3ca was made using X-ray crystallographic analysis
mation giving iodo-oxyimides 3ia (yield 51%) and 3ja (yield (Figure 2). Details of the data collection and refinement are pro-
3%). The reaction of NHPI (2a) with p-methoxystyrene under vided in Supporting Information File 1 and can be obtained free
8
standard conditions led to a complex mixture of products, of charge via the web at https://www.ccdc.cam.ac.uk/structures/
possibly due to an increased tendency of the substrate to elec- (CCDC-1845323).
trophilic addition of iodine. The use of allylbenzene in the reac-
Proposed mechanism of the
tion did not result in the formation of the desired iodo-
oxyimide, presumably due to a side process of oxidation of the iodo-oxyimidation
allylic methylene fragment. The use of N-hydroxyphthalimide Based on the literature data describing the formation of the
(
2a) gives iodo-oxymidation products with yields generally phthalimide-N-oxyl radical (PINO) from NHPI under the action
higher (25% on average) than that of N-hydroxysuccinimide of PhI(OAc)2 [34,55,59,76,77], and based on information about
2b). the reaction of the PINO radical with styrenes [45] and interac-
(
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Figure 1: Scope of the iodo-oxyimidation of vinylarenes with I2/PhI(OAc)2 system. Reaction conditions: vinylarene 1a–k (0.5 mmol), N-hydroxyimide
2a,b (0.5 mmol), I2 (0.25 mmol), PhI(OAc)2 (0.3 mmol), DCM (3.0 mL), 20–25 °C, 10 min, under air. rr = regioisomers ratio. aIBX (0.5 mmol) was used
instead of PhI(OAc)2, reaction time: 24 h. bDMP (0.15 mmol) was used instead of PhI(OAc)2, reaction time 30 min.
tion of benzyl radicals with iodine [78,79], a mechanism Electrochemical studies
for the reaction of iodo-oxyimidation of styrenes under the Cyclic voltammetry (CV) experiments on a working glassy-car-
action of the NHPI/I2/PhI(OAc)2 system was proposed bon electrode were carried out for deeper understanding of the
(
Scheme 3).
plausible reaction mechanism. As CH2Cl2 is not suitable as a
solvent due to the poor solubility of NHPI, thus MeCN was
On the first step, NHPI (2a) is oxidized by PhI(OAc)2 to form used. Tetrabutylammonium tetrafluoroborate, which cannot be
PINO radical. The addition of PINO to the double C=C bond of oxidized in such experimental conditions [80], was chosen as a
styrene (1a) leads to the formation of intermediate A. At the supporting electrolyte. Cyclic voltammograms of styrene (1a),
final step the iodine traps benzyl radical A to form the final NHPI (2a), I2 and PhI(OAc)2 in MeCN solution were regis-
product 3aa.
tered (Figure 3).
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The NHPI oxidation peak is observed at +2.18 V, whereas
iodine is oxidized at slightly higher potential (+2.27 V),
and styrene oxidation peak is not so pronounced. Therefore,
we can conclude that under experimental conditions
NHPI is oxidized preferentially over iodine providing PINO
radicals that leads to the observed regioselectivity. The contri-
bution of the oxidation of styrene to the overall process is
unlikely.
Practical application of the iodo-oxyimidation
The applicability of the developed method for the gram-scale
preparation was demonstrated by the synthesis of 3aa (3.1 g,
7
9%) without column chromatography (Scheme 4).
The synthetic utility of the obtained products 3aa and 3ab was
demonstrated by the substitution of the iodine atom with
O- (methanol), S- (benzenesulfinate) and N- (azide) nucleo-
philes (Scheme 5).
Figure 2: Molecular structure of 3ca. Atoms are presented as
anisotropic displacement parameters (ADP) ellipsoids (50% probabili-
ty). For clarity, only one set of positions of the disordered ethylene
bridge and Ph groups is shown.
It is noteworthy that the reaction of compound 3aa with sodi-
um benzenesulfinate results in the nucleophilic substitution of
Scheme 3: The proposed mechanism of iodo-oxyimidation of styrene (1a) using the NHPI/I2/PhI(OAc)2 system with the formation of product 3aa.
Scheme 4: Gram-scale synthesis of compound 3aa.
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Figure 3: CV curves of styrene (1a, purple), NHPI (2a, red), I2 (blue) and PhI(OAc)2 (green) in 0.1 M n-Bu4NBF4/MeCN at a scan rate of 100 mV/s on
a working glassy-carbon electrode.
Scheme 5: Synthetic utility of the iodo-oxyimides 3aa and 3ab.
both the iodine atom and the oxyphthalimide moiety to form a 91%). In contrast to previous studies in which oxidants
vicinal disulfone 4b.
promote the electrophilic addition of iodine to the C=C bond,
radical addition predominates in the discovered process.
Radical pathway starts from the attack of imide-N-oxyl
Conclusion
Iodo-oxyimidation of vinylarenes using N-hydroxyphthalimide radicals on the double C=C bond, which allows for anti-
and N-hydroxysuccinimide was developed. PhI(OAc)2 was the Markovnikov type regioselectivity of C–O and C–I bond
best oxidant for the synthesis of the target products (yields up to formation. Electrochemical mechanistic studies based
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on cyclic voltammetry (CV) data confirm proposed reaction ORCID® iDs
mechanism. Possible ways of using the obtained iodo-oxyimi-
dated products via substitution of iodine atom were demon-
strated.
Igor B. Krylov - https://orcid.org/0000-0001-7138-7319
Stanislav A. Paveliev - https://orcid.org/0000-0003-1668-9693
Yan V. Zubavichus - https://orcid.org/0000-0003-2266-8944
Alexander O. Terent’ev - https://orcid.org/0000-0001-8018-031X
Experimental
General procedure for the synthesis of
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