Metal-Free Catalytic Approach for Allylic C-H Amination Using N-Heterocycles via sp3 C-H Bond Activation

Article abstract of DOI:10.1021/acs.joc.5b01383

A versatile metal-free synthesis of allylic N-heterocycles has been developed using a TBAI/TBHP oxidation system. This general protocol could be applied for the C-N bond formation of electron-deficient phthalimides, imidazoles, triazoles, and sulfonamides

Full text of DOI:10.1021/acs.joc.5b01383

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Brief Communication
A Metal-Free Catalytic Approach for Allylic C-H Amination
Using N-Heterocycles via sp3 C-H Bond Activation
Jinwei Sun, Yi Wang, and Yi Pan
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.5b01383 • Publication Date (Web): 09 Sep 2015
Downloaded from http://pubs.acs.org on September 10, 2015
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A Metal-Free Catalytic Approach for Allylic C-H Amination Using N-
Heterocycles via sp3 C-H Bond Activation
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Jinwei Sun, Yi Wang* and Yi Pan
School of Chemistry & Chemical Engineering, Nanjing University, Nanjing, 210093, China.
ABSTRACT: A versatile metal–free synthesis of allylic N-heterocycles has been developed using TBAI/TBHP oxidation
system. This general protocol could be applied for the C-N bond formation of electron-deficient phthalimides, imidazoles,
triazoles and sulfonamides with cyclic and acylic olefins. The practical use of the method is demonstrated by the ami-
dation of functionalized biologically active substrates.
C(sp3)-H bond activation of allylic hydrogen has demonstrated promise for the construction of highly functionalized ole-
fins. Much attention has been drawn in recent years on selective allylic C−H transformations including oxygenation,1-5
alkylation,6-9 and esterification.10-12
The allylic amines are presented in a wide variety of pharmaceuticals and bioactive products.13 Efficient approaches em-
ploying prefunctionalized allylic coupling partners have been developed for the introduction of C-N bond into organic
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molecules and biological systems.14 In contrast, direct oxidative coupling of C-H bond and N-H bond has shown
advantages over the condensation of amines and carboxylic acid derivatives in terms of atom economy. Recent
developments on direct amination of allylic sp3 C-H using transition metal catalysts have provided great tools for homolyt-
ic allylic C−H bond abstraction.15-23 Metal-free oxidation methods were also been established for the amination of ethers,
ketones and arenes through radical pathways.24-29
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Although significant advances have been achieved in this field, more efficient and versatile strategies for allylic C(sp3)–H
bond functionalization are still in demand. Up to date, only a few examples of metal-free direct allyic amination have
been reported.30,31 The selective addition of electron-deficient N-heterocycles to olefins has scarcely been studied.
Along with our interest in selective sp3 C−H bond functionalization32 and inspired by Beller’s palladium-catalyzed
hydroamidation of 1,3-dienes33,34 (scheme 1a), we hypothesized that a radical initiated allylic amination process would
benefit from the simple conditions and high regioselectivity of the stabilized allyl radicals (scheme 1b). After investigating
a range of N-heterocyclic amides and azoles for cross dehydrogenative coupling (CDC) reactions35-42 with linear and cyclic
olefins using a well-established TBAI/TBHP oxidation system,43-48 we herein report a general metal-free amination protocol
for the atom-efficient construction of a broad range of N-allylic heterocycles.
Scheme 1 Regioselective synthesis of allylic amides using different catalytic systems
In initial reaction development, we tested several peroxides and catalysts with cyclohexene 1a and nitro-phthalimide 2a.
We first used DTBP as oxidant and catalytic amount of Cu(OAc)2 in benzene at 80 °C for 12 h, trace amount of coupling
product was obtained (entry 1). CuI and Fe(acac)3 (0.1 eq) were ineffective (entry 2, 3). When using Pd(OAc)2, the desired
product was furnished in moderate yield (entry 4, 65%).
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Table 1 Optimization of the reaction conditions
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Solvent
Entry
1
Oxidant
Catalyst
Cu(OAc)2 (0.1 eq)
CuI (0.1 eq)
Yield(%)
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DTBP (2 eq)
DTBP (2 eq)
DTBP (2 eq)
DTBP (2 eq)
TBHP (2 eq)
TBHP (2 eq)
TBHP (2 eq)
TBHP (2 eq)
TBHP (2 eq)
TBHP (2 eq)
TBHP (2 eq)
TBHP (2 eq)
TBHP (2 eq)
TBHP (3 eq)
TBHP (2 eq)
TBHP (2 eq)
TBHP (2 eq)
TBHP (2 eq)
TBHP (2 eq)
TBHP (2 eq)
Benzene
Benzene
Benzene
Benzene
Benzene
Benzene
Benzene
Benzene
Benzene
Benzene
Benzene
Benzene
Benzene
Benzene
Benzene
DMSO
Trace
0
2
3
Fe(acac)3 (0.1 eq)
Pd(OAc)2 (0.1 eq)
-
0
4
65
0
5
6
CuBr (0.1 eq)
CuI (0.1 eq)
Trace
12
7
8
Cu(acac)2 (0.1 eq)
Fe(acac)3 (0.1 eq)
KI (0.1 eq)
15
9
0
10
11
Trace
62
78
83
81
Pd(OAc)2 (0.1 eq)
TBAI (0.1 eq)
TBAI (0.2 eq)
TBAI (0.2 eq)
TBAI (0.3 eq)
TBAI (0.2 eq)
TBAI (0.2 eq)
TBAI (0.2 eq)
TBAI (0.2 eq)
TBAI (0.2 eq)
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82
13
DMF
28
56
68
32
Toluene
EtOAc
MeCN
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Switching the oxidant to TBHP, no product was detected in the absence of catalyst (entry 5). Low conversions were
observed with copper, iron and potassium catalysts (entries 6-10). Palladium acetate provided similar moderate yield
(62%, entry 11). To our delight, tetrabutylammonium iodide (TBAI) could promote the reaction to form the target
coupling product with high regioselectivity and good yield (entry 12). Altering the loading of catalyst and oxidant
provided similar results (entries 13-15). The reaction did occur when carried out in other solvents, but much lower
conversions were observed (entries 16 -20).
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Scheme 2 Amidation of allylic alkanes with phthalimides
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With the optimized conditions (Table 1, entry 13), we investigated other phthalimides for this oxidative amination of
olefins. Substrates with electron-withdrawing group went through cross dehydrogenative coupling process with linear
and cyclic olefins (Scheme 2). The yields decreased slightly with larger cyclic rings (5a-5d). Bromo-substituted
phthalimides provided higher yields than the unsubstituted substrates (5k and 5l).
Scheme 3 Amidation of various allylic olefins with imidazoles and triazoles
Next, we tried to extend the scope of this methodology to similar amides and azoles. As we expected, this direct allylic
amination protocol could be applied to N-heteroarene systems such as benzotriazoles and benzimidazoles (Scheme 3).
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Cyclopentene, cyclohexene, cyclooctene and tetramethylethylene could all react with benzimidazoles to afford the allylic
amination compounds 6a-6f in high yields. 2-chlorobenzotriazole also reacted smoothly to furnish the amination
products 6g-6i in 82%-86% yields. Notably, benzylic hydrogen in tetrahydronaphthalene could also tolerate these
conditions to furnish 6j in 78% yield.
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Scheme 4 Amidation of various allylic alkanes and esters with saccharin
To further explore the generality of this protocol, we also tested the pharmacologically useful sulfonamide derivatives49,50
.
A variety of olefins with allylic sp3 hydrogens were activated by the TBAI-TBHP oxidation system (Scheme 4). The
reactions of indene and tetramethylethylene with saccharin resulted in the formation of 7a and 7b in 72% and 68% yield,
respectively. Also, the reactions with methyl and ethyl crotonate furnished the corresponding products in similar yields
(7c, 66% and 7d, 64%). Interestingly, naturally insufficient β-pinene could tolerate the peroxide to form its saccharin
derivative without commonly occurred oxidative polymerization (7e, 62%).
Scheme 5 Amidation of tetramethylethylene with uracil derivatives
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Finally, we chose one of the nucleobases uracil as an example of functionalized biologically important amide substrate to
demonstrate the utility of our procedure. Undeniably, the reaction of tetramethylethylene with fluorinated uracil 8a
provided di-substituted product 8b in 40% yield. In a similar manner, partially protected chloro-uracil derivative 8c was
converted into the mono-N-allylic product 8d in 35% yield (Scheme 5).
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Scheme 6 Radical trapping control experiment
According to previous reports,46-48 it is believed that the active hypoiodite [n-Bu4N]+[IO] or iodite [n-Bu4N]+[IO2] species
is the crucial intermediate in sp3 C–H amination reactions. To investigate the mechanism of this reaction, a control
experiment was carried out by using nitro-phthalimide and cyclohexene with the radical-trapping reagent 2,2,6,6-
tetramethyl-1-piperidinyloxy (TEMPO) (Scheme 6). As expected, the formation of the desired product 5b was suppressed.
Only the TEMPO–cyclohexane adduct 5b’ was obtained (determined by LC-MS analysis). This control experiment
suggests that the coupling reaction might go through a radical pathway. Therefore, a plausible mechanism is proposed
based on the results (Scheme 7). First n-Bu4NI was oxidized by TBHP to form the active hypoiodite 9a or iodite 9b
species. Then the homolysis of allylic C–H bond with 9 gives the allylic radical 10, which is oxidized by active iodine
species to give the allylic cation 11. At last, the nucleophilic attack of amine 2 to the allylic cation 11 furnishes the desired
product 5. The regiochemistry obtained with tetraethylethylene (5j, 6f, 6i, 7b, 8b and 8d) which is not consistent with the
proposed cationic mechanism, maybe due to the fact that the rearranged carbon cation is sterically hindered and
therefore not favored for the amination.
Scheme 7 Possible mechanism for metal-free synthesis of N-allyl heterocycles
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CONCLUSIONS
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In summary, we have demonstrated a general protocol for the CDC coupling of functionalized electron-poor N-
heterocycles with cyclic and acyclic olefins via sp3 C-H bond activation. This metal-free amination pathway presents a
direct access to a variety of allyl-substituted heterocycles as useful synthetic intermediates and important bioactive agents.
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EXPERIMENTAL SECTION
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General Considerations. Commercially available reagents were used as received without purification. TBHP (5.5
M in decane) was purchased from Sigma–Aldrich. Column chromatography was carried out on silica gel (300–400
mesh). Analytical thin–layer chromatography was performed on glass plates of Silica Gel GF–254 with detection by
UV. 1H, 13C and 19F NMR spectra were recorded on a 400M spectrometer. The chemical shift references were as fol-
1
13
lows: H NMR (CDCl3) 7.26 ppm. C NMR (CDCl3) 77.16 ppm. HRMS spectra were carried out on TOF MS EI+ and
ESI. Melting point determination was taken on a Melt–Temp apparatus (X-4) and was uncorrected.
General procedure. To a Schlenk tube equipped with a magnetic stir bar were added TBAI (37 mg, 0.1 mmol) and
heterocyclic sbustrate (2, 3 or 4, 0.5 mmol) with olefin 1 (1 mmol) in 2 mL of benzene. Then TBHP (5.5 M in decane,
1 mmol, 0.2 mL) was added before the vial was sealed and the reaction mixture was stirred at the 80 °C for 12 h. After
required reaction time, the mixture was cooled down to room temperature, diluted in ethyl acetate, and washed
with brine. The aqueous phase was extracted with ethyl acetate. The combined organic layers were dried over
Na2SO4 and concentrated in vacuo, and the resulting residue was purified by silica gel column chromatography
(hexane/ethyl acetate) to afford the product.
2-(cyclopent-2-enyl)-5-nitroisoindoline-1,3-dione (5a): Light yellow solid. Melting point: 77-78 °C. Yield: 107
mg (83%).1H NMR (400 MHz, CDCl3) δ 8.61 (d,
6.13 (dq, = 4.5, 2.3 Hz, 1H), 5.62 (dq, = 4.5, 2.2 Hz, 1H), 5.41 (dtd,
J = 8.1 Hz, 1H), 8.57 (dd, J = 8.1, 2.0 Hz, 1H), 8.00 (d, J = 8.1 Hz, 1H),
J
J
J
= 7.2, 4.9, 2.7 Hz, 1H), 2.82 (dddd, J = 14.0, 9.4,
13
4.7, 2.7 Hz, 1H), 2.51 – 2.42 (m, 1H), 2.37 (dtd, J = 13.9, 9.2, 4.5 Hz, 1H), 2.10 (ddt, J = 14.0, 9.5, 4.7 Hz, 1H). C NMR
(100 MHz, CDCl3) δ 166.1, 165.8, 151.8, 136.7, 136.6, 133.6, 129.2, 127.3, 124.4, 118.6, 57.0, 32.4, 28.2. HRMS (TOF MS EI+)
m/z calcd for [C13H10N2O4] 258.0641, found 258.0635.
2-(cyclohex-2-enyl)-5-nitroisoindoline-1,3-dione (5b): Pale yellow solid. Melting point: 86-87 °C. Yield: 105 mg
(78%).1H NMR (400 MHz, CDCl3) δ 8.63 (d,
5.92 (m, 1H), 5.54 (d, = 10.1 Hz, 1H), 4.98 – 4.88 (m, 1H), 2.24 – 2.06 (m, 3H), 1.99 – 1.88 (m, 2H), 1.79 –1.66 (m, 1H).
J = 1.9 Hz, 1H), 8.58 (dd, J = 8.1, 2.0 Hz, 1H), 8.01 (d, J = 8.1 Hz, 1H), 6.02 –
J
13C NMR (100 MHz, CDCl3) δ 166.1, 165.8, 151.9, 136.6, 133.6, 131.0, 129.3, 125.7, 124.4, 118.7, 48.5, 27.2, 24.4, 21.8. HRMS
(TOF MS EI+) m/z calcd for [C14H12N2O4] 272.0797, found 272.0804.
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2-(cyclohept-2-enyl)-5-nitroisoindoline-1,3-dione (5c): White solid. Melting point: 108-109 °C. Yield: 105 mg
(74%). 1H NMR (400 MHz, CDCl3) δ 8.65 (d,
= 1.9 Hz, 1H), 8.59 (dd, J = 8.1, 2.0 Hz, 1H), 8.03 (d, J = 8.1 Hz, 1H), 6.01
1
2
3
J
4
– 5.83 (m, 1H), 5.71 (dt,
J
= 11.4, 2.5 Hz, 1H), 5.02 (d,
J = 11.7 Hz, 1H), 2.41 – 2.25 (m, 2H), 2.23 – 2.11 (m, 1H), 2.10 – 2.02
5
6
(m, 1H), 1.86 – 1.76 (m, 1H), 1.69 (dddd,
J
= 14.1, 12.6, 8.4, 3.1 Hz, 2H), 1.51 – 1.38 (m, 1H). 13C NMR (100 MHz, CDCl3) δ
7
8
9
165.9, 165.6, 151.9, 136.6, 133.6, 132.4, 132., 129.3, 124.5, 118.8, 52.6, 33.0, 29.1, 28.7, 26.3. HRMS (TOF MS EI+) m/z calcd for
[C15H14N2O4] 286.0954, found 286.0957.
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5-nitro-2-(1,2,3,4-tetrahydronaphthalen-1-yl)isoindoline-1,3-dione (5d): Pale yellow solid. Melting point: 130-
131 °C. Yield: 113 mg (70%). 1H NMR (400 MHz, CDCl3) δ 8.66 – 8.57 (m, 2H), 8.03 (d,
J = 8.1 Hz, 1H), 7.16 (d, J = 4.1 Hz,
2H), 7.06 (dt,
1H), 2.85 (d,
J
= 8.4, 4.2 Hz, 1H), 6.90 (d,
J
= 7.7 Hz, 1H), 5.59 (dd,
J = 10.4, 5.8 Hz, 1H), 3.03 (ddd, J = 16.3, 11.5, 4.5 Hz,
J
= 16.6 Hz, 1H), 2.39 (ddd,
J
= 10.6, 9.8, 8.3 Hz, 1H), 2.17 – 2.10 (m, 2H), 1.93 – 1.78 (m, 1H). 13C NMR (100
MHz, CDCl3) δ 166.1, 165.8, 151.9, 138.1, 136.5, 133.9, 133.5, 129.5, 129.4, 127.4, 126.3, 125.8, 124.6, 118.8, 50.2, 29.4, 28.1, 22.3.
HRMS (TOF MS EI+) m/z calcd for [C18H14N2O4] 322.0954, found 322.0958.
2-(cyclopent-2-enyl)isoindoline-1,3-dione (5e): White solid. Melting point: 73-74 °C. Yield: 69 mg (66%).
1H NMR (400 MHz, CDCl3) δ 7.80 (dd,
5.62 (dq, = 4.5, 2.2 Hz, 1H), 5.41–5.35 (m, 1H), 2.80 (dddd,
2.2 Hz, 1H), 2.33 (dtd, = 13.7, 9.2, 4.5 Hz, 1H), 2.10 (ddd,
J = 5.4, 3.1 Hz, 2H), 7.68 (dd, J = 5.5, 3.0 Hz, 2H), 6.08 (dq, J = 4.5, 2.3 Hz, 1H),
J
J
= 16.4, 9.4, 4.7, 2.6 Hz, 1H), 2.44 (dddd,
J = 16.2, 9.0, 4.7,
J
J
= 18.5, 9.5, 4.9 Hz, 1H). 13C NMR (100 MHz, CDCl3) δ 168.3,
135.7, 133.9, 132.3, 128.1, 123.2, 56.2, 32.4, 28.3. HRMS (TOF MS EI+) m/z calcd for [C13H11NO2] 213.0790, found 213.0794.
2-(cyclohex-2-enyl)isoindoline-1,3-dione (5f): White solid. Melting point: 101-102 °C. Yield: 72 mg (63%).1H
NMR (400 MHz, CDCl3) δ 7.82 (dd, J = 5.5, 3.0 Hz, 2H), 7.70 (dd, J = 5.4, 3.1 Hz, 2H), 6.03 – 5.75 (m, 1H), 5.55 (d, J =
10.1 Hz, 1H), 5.03 – 4.62 (m, 1H), 2.24 – 2.02 (m, 3H), 1.99 – 1.82 (m, 2H), 1.80 – 1.66 (m, 1H). 13C NMR (100 MHz, CDCl3)
δ 168.3, 134.0, 132.2, 130.2, 126.7, 123.2, 47.6, 27.3, 24.4, 21.9. HRMS (TOF MS EI+) m/z calcd for [C14H13NO2] 227.0946,
found 227.0940.
2-(2,3-dihydro-1H-inden-1-yl)isoindoline-1,3-dione (5g): White solid. Melting point: 126-127 °C. Yield: 77 mg
(58%). 1H NMR (400 MHz, CDCl3) δ 7.82 (dd,
J = 5.4, 3.0 Hz, 2H), 7.71 (dd, J = 5.4, 3.1 Hz, 2H), 7.30 (d, J = 7.3 Hz, 1H),
7.23 (d,
(qdd,
J
= 7.5 Hz, 1H), 7.18 – 7.04 (m, 2H), 5.89 (dd,
J = 8.7, 6.8 Hz, 1H), 3.51 – 3.21 (m, 1H), 3.07 – 2.93 (m, 1H), 2.52
J
= 9.0, 7.7, 3.6 Hz, 2H). 13C NMR (100 MHz, CDCl3) δ 168.1, 144.0, 140.6, 134.1, 132.2, 128.2, 126.7, 125.0, 123.5, 123.3,
54.9, 31.3, 29.9. HRMS (TOF MS EI+) m/z calcd for [C17H13NO2] 263.0946, found 263.0940.
2-(cyclopent-2-enyl)-4-nitroisoindoline-1,3-dione (5h): Light yellow solid. Melting point: 127-128 °C. Yield: 109
mg (85%). 1H NMR (400 MHz, CDCl3) δ 8.62 – 8.59 (m, 1H), 8.57 (dd,
J
= 8.1, 2.0 Hz, 1H), 8.00 (d,
J
= 8.1 Hz, 1H), 6.13
= 14.0, 9.4, 4.7,
(dq, J = 4.5, 2.3 Hz, 1H), 5.62 (dq, J = 4.5, 2.2 Hz, 1H), 5.41 (dtd, J = 7.2, 4.9, 2.7 Hz, 1H), 2.82 (dddd, J
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= 13.9, 9.2, 4.5 Hz, 1H), 2.10 (ddt, J
= 14.0, 9.5, 4.7 Hz, 1H). 13C NMR (100
2.7 Hz, 1H), 2.51 – 2.42 (m, 1H), 2.37 (dtd,
J
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3
4
MHz, CDCl3) δ 165.7, 162.8, 145.2, 136.6, 135.3, 134.3, 128.4, 127.1, 126.9, 123.8, 57.0, 32.4, 28.0. HRMS (ESI): Calcd. for
C13H10N2NaO4 (M+Na)+ 281.0538, found 281.0531.
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2-(cyclohex-2-enyl)-4-nitroisoindoline-1,3-dione (5i): Pale white solid. Melting point: 105-107 °C. Yield: 114 mg
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8
(84%). 1H NMR (400 MHz, CDCl3) δ 8.07 (dd,
J = 7.7, 5.1 Hz, 2H), 7.89 (t, J = 7.8 Hz, 1H), 6.01 – 5.88 (m, 1H), 5.52 (d, J
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= 10.1 Hz, 1H), 5.00 – 4.84 (m, 1H), 2.25 – 2.01 (m, 3H), 1.99 – 1.85 (m, 2H), 1.78 – 1.64 (m, 1H). 13C NMR (100 MHz,
CDCl3) δ 165.7, 162.8, 145.2, 135.3, 134.2, 130.9, 128.5, 126.9, 125.7, 123.7, 48.45, 27.1, 24.3, 21.8. HRMS (ESI): Calcd. for
C14H12N2NaO4 (M+Na)+ 295.0695, found 295.0687.
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2-(2,3-dimethylbut-2-enyl)-4-nitroisoindoline-1,3-dione (5j): Light yellow solid. Melting point: 110-111 °C. Yield:
98 mg (72%). 1H NMR (400 MHz, CDCl3) δ 8.13 – 8.03 (m, 2H), 7.90 (dd,
J = 8.0, 7.5 Hz, 1H), 4.34 (s, 2H), 1.90 (s, 3H),
1.67 (s, 3H), 1.60 (s, 3H). 13C NMR (100MHz, CDCl3) δ 166.1, 163.2, 145.2, 135.3, 134.3, 131.2, 128.5, 127.0, 123.9, 121.5, 41.6, 21.2,
20.6, 16.5. HRMS (TOF MS EI+) m/z calcd for [C14H14N2O4] 274.0954, found 274.0958.
5-bromo-2-(cyclopent-2-enyl)isoindoline-1,3-dione (5k): White solid. Melting point: 123-125 °C. Yield: 98 mg
(68%). 1H NMR (400 MHz, CDCl3) δ 7.91 (d,
(dq, = 4.5, 2.3 Hz, 1H), 5.60 (dq,
(dtd,
J = 1.4 Hz, 1H), 7.81 (dd, J = 7.9, 1.6 Hz, 1H), 7.66 (d, J = 7.9 Hz, 1H), 6.08
J
J
= 4.4, 2.2 Hz, 1H), 5.39 – 5.28 (m, 1H), 2.84 – 2.73 (m, 1H), 2.48 – 2.38 (m, 1H), 2.32
J
= 13.8, 9.2, 4.5 Hz, 1H), 2.07 (ddd, J
= 18.6, 9.5, 4.8 Hz, 1H). 13C NMR (100 MHz, CDCl3) δ 167.4, 166.8, 136.9, 135.9,
133.9, 130.8, 128.8, 127.7, 126.5, 124.5, 56.4, 32.3, 28.2. HRMS (TOF MS EI+) m/z calcd for [C13H10BrNO2] 290.9895, found
290.9888.
5-bromo-2-(cyclohex-2-enyl)isoindoline-1,3-dione (5l): White solid. Melting point: 123-125 °C. Yield: 107 mg
(70%). 1H NMR (400 MHz, CDCl3) δ 7.94 (d,
J = 1.6 Hz, 1H), 7.83 (dd, J = 7.9, 1.6 Hz, 1H), 7.68 (d, J = 7.9 Hz, 1H), 5.97
– 5.90 (m, 1H), 5.53 (d, J = 10.1 Hz, 1H), 4.92 – 4.83 (m, 1H), 2.23 – 2.03 (m, 3H), 1.98 – 1.85 (m, 2H), 1.78 – 1.67 (m, 1H).
13C NMR (100 MHz, CDCl3) δ 167.5, 166.9, 137.0, 133.9, 130.8, 130.5, 128.9, 126.6, 126.3, 124.6, 47.9, 27.2, 24.4, 21.9. HRMS
(TOF MS EI+) m/z calcd for [C14H12BrNO2] 305.0051, found 305.0057.
1-(cyclopent-2-enyl)-1H-benzo[d][1,2,3]triazole (6a): Yellow oil. Yield: 69 mg (76%). 1H NMR (400 MHz, CDCl3)
δ 8.03 (d,
J
= 8.3 Hz, 1H), 7.50 (d,
J
= 8.3 Hz, 1H), 7.40 (t,
J = 7.5 Hz, 1H), 7.32 (t, J = 7.6 Hz, 1H), 6.27 (td, J = 4.4, 2.2 Hz,
1H), 6.12 (ddd,
J
= 8.6, 5.1, 2.4 Hz, 1H), 5.95 (td,
J
= 4.3, 2.1 Hz, 1H), 2.86 – 2.74 (m, 1H), 2.73 – 2.55 (m, 2H), 2.19 (tt, J =
6.8, 4.2 Hz, 1H). 13C NMR (100 MHz, CDCl3) δ 146.8, 137.1, 132.0, 128.5, 126.9, 123.8, 120.1, 110.3, 65.9, 32.1, 30.2. HRMS (ESI):
Calcd. for C11H11N3Na (M+Na)+ 208.0851, found 208.0838.
1-(cyclohex-2-enyl)-1H-benzo[d][1,2,3]triazole (6b): Yellow oil. Yield: 72 mg (73%). 1H NMR (400 MHz, CDCl3)
δ 8.04 (dd, J = 8.3, 0.9 Hz, 1H), 7.61 – 7.58 (m, 1H), 7.41 (ddd, J = 8.3, 6.9, 1.0 Hz, 1H), 7.33 (ddd, J = 8.0, 6.9, 1.0 Hz, 1H),
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6.21 – 6.11 (m, 1H), 5.87 (ddd,
J = 7.4, 2.2, 1.3 Hz, 1H), 5.64 – 5.56 (m, 1H), 2.34 – 2.20 (m, 3H), 2.17 – 2.07 (m, 1H), 1.99 –
1
1.88 (m, 1H), 1.87 – 1.75 (m, 1H). 13C NMR (100 MHz, CDCl3) δ 146.6, 132.9, 132.2, 126.9, 125.1, 123.8, 120.1, 110.6, 56.3, 29.8,
24.7, 20.6. HRMS (ESI): Calcd. for C12H13N3Na (M+Na)+ 222.1007, found 222.0990.
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(Z)-1-(cyclooct-2-enyl)-1H-benzo[d][1,2,3]triazole (6c): Yellow oil. Yield: 75 mg (66%). H NMR (400 MHz,
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8
CDCl3) δ 8.07 (d, J = 8.3 Hz, 1H), 7.56 (d, J = 8.3 Hz, 1H), 7.48 – 7.43 (m, 1H), 7.39 – 7.32 (m, 1H), 5.98 – 5.85 (m, 2H),
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5.78 (ddd,
J = 11.7, 7.1, 4.3 Hz, 1H), 2.44 (ddd, J = 17.1, 11.5, 4.6 Hz, 2H), 2.36 – 2.16 (m, 2H), 1.89 – 1.73 (m, 4H), 1.62 (dt,
J
= 11.9, 8.6 Hz, 1H), 1.57 – 1.45 (m, 1H). 13C NMR (100 MHz, CDCl3) δ 146.4, 132.5, 131.8, 128.9, 127.0, 124.0, 120.2, 110.1, 57.9,
35.7, 29.1, 26.6, 26.2, 24.6. HRMS (ESI): Calcd. for C14H17N3Na (M+Na)+ 250.1320, found 250.1308.
1-(cyclopent-2-enyl)-5,6-dimethyl-1H-benzo[d][1,2,3] triazole (6d): Light yellow solid. Melting point: 56-57 °C.
Yield: 78 mg (75%). 1H NMR (400 MHz, CDCl3) δ 7.75 (s, 1H), 7.23 (s, 1H), 6.25 (dd,
J = 5.6, 2.2 Hz, 1H), 6.05 (ddd, J =
8.4, 5.0, 2.4 Hz, 1H), 5.96 – 5.90 (m, 1H), 2.83 – 2.74 (m, 1H), 2.69 – 2.55 (m, 2H), 2.38 (s, 3H), 2.36 (s, 3H), 2.22 – 2.12
(m, 1H). 13C NMR (100 MHz, CDCl3) δ 146.0, 137.1, 136.8, 133.5, 131.1, 128.7, 119.1, 109.7, 65.7, 32., 30.2, 21.0, 20.5. HRMS (ESI):
Calcd. for C13H15N3Na (M+Na)+ 236.1164, found 236.1162.
1-(cyclohex-2-enyl)-5,6-dimethyl-1H-benzo[d][1,2,3] triazole (6e): Light yellow solid. Melting point: 69-70 °C.
Yield: 80 mg (70%). 1H NMR (400 MHz, CDCl3) δ 7.75 (s, 1H), 7.31 (s, 1H), 6.30 – 6.04 (m, 1H), 5.84 (d,
J = 10.1 Hz, 1H),
5.51 (td,
J = 5.7, 2.8 Hz, 1H), 2.38 (s, 3H), 2.36 (s, 3H), 2.23 (ddd, J = 19.7, 11.5, 3.0 Hz, 3H), 2.14 – 2.03 (m, 1H), 1.92 (dd,
J
= 9.9, 3.7 Hz, 1H), 1.84 – 1.72 (m, 1H). 13C NMR (100 MHz, CDCl3) δ 145.8, 137.1, 133.5, 132.5, 131.2, 125.3, 119.1, 109.9, 56.0,
29.6, 24.7, 21.0, 20.6, 20.4. HRMS (ESI): Calcd. for C14H17N3Na (M+Na)+ 250.1320, found 250.1317.
1-(2,3-dimethylbut-2-enyl)-5,6-dimethyl-1H-benzo[d] [1,2,3]triazole (6f): Light yellow solid. Melting point:
108-109 °C. Yield: 89 mg (78%).1H NMR (400 MHz, CDCl3) δ 7.72 (s, 1H), 7.12 (s, 1H), 5.17 (s, 2H), 2.36 (s, 3H), 2.34 (s,
3H), 1.98 (s, 3H), 1.72 (s, 3H), 1.45 (s, 3H).13C NMR (100 MHz, CDCl3) δ 145.4, 137.3, 133.4, 132.0, 130.8, 122.0, 118.9, 109.1,
50.9, 21.0, 20.6, 20.4, 16.0. HRMS (ESI): Calcd. for C14H19N3Na (M+Na)+ 252.1477, found 252.1472.
1
2-chloro-1-(cyclopent-2-enyl)-1H-benzo[d] imidazole (6g): Colorless oil. Yield: 93 mg (86%). H NMR (400
MHz, CDCl3) δ 7.66 (d,
J
= 8.0 Hz, 1H), 7.35 (d,
J
= 7.8 Hz, 1H), 7.25 – 7.11 (m, 2H), 6.19 (dt,
J = 7.7, 2.1 Hz, 1H), 5.83
(ddd, J = 5.7, 4.0, 1.9 Hz, 1H), 5.78 (ddd,
J
= 10.5, 5.4, 2.9 Hz, 1H), 2.76 (ddt, J
= 13.8, 11.3, 4.6 Hz, 1H), 2.63 – 2.49 (m,
2H), 2.13 – 1.98 (m, 1H). 13C NMR (100 MHz, CDCl3) δ 142.2, 140.4, 136.0, 133.9, 128.9, 122.6, 122.4, 119.5, 111.2, 62.8, 32.0, 29.0.
HRMS (ESI): Calcd. for C12H12ClN2 (M+H)+ 219.0689, found 219.0681.
1
2-chloro-1-(cyclohex-2-enyl)-1H-benzo[d]imidazole (6h): Colorless oil. Yield: 99 mg (85%). H NMR (400
MHz, CDCl3) δ 7.70 – 7.62 (m, 1H), 7.50 (dd,
J
= 7.1, 1.5 Hz, 1H), 7.26 – 7.16 (m, 2H), 6.17 – 6.02 (m, 1H), 5.77 (dd,
J =
10.1, 2.1 Hz, 1H), 5.31 – 5.19 (m, 1H), 2.30 – 2.18 (m, 2H), 2.08 (td,
J
= 9.1, 3.5 Hz, 2H), 2.03–1.92 (m, 1H), 1.89–1.74 (m,
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1H). 13C NMR (100 MHz, CDCl3) δ 142.2, 140.4, 134.1, 132.2, 126.3, 122.7, 122.4, 119.5, 111.8, 53.9, 28.6, 24.5, 21.5. HRMS (ESI):
Calcd. for C13H14ClN2 (M+H)+ 233.0846, found 233.0841.
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2-chloro-1-(2,3-dimethylbut-2-enyl)-1H-benzo [d]imidazole (6i): Colorless oil. Yield: 95 mg (82%). H NMR
5
6
(400 MHz, CDCl3) δ 7.70 – 7.64 (m, 1H), 7.26 – 7.20 (m, 3H), 4.83 (s, 2H), 1.97 (s, 3H), 1.74 (s, 3H), 1.39 (s, 3H). 13
C
7
8
9
NMR (100 MHz, CDCl3) δ 141.8, 141.2, 135.4, 130.0, 123.1, 122.7, 121.8, 119.5, 110.0, 47.2, 21.2, 20.6, 15.2. HRMS (ESI): Calcd. for
C13H16ClN2 (M+H)+ 235.1002, found 235.0997.
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2-chloro-1-(1,2,3,4-tetrahydronaphthalen-1-yl)-1H-benzo[d]imidazole (6j): Yellow oil. Yield: 108 mg (78%).
1H NMR (400 MHz, CDCl3) δ 7.70 (d,
7.8 Hz, 1H), 6.63 (d, = 7.2 Hz, 1H), 5.96 – 5.85 (m, 1H), 3.12 – 2.89 (m, 2H), 2.35 – 2.22 (m, 2H), 2.19 – 2.08 (m, 1H),
J = 8.1 Hz, 1H), 7.20 (dt, J = 20.9, 7.4 Hz, 3H), 7.07 – 6.95 (m, 2H), 6.76 (d, J =
J
2.03 – 1.89 (m, 1H). 13C NMR (100 MHz, CDCl3) δ 142.2, 141.0, 137.6, 133.6, 133.1, 129.4, 127.9, 127.4, 126.7, 122.8, 122.4, 119.5,
111.8, 56.0, 29.6, 29.4, 22.0. HRMS (ESI): Calcd. for C17H16ClN2 (M+H)+ 283.1002, found 283.0998.
(R)-2-(2,3-dihydro-1H-inden-1-yl)benzo[d] isothiazol-3(2H)-one 1,1-dioxide (7a): White solid. Melting point:
1
112-113 °C. Yield: 107 mg (72%). H NMR (400 MHz, CDCl3) δ 7.94 (dd,
J
= 7.0, 1.0 Hz, 1H), 7.86 (dd,
J
= 6.9, 0.8 Hz,
1H), 7.79 (td, J = 7.5, 1.3 Hz, 1H), 7.74 (td, J = 7.4, 1.3 Hz, 1H), 7.36 (d, J = 7.6 Hz, 1H), 7.30 – 7.14 (m, 3H), 5.72 (t, J = 7.3
= 13.4, 6.9, 0.9 Hz, 2H). 13C NMR (100 MHz, CDCl3) δ 158.4,
Hz, 1H), 3.42 – 3.30 (m, 1H), 3.05 – 2.93 (m, 1H), 2.62 (ddd,
J
144.2, 138.3, 137.7, 134.7, 134.3, 128.7, 127.3, 126.7, 125.0, 124.9, 124.7, 120.8, 57.3, 31.1, 29.8. HRMS (ESI): Calcd. for
C16H13NNaO3S (M+Na)+ 322.0514, found 322.0509.
2-(2,3-dimethylbut-2-en-1-yl) benzo [d] isothiazol-3 (2H)-one 1,1-dioxide (7b): White solid. Melting point:
110-111 °C. Yield: 89 mg (68%). 1H NMR (400 MHz, CDCl3) δ 8.06 – 8.00 (m, 1H), 7.92 – 7.77 (m, 3H), 4.43 (s, 2H), 1.90
(s, 3H), 1.72 (s, 6H). 13C NMR (100 MHz, CDCl3) δ 159.3, 138.0, 134.7, 134.3, 132.1, 127.5, 125.2, 120.9, 120.8, 42.2, 21.3, 20.5,
16.4. HRMS (TOF MS EI+) m/z calcd for [C13H15NO3S] 265.0773, found 265.0779.
(E)-methyl 4-(1,1-dioxido-3-oxobenzo [d] isothiazol-2 (3H)-yl) but-2-enoate (7c): Colorless oil. Yield: 91 mg
(66%). 1H NMR (400 MHz, CDCl3) δ 8.13 – 8.02 (m, 1H), 7.98 – 7.80 (m, 3H), 6.97 (dt,
J = 15.7, 5.5 Hz, 1H), 6.12 (dt, J =
15.7, 1.7 Hz, 1H), 4.50 (dd,
J
= 5.5, 1.7 Hz, 2H), 3.73 (s, 3H). 13C NMR (100 MHz, CDCl3) δ 166.0, 158.7, 139.8, 137.8, 135.2,
134.7, 127.2, 125.5, 124.4, 121.3, 51.9, 39.2. HRMS (TOF MS EI+) m/z calcd for [C12H11NO5S] 281.0358, found 281.0363.
(E)-ethyl 4-(1,1-dioxido-3-oxobenzo [d] isothiazol-2(3H)-yl) but-2-enoate (7d): Colorless oil. Yield: 95 mg
(64%). 1H NMR (400 MHz, CDCl3) δ 8.11 – 8.04 (m, 1H), 7.97 – 7.82 (m, 3H), 6.96 (dt,
= 7.1 Hz, 3H). 13C NMR (100 MHz, CDCl3)
J = 15.6, 5.4 Hz, 1H), 6.10 (dt, J =
15.6, 1.7 Hz, 1H), 4.50 (dd, J = 5.4, 1.7 Hz, 2H), 4.18 (q, J = 7.1 Hz, 2H), 1.26 (t, J
δ 165.5, 158.7, 139.4, 137.8, 135.2, 134.7, 127.2, 125.5, 124.7, 121.3, 60.8, 39.2, 14.3. HRMS (TOF MS EI+) m/z calcd for
[C13H13NO5S] 295.0514, found 295.0506.
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2-((1R,3R,5S)-6,6-dimethyl-2-methylenebicyclo[3.1.1] heptan-3-yl)benzo[d]isothiazol-3(2H)-one 1,1-dioxide
(7e): White solid. Melting point: 130-131 °C. Yield: 97mg (62%). 1H NMR (400 MHz, CDCl3) δ 8.04 (dd,
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2
3
J
= 6.7, 1.4 Hz,
4
1H), 7.93 – 7.78 (m,3H), 5.72 – 5.63 (m, 1H), 4.36 (ddd,
J
= 15.7, 3.7, 1.9 Hz, 1H), 4.17 (dd,
J = 15.7, 1.3 Hz, 1H), 2.38 (dt, J
5
6
= 8.7, 5.6 Hz, 2H), 2.31 (s, 1H), 2.28 – 2.17 (m, 2H), 2.08 (ddd,
J
= 5.6, 2.9, 1.8 Hz, 1H), 1.27 (s, 3H), 0.83 (s, 3H).13C NMR
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(100 MHz, CDCl3) δ 159.2, 141.1, 138.0, 134.8, 134.3, 127.5, 125.3, 122.5, 121.0, 43.9, 43.8, 40.7, 38.3, 31.6, 31.4, 26.2, 21.0. HRMS
(TOF MS EI+) m/z calcd for [C17H19NO3S] 317.1086, found 317.1090.
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1,3-bis(2,3-dimethylbut-2-enyl)-5-fluoropyrimidine-2,4(1H,3H)-dione (8b): White solid. Melting point: 73-
74 °C. Yield: 58 mg (40%). 1H NMR (400 MHz, CDCl3) δ 7.06 (d, J = 5.5 Hz, 1H), 4.66 (s, 2H), 4.39 (s, 2H), 1.85 (s, 3H),
1.79 (s, 3H), 1.76 (s, 3H), 1.67 (s, 3H), 1.58 (s, 3H), 1.50 (s, 3H). 13C NMR (100 MHz, CDCl3) δ 157.5 (d,
= 469 Hz), 124.9, 124.5, 121.6, 121.3, 50.1, 44.4, 21.3, 21.1, 20.5, 20.4, 16.4, 15.1. {1H}19F NMR
J = 25 Hz), 150.8,
140.2 (d, J = 234 Hz), 131.8 (d, J
(376 MHz, CDCl3) δF -164.5 (CF). HRMS (TOF MS EI+) m/z calcd for [C16H23FN2O2] 294.1744, found 294.1750.
6-chloro-1-(2,3-dimethylbut-2-enyl)-3-methylpyrimi dine-2,4(1H,3H)-dione (8d): Colorless oil. Yield: 41 mg
1
(35%). H NMR (400 MHz, CDCl3) δ 5.92 (s, 1H), 4.77 (s, 2H), 3.34 (s, 3H), 1.78 (s, 3H), 1.71 (s, 3H), 1.51 (s, 3H). 13
C
NMR (100 MHz, CDCl3) δ 161.1, 151.7, 146.3, 129.6, 121.5, 102.1, 49.3, 28.6, 21.4, 20.3, 14.5. HRMS (TOF MS EI+) m/z calcd for
[C11H15ClN2O2] 242.0822, found 242.0825.
Radical-trapping procedure. To a Schlenk tube equipped with a magnetic stir bar were added TBAI (37 mg, 0.1
mmol) and nitro-phthalimide ( 0.5 mmol) with olefin 1 (1 mmol) in 2 mL of benzene. Then TBHP (5.5 M in decane, 1
mmol, 0.2 mL) and 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) (2mol) were added before the vial was sealed and
the reaction mixture was stirred at the 80 °C for 12 h. After required reaction time, the mixture was cooled down to
room temperature. As expected, the formation of desired product 5b was suppressed, and only the TEMPO–
cyclohexane adduct 5b’ was observed (determined by LC-MS analysis, calc for [M+H]+ [C15H28NO]+: 238.22, observed:
238.15). The result indicates that the transformation may proceed through a radical pathway.
ASSOCIATED CONTENT
Supporting Information：
1H, 13C and 19F NMR spectra of all new compounds. This material is available free of charge via the Internet at
http://pubs.acs.org/
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AUTHOR INFORMATION
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Corresponding Author
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5
*E-mail: yiwang@nju.edu.cn
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Notes
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The authors declare no competing financial interest.
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ACKNOWLEDGMENT
We gratefully acknowledge the financial support from the National Natural Science Foundation of China (No. 21402088
and No. 21472082) and the Fundamental Research Funds for the Central Universities (No. 2062014749).
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