Amination of Diazocarbonyl Compounds: N-H Insertion under Metal-Free Conditions

Article abstract of DOI:10.1021/acs.joc.6b00233

Transition-metal-free intermolecular N-H insertion of α-diazocarbonyl compounds is reported. Among the series of nitrogen sources examined, dibenzenesulfonimide was found to be the choice in terms of the yields and the reaction time. Primary mechanistic e

Full text of DOI:10.1021/acs.joc.6b00233

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Article
Amination of Diazocarbonyl Compounds: N-
H Insertion under Metal-Free Conditions
Xuesong Luo, Gui Chen, Lin He, and Xueliang Huang
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.6b00233 • Publication Date (Web): 08 Mar 2016
Downloaded from http://pubs.acs.org on March 12, 2016
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Amination of Diazocarbonyl Compounds: N-H Insertion under Metal-Free
Conditions
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Xuesong Luo,‡a Gui Chen,‡b Lin He*a and Xueliang Huang*b
a School of Chemistry and Chemical Engineering, Shihezi University, Xinjiang Uygur Autonomous
Region, 832000, China.
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b Key Laboratory of Coal to Ethylene Glycol and Its Related Technology, Fujian Institute of Research on
the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian, 350002, China.
KEYWORDS: N-H insertion, metal-free, diazocarbonyl compounds, dibenzenesulfonimide
Abstract
Transition-metal-free intermolecular N-H insertion of α-diazocarbonyl compounds is reported.
Among series of nitrogen sources examined, dibenzenesulfonimide was found to be the choice in
terms of the yields and the reaction time. Primary mechanistic experiments suggest that a
pathway involving a sequence of protonation and nucleophilic substitution was preferred.
Introduction
Donor/acceptor (D/A) carbenoids generated from aryl diazoesters are versatile reaction
intermediates. They can undergo various transformations including three-membered ring
(cyclopropane, cyclopropene) formation, X-H bond insertion (X = C, N, O, S, etc.), ylide generation
and cross-coupling reactions.1,2 Of particular interest, N-H bond insertion has received
considerable attention due to its facile construction of nitrogen-containing molecules, such as
α-amino esters/ketones and N-heterocycles,3,4 which are precursors for α-amino acids and
pharmaceutically useful compounds.
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Scheme 1. The N-H bonds insertion of diazo compounds.
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Thus, it is not surprising that significant advances have been achieved towards transition-metal
(mainly Cu, Rh, Pd) catalyzed N-H insertion reactions.3h-3n As for metal-free process,4,5 Mattson
and coworkers developed a difluoroboronate urea type catalyst, which can serve as a strong
hydrogen bond donor to activate α-nitro-α-diazo esters, hence achieving an organocatalytic
approach to N-H insertion reactions (Scheme 1a, left).4b-4d Among all these catalytic
transformations, aniline derivatives or carbamates were employed as the nitrogen sources.
Recently, the research group of Davies disclosed a catalyst-free, thermal induced N-H insertion of
donor/acceptor carbenes (Scheme 1a, right).4a This protocol was operationally simple, and more
importantly, a broad range of nitrogen sources including primary amines, secondary amines, and
aniline derivatives could be inserted. During our recent study on aminofluorination of diazo
compounds (Scheme 1b),6 we have observed small amount of amination product, when water
was employed as the reaction media. Replacement of N-fluorobenzenesulfonimide (NFSI) with
dibenzenesulfonimide resulted in a rapid formation of α-amino-ester derivative (Scheme 1c).
Although the reaction of diazo compounds with acids, such as carboxylic acids,7 hydrogen
halides8 and sulfonic acids9 are known in the literature, to our knowledge, insertion of D/A
carbenoid precusors to imides has not been realized to date. Considering the ubiquitous motif of
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sulfonamides in pharmaceutical chemistry,10a we decided to explore this metal-free N-H insertion
reactions systematically, and reported our preliminary results on this topic.11
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Results and Discussion
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Table 1. Optimization of the reaction conditions.
At the outset, dibenzenesulfonimide was selected as nitrogen source as its structure is similar to
that of NFSI. To our delight, upon addition of ethyl diazophenylacetate 1a12 to a solution of
dibenzenesulfonimide 2 in 1,2-dichloroethane (DCE) at room temperature, bubbles were
generated immediately. The orange solution was changed to colorless within half an hour. The
desired product 3a was obtained in 74% yield upon isolation (Table 1, entry 1). Reaction
temperature had little affects on the yields of 3a (Table 1, entries 2-4). Besides DCE, other
solvents were also examined. Dichloromethane (DCM), acetonitrile (MeCN), tetrahydrofuran
(THF) or toluene (PhMe) gave low to moderate yields (Table 1, entries 5 and 7-9). When
trifluorotoluene (PhCF3), which is the best choice for the thermal induced N-H insertion
reactions,4a was used, only moderate yield of 3a was obtained (Table 1, entry 10). Chloroform
(CHCl3) was proved to be optimal, giving 3a in 84% isolated yield (Table 1, entry 6). Notably, the
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reaction can also be performed in water, and a relatively longer reaction time (15 h) was required
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(Table 1, entry 11). It is worthwhile to mention that slow addition of 1a was not necessary for the
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current N-H insertion reaction.
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Table 2. Reaction scope of sulfonamides.
Besides dibenzenesulfonimide, the effects of other nitrogen sources were also evaluated.
4-Methyl-N-((4-nitrophenyl)sulfonyl)benzenesulfonamide (2b) gave similar yield of desired
product 3ab (Table 2, 81%). Replacing either sulfonyl group in 2b with acetyl group led to lower
reactivity, presumably because of the lower acidity of the corresponding imides (Table 2, 2c and
2d). Thus an elevated reaction temperature and extended reaction time were required, giving 3ac
and 3ad in moderate yields. Phthalimide 2h (pKa 8.3) could not be inserted even at elevated
temperature. Phenyl, methyl or benzyl substituted sulfonamides (pKa around 16) proved to
unreactive under current system (Table 2, 2e-2g). As expected, pyrrolidine 2i (pKa 44) could not
react with 1a either. This reaction phenomenon indicates that a pathway involving a sequence of
protonation and nucleophilic substitution is likely (vide infra).
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Table 3. Reaction scope of diazo compounds.
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The generality and limitation regarding diazo compounds for the reactions with
dibenzenesulfonimide were examined (Table 3). Most of the diazo compounds listed in Table 3
reacted with dibenzenesulfonimide smoothly to give the corresponding products in moderate to
good yields. Increasing the sizes of the ester groups (R2) has no big influence on the reaction
(Table 3, 2a−d). Methyl, isobutyl, or even more bulky menthol group gave similar yields of
corresponding products (Table 3, 3a−d). Notably, a pair of diastereoisomers 3d was obtained in a
ratio of 1:1 with (+)-menthol as the chiral auxiliary. The effects of substituents on the phenyl ring
have also been examined. Both electron-withdrawing (fluoro, chloro, bromo) and
electron-donating groups (methoxyl, methylthio, methyl) on the aromatic ring of 1 were tolerated
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under the standard conditions, and the corresponding products were obtained in moderate to
good yields (Table 3, 3e-3o). Furthermore, phenyl ring bearing substituted groups at the ortho-,
meta- and para- positions had no obvious impacts on the yields of the products (Table 3, 3e-3o).
The reaction of diazoacetates possessing two substituents on the aromatic ring showed lower
efficiency (Table 3, 3i and 3p). Naphthyl acetate derived diazo compound was also viable reaction
partner (Table 3, 3q). Of note, functional groups containing vinyl or alkynyl moiety remained
intact (Table 3, 3r and 3s). Interestingly, tocopherol derived diazoacetate could also undergo the
reaction, giving the desired product in good yield (Table 3, 3t). Notably, the reaction could be
scaled up to gram scale without sacrificing the yield of 3a (5 mmol scale, 1.80 g 3a was obtained
with 78% yield). It is also should be mentioned that when diazo compounds aliphatic carboxylic
acid were employed, no formation of aminated products were observed.
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Scheme 2. Desulfonylation of 3ab.
It’s worthy to mention that the sulfonamide groups on 3ab could be easily removed according to
the literature procedures (Scheme 2).13 Deprotection of 4-nitrobenzenesulfonyl group was
achieved by treatment with PhSH/K2CO313a in MeCN, giving 4a in 81% yield.
Having uncovered an efficient method for the N-H bond insertion of disulfonimides, we sought to
gain more insights into the reaction mechanism. Thus a series of additional experiments were
carried out subsequently. In the presence of 1 equivalent organic base (Et3N) or inorganic base
(Na2HPO4), the reaction did not take place at all (Scheme 3a). Using D2O as solvent, 97% of
deuterium was incorporated into the final product (Scheme 3b). Kinetic isotope effect (KIE) for
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the N-H insertion reaction was found to be 1.8 using a mixture of D2O/H2O (1:1) as solvent
(Scheme 3c), suggesting that protonation of the diazo compounds was the rate determined
step.14 Fitted the relative rates by Hammett equation, a fairly linear correlation between
log(kX/kH) and σ was obtained with a reaction constant of ρ = -2.39 (Figure 1). The large negative
ρ value also suggests that a positive charge reaction center was developed during the reaction
progress and formation of the procarbonium ion is a rate determined step.15
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Scheme 3. Preliminary mechanistic studies.
1.5
MeO
1.0
Me
0.5
H
F
0.0
Cl
Br
-0.5
-1.0
-0.3 -0.2 -0.1 0.0 0.1 0.2 0.3
σ
Figure 1. Hammett plot of log(kX/kH) vs σ for the reaction of dibenzenesulfonimide with
para-substituted diazophenylacetate 1 in CHCl3 at room temperature, [1] = 0.15 M,
[dibenzenesulfonimide] = 0.10 M, slope = -2.39, y-intercept = 0.114, r2 = 0.945.
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Based on previous reports7-9 and our own observations, a plausible mechanism for the
catalyst-free N-H insertion reaction between diazo compounds and dibenzenesulfonimide is
proposed (Scheme 4). Dibenzenesulfonimide 2a is known as a weak acid with pKa of 1.45,16
which may be partially ionized to generate a proton ion and a dibenzenesulfonimide anion
(Scheme 4a). The major species in chloroform may still be dibenzenesulfonimide 2a. So that the
reaction mechanism should be similar to that of X-H (X = Cl, F) bonds insertion.1b Protonation of
the mild nucleophilic diazo carbon leads to a tight ion pair of diazonium ion A and
dibenzenefulfonimide anion B. Displacement of nitrogen on A by dibenzenefulfonimide anion B
furnishes the final product 3a (Scheme 4b).6
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Scheme 4. Proposed mechanism for the N-H bond insertion.
Conclusion
In conclusion, we have developed an efficient catalyst-free N-H bonds insertion of α-diazo
compounds under mild conditions. This method provides a facile approach for inserting diazo
compounds into the N-H bonds of sulfonimides. Mechanistic studies reveal that the N-H insertion
undergoes protonation of diazo compounds to generate a procarbonium ion, followed by
displacement of dinitrogen by benzenesulfonimide anion via SN2 type reaction to furnish the final
products.
EXPERIMENTAL SECTION
General Information. Unless otherwise indicated, all glassware was dried before use and the
experimental reactions were performed under an atmosphere of air. All diazocarbonyls were
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synthesized according to known procedures reported in the literature. 12b-e All solvents were
distilled from appropriate drying agents prior to use. Reaction progress was monitored by thin
layer chromatography (TLC). Visualization was achieved by ultraviolet light at 254 nm or by
staining using triketohydrindene hydrate. Flash column chromatography was performed using
silica gel 60 (200−300 mesh). Pressed KBr disks for infrared spectra were recorded using a FT-IR
spectrometer. Wavelengths (ν) are reported in cm−1. Melting points were recorded using a
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1
melting point thermometer. All H NMR and 13C NMR spectra were recorded in CDCl3. Chemical
shifts were given in parts per million (ppm, δ) referenced to the peak of tetramethylsilane,
defined at δ = 0.00 (1H NMR) or the solvent peak of CDCl3 defined at δ = 7.26 (1H NMR); the
solvent peak of CDCl3, defined at δ = 77.0 (13C NMR); Coupling constants are quoted in Hz (J). 1H
NMR spectroscopy splitting patterns are designated as singlet (s), doublet (d), triplet (t), quartet
(q). Splitting patterns that could not be interpreted or easily visualized were designated as
multiplet (m) or broad (br). High-resolution mass spectra were obtained using a high-resolution
ESI-TOF mass spectrometer.
CAUTION! Even though we have noted no explosive tendencies of the diazo compounds, it is
strongly recommended that they should be handled with great care and proper protection.
General procedure for preparation of diazoesters
Method A: According to a known procedure12b,12d-e, to the solution of ethyl phenylacetate (5
mmol) and p-toluenesulfonylazide (TsN3) (1.24 g, 6 mmol) in anhydrous CH3CN or THF (40 mL)
was added 1,8-diazabicyclo-[5.4.0]-undec-7-ene (DBU) (1.14 g, 7.5 mmol) slowly at room
temperature. Then the reaction mixture was stirred at room temperature for 15 hours. After
water (40 mL) was added, the resulting mixture was extracted with diethyl ether (3 × 40 mL). The
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combined organic layer was washed with brine (20 mL) and dried over anhydrous Na2SO4. After
removing the solvent under reduced pressure, the residual was purified by column
chromatography on silica gel to give 1a-1r.
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Method B: According to a known procedure12c, Pd(PPh3)4 (144 mg, 5 mol%), NaOH (300.0 mg, 7.5
mmol) were suspended in ethanol (10.0 mL) and stirred for 30 min under argon. Then aryl iodide
(2.5 mmol) and ethyl 2-diazo-3-oxobutanoate (468 mg, 3.0 mmol) was added. The resulting
solution was stirred at room temperature for 5 h. The mixture was filtered through a short path
of silica gel with ethyl acetate as eluent. After removing the solvent under reduced pressure, the
residual was purified by column chromatography on silica gel to give the products 1s and 1t.
General procedure for the N-H insertion of diazoesters
The mixture of diazoesters 1 (0.3 mmol) and dibenzenesulfonimide (0.6 mmol, 178 mg) in 3 mL
CHCl3 was stirred until disappearing of diazoesters 1 (monitored by TLC). After removing the
solvent under reduced pressure, the residual was purified by column chromatography on silica gel
to give 3.
1H and 13C NMR Spectra data for the prepared substrates
Ethyl 2-diazo-2-phenylacetate (1a)
1H NMR (400 MHz, CDCl3) δ 7.48 (d, J = 7.6 Hz, 2H), 7.38 (t, J = 7.6 Hz, 2H), 7.17 (t, J = 7.6 Hz, 1H),
4.34 (q, J = 7.1 Hz, 2H), 1.34 (t, J = 7.1 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ 165.2, 128.9, 125.7,
125.6, 123.9, 60.9, 14.4.
Methyl 2-diazo-2-phenylacetate (1b)
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1H NMR (400 MHz, CDCl3) δ 7.48 (d, J = 7.5 Hz, 2H), 7.38 (t, J = 7.5 Hz, 2H), 7.18 (t, J = 7.5 Hz, 1H),
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3.86 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 165.6, 128.9, 125.8, 125.4, 123.9, 51.9.
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Isobutyl 2-diazo-2-phenylacetate (1c)
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1H NMR (400 MHz, CDCl3) δ 7.48 (d, J = 7.5 Hz, 2H), 7.38 (t, J = 7.5 Hz, 2H), 7.17 (t, J = 7.5 Hz, 1H),
4.06 (d, J = 6.6 Hz, 2H), 2.07–1.94 (m, 1H), 0.97 (d, J = 6.6 Hz, 6H); 13C NMR (100 MHz, CDCl3) δ
165.2, 128.9, 125.7, 125.6, 123.9, 70.9, 27.87, 19.0.
(1S,2R,5S)-2-isopropyl-5-methylcyclohexyl 2-diazo-2-phenylacetate (1d)
1H NMR (400 MHz, CDCl3) δ 7.49 (d, J = 7.6 Hz, 2H), 7.36 (t, J = 7.6 Hz, 2H), 7.15 (t, J = 7.6 Hz, 1H),
4.91–4.85 (m,1H), 2.14–2.10 (m, 1H), 1.96–1.88(m, 1H), 1.73– 1.67 (m, 2H),1.54–1.48(m, 1H),
1.44–1.41(m, 1H), 1.15– 1.02(m, 2H), 0.93– 0.90(m, 6H), 0.88– 0.84(m, 1H), 0.81 (d, J = 7.0 Hz,
3H); 13C NMR (100 MHz, CDCl3) δ 164.6, 128.8, 125.7, 125.5, 123.8, 74.9, 47.1, 41.3, 34.2, 31.4,
26.5, 23.6, 21.9, 20.6, 16.5.
Ethyl 2-diazo-2-(4-fluorophenyl)acetate (1e)
1H NMR (400 MHz, CDCl3)δ 7.45–7.41 (m, 2H), 7.09–7.05 (m, 2H), 4.31 (q, J = 7.1 Hz, 2H), 1.33 (t,
J = 7.1 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ 165.1, 160.8 (d, JC-F = 245 Hz), 125.7 (d, JC-F = 7.9 Hz),
121.3 (d, JC-F= 3.2 Hz), 115.8 (d, JC-F = 21.8 Hz), 60.9, 14.3.
Ethyl 2-(4-chlorophenyl)-2-diazoacetate (1f)
1H NMR (400 MHz, CDCl3) δ 7.41 (d, J = 8.7 Hz, 2H),7.32 (d, J = 8.7 Hz, 2H),4.32(q, J = 7.1 Hz,
2H),1.33 (t, J = 7.1 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ 164.8, 131.3, 129.0, 125.0, 124.2, 61.1,
14.4.
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Ethyl 2-(4-bromophenyl)-2-diazoacetate (1g)
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1H NMR (400 MHz, CDCl3) δ 7.49 (d, J = 8.7 Hz, 2H), 7.36 (d, J = 8.7 Hz, 2H),4.33(q, J = 7.1 Hz,
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2H),1.34 (t, J = 7.1 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ 164.8, 131.9, 125.3, 124.8, 119.2, 61.1,
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14.4.
Ethyl 2-(3-chlorophenyl)-2-diazoacetate (1h)
1H NMR (400 MHz, CDCl3) δ 7.55 (s, 1H), 7.34–7.27 (m,2H),7.14 (d, J = 7.4 Hz, 1H),4.34(q, J = 7.1
Hz, 2H),1.34 (t, J = 7.1 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ 164.6, 135.0, 130.0, 127.8, 125.6,
123.6, 121.5, 61.2, 14.4.
Ethyl 2-diazo-2-(3,4-dichlorophenyl)acetate (1i)
1H NMR (400 MHz, CDCl3) δ 7.65 (d, J = 2.2 Hz, 1H), 7.42 (d, J = 8.5 Hz, 1H),7.28 (dd, J = 8.5 Hz, J =
2.2 Hz, 1H), 4.34 (q, J = 7.1 Hz, 2H), 1.34 (t, J = 7.1 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ 164.3,
133.1, 130.6, 129.2, 126.1, 125.1, 122.5, 61.3, 14.4.
Ethyl 2-diazo-2-(4-(tosyloxy)phenyl)acetate (1j)
1H NMR (400 MHz, CDCl3) δ 7.70 (d, J = 7.6 Hz, 2H), 7.40 (d, J = 8.0 Hz, 2H), δ 7.31 (d, J = 7.6 Hz,
2H), 6.98 (d, J = 8.0 Hz, 2H), 4.32 (q, J = 6.8 Hz, 2H), 2.45 (s, 3H), 1.33 (t, J = 6.8 Hz, 3H); 13C NMR
(100 MHz, CDCl3) δ 164.8, 147.2, 145.4, 132.2, 129.8, 128.5, 124.9, 124.7, 122.9, 61.1, 21.7, 14.4.
Ethyl 2-(4-(benzyloxy)phenyl)-2-diazoacetate (1k)
1H NMR (400 MHz, CDCl3) δ 7.42 (d, J = 7.0 Hz, 2H), 7.40–7.37 (m, 4H), 7.34–7.30 (m, 1H), 5.06 (s,
2H), 4.31 (q, J = 7.1 Hz, 2H), 1.33 (t, J = 7.1 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ 165.7, 157.1,
136.8, 128.6, 128.0, 127.4, 125.9, 117.4, 115.6, 70.1, 60.9, 14.5.
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Ethyl 2-diazo-2-(4-methoxyphenyl)acetate (1l)
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1H NMR (400 MHz, CDCl3) δ 7.37 (d, J = 8.9 Hz, 2H), 6.93 (d, J = 8.9 Hz, 2H), 4.30 (q, J = 7.1 Hz, 2H),
3.78 (s, 3H), 1.32 (t, J = 7.1 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ 165.6, 157.9, 125.7, 116.9, 114.4,
60.8, 55.2, 14.4.
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Ethyl 2-diazo-2-(4-(methylthio)phenyl)acetate (1m)
1H NMR (400 MHz, CDCl3) δ 7.40 (d, J = 8.8Hz, 2H), 7.27 (d, J = 8.8Hz, 2H), 7.32 (q, J = 6.8Hz, 4H),
2.48 (s, 3H), 1.36 (t, J = 7.2Hz, 3H); 13C NMR (100 MHz, CDCl3) δ 165.2, 135.9, 127.3, 124.4, 122.2,
61.0, 16.0, 14.5.
Ethyl 2-diazo-2-(3,4-dimethylphenyl)acetate (1n)
1H NMR (400 MHz, CDCl3) δ 7.36 (d, J = 8.2 Hz, 2H), 7.18 (d, J = 8.2 Hz, 2H), 4.31(q, J = 7.1 Hz, 2H),
2.33 (s, 3H), 1.33 (t, J = 7.1 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ 165.4, 135.5, 129.6, 124.0, 122.2,
60.8, 20.9, 14.4.
Ethyl 2-diazo-2-(o-tolyl)acetate (1o)
1H NMR (400 MHz, CDCl3) δ 7.40-7.38 (m, 1H), 7.26-7.25 (m, 3H), 4.30 (q, J = 7.2 Hz, 2H), 2.31 (s,
3H), 1.31 (t, J = 7.2Hz, 3H); 13C NMR (100 MHz, CDCl3) δ 166.1, 137.6, 130.8, 130.8, 128.8, 126.3,
124.2, 61.1, 19.9, 14.5.
Ethyl 2-diazo-2-(4-methoxyphenyl)acetate (1p)
1H NMR (400 MHz, CDCl3) δ 7.20 (d, J = 1.5 Hz, 1H), 6.91–6.85 (m, 2H), 4.32 (q, J = 7.1 Hz, 2H),
3.90 (s, 3H), 3.88 (s, 3H), 1.34 (t, J = 7.1 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ 165.7, 149.4, 147.2,
117.5, 116.3, 111.6, 108.2, 60.9, 55.9, 55.8, 14.5.
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Ethyl 2-diazo-2-(naphthalen-2-yl)acetate (1q)
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1H NMR (400 MHz, CDCl3) δ 8.01 (s, 1H), 7.85 (d, J = 8.5 Hz, 1H), 7.80 (d, J = 7.3 Hz, 2H), 7.54 (d, J
= 8.3 Hz, 1H), 7.50–7.42 (m, 2H), 4.38 (q, J = 6.8 Hz, 2H), 1.38 (t, J = 6.8 Hz, 3H); 13C NMR (100
MHz, CDCl3) δ 165.3, 133.6, 131.4, 128.6, 127.6, 127.5, 126.6, 125.7, 122.8, 122.5, 121.9, 61.0,
14.5.
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Vinyl 2-diazo-2-phenylacetate (1r)
1H NMR (400 MHz, CDCl3) δ 7.48 (d, J = 7.6 Hz, 2H), 7.38 (t, J = 8.0 Hz, 2H), 7.18 (t, J = 8.0 Hz, 1H),
6.02–5.93 (m, 1H), 5.40 (dd, J = 17.2 Hz, J = 1.2 Hz, 1H), 5.27 (d, J = 10.4Hz, 1H), 4.76 (d, J = 5.2 Hz,
2H); 13C NMR (100 MHz, CDCl3) δ 164.7, 132.0, 128.8, 125.7, 125.3, 123.9, 118.2, 65.3.
Vinyl 2-diazo-2-phenylacetate (1s)
1H NMR (400 MHz, CDCl3) δ 7.54–7.52 (m, 4H), 7.47 -7.45 (m, 2H), 7.33-7.32 (m, 3H), 4.33 (q, J =
7.1 Hz, 2H), 1.34 (t, J = 7.1 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ 164.8,132.1, 131.5, 128.3,128.2,
125.7, 123.4, 123.2, 120.3, 89.6, 89.1, 61.1, 14.4.
Ethyl
2-diazo-2-(4-((((R)-2,5,7,8-tetramethyl-2-((4R,8R)-4,8,12-trimethyltridecyl)chroman-6-yl)oxy)me
thyl)phenyl)acetate (1t)
1H NMR (400 MHz, CDCl3) δ 7.49 (s, 4H), 4.66 (s, 2H), 4.32 (q, J = 7.2 Hz, 2H), 2.57 (t, J = 6.4 Hz,
2H)，2.20 (s, 3H), 2.15 (s, 3H), 2.10 (s, 3H), 1.85-1.71 (m, 2H), 1.60-1.47 (m, 3H), 1.45-1.38 (m, 3H),
1.35-1.31 (m, 5H), 1.29-1.24 (m, 10H), 1.16-0.97 (m, 6 H), 0.87-0.84 (m, 12H); 13C NMR (100 MHz,
CDCl3) δ 165.2, 148.2, 148.0, 135.7, 128.4, 127.9, 125.9, 125.1, 124.0, 123.0, 117.6, 74.8, 74.3,
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61.0, 40.1, 39.5, 37.7-37.4 (m), 32.9-32.8 (m), 31.4, 28.1, 24.9, 24.5, 23.9, 22.8, 21.1, 20.8,
19.8-19.7 (m), 14.6, 13.0, 12.1, 11.9.
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1H and 13C NMR Spectra data for the prepared products
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Ethyl 2-phenyl-2-(N-(phenylsulfonyl)phenylsulfonamido)acetate (3a)
Compound 3a was obtained as a white solid in 84% yield, 115.7 mg, Rf = 0.39 (petroleum ether :
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ethyl acetate = 5 : 1); mp 137-138 C; H NMR (400 MHz, CDCl3, TMS) δ 7.66 (t, J = 8.0 Hz, 6H),
7.55 (t, J = 7.2 Hz, 2H), 7.41-7.34 (m, 7H), 6.12 (s, 1H), 4.17-4.09 (m, 1H), 3.90-3.82 (m, 1H), 0.97
(t, J = 7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ 167.0, 138.9, 133.6, 133.0, 131.1, 128.6, 128.52,
128.50, 128.1, 64.2, 61.9, 13.6; IR (KBr) 3060, 2950, 1738, 1498, 1354, 1331, 1081, 1017, 777,
751, 546 cm-1; HRMS-(DART) (m/z): (M + H)+ calcd for C22H22NO6S2, 460.0889; found 460.0882.
Methyl 2-phenyl-2-(N-(phenylsulfonyl)phenylsulfonamido)acetate (3b)
Compound 3b was obtained as a white solid in 70% yield, 93 mg, Rf = 0.33 (petroleum ether :
ethyl acetate = 10 : 1); mp 162-163 oC; 1H NMR (400 MHz, CDCl3, 7.26) δ 7.68 (d, J = 8.0 Hz, 4H),
7.61-7.55 (m, 4H), 7.41 (t, J = 7.6 Hz, 4H), 7.38-7.32 (m, 3H), 6.13 (s, 1H), 3.50 (s, 3H); 13C NMR
(100 MHz, CDCl3) δ 167.6, 139.7, 133.6, 132.8, 131.1, 128.7, 128.5, 128.2, 64.2, 52.5; IR (KBr)
3061, 2947, 1738, 1583, 1331, 1284, 1169, 915, 895, 778, 546 cm-1; HRMS-(DART) (m/z): (M +
NH4)+ calcd for C21H23N2O6S2, 463.0998; found 463.0992.
Isobutyl 2-phenyl-2-(N-(phenylsulfonyl)phenylsulfonamido)acetate (3c)
Compound 3c was obtained as a white solid in 73% yield, 106 mg, Rf = 0.39 (petroleum ether :
ethyl acetate = 10 : 1); mp 101-102 oC; 1H NMR (400 MHz, CDCl3) δ 7.67 (d, J = 7.6 Hz, 4H), 7.61 (d,
J = 6.8 Hz, 2H), 7.56 (t, J = 7.6 Hz, 2H), 7.42-7.34 (m, 7H), 6.18 (s, 1H), 4.00-3.95 (m, 1H), 3.55-3.50
(m, 1H), 1.65-1.58 (m, 1H), 0.79 (t, J = 7.2 Hz, 6H); 13C NMR (100 MHz, CDCl3) δ 167.3, 139.9,
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133.6, 133.1, 131.2, 128.6, 128.5, 128.1, 72.3, 64.5, 27.4, 19.0; IR (KBr) 3064, 2959, 2847, 1738,
1359, 1224, 1050, 683, 581, 544 cm-1; HRMS-(DART) (m/z): (M + NH4)+ calcd for C24H29N2O6S2,
505.1467; found 505.1462.
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(1S,2R,5S)-2-isopropyl-5-methylcyclohexyl
2-phenyl-2-(N-(phenylsulfonyl)phenylsulfonamido)acetate (3d)
Compound 3d was obtained as a white solid in 76% yield, 129 mg, Rf = 0.41 (petroleum ether :
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ethyl acetate = 5 : 1); mp 53-54 C; H NMR (400 MHz, CDCl3) δ 7.71-7.62 (m, 6H) 7.55-7.54 (m,
2H), 7.42-7.31 (m, 7H), 6.12 (s, 0.5H), 6.03 (s, 0.5H), 4.74-4.64 (m, 1H), 1.89 (d, J = 9.6 Hz, 1H),
1.60 (t, J = 12 Hz, 1H), 1.38 (br, 1H), 1.03-0.93 (m, 2H), 0.87 (t, J = 6.8 Hz, 4H), 0.78 (m, 4H), 0.69
(dd, J1 = 22.0 Hz, J = 6.8 Hz, 4H); 13C NMR (100 MHz, CDCl3) δ 166.73, 166.69, 139.9, 133.5, 133.2,
133.0, 131.4, 131.3, 128.56, 128.52, 128.49, 128.1, 128.0,76.7, 64.6, 64.5, 46.4, 46.0, 40.2, 49.9,
34.0, 31.32, 31.35, 25.5, 25.2, 22.7, 22.5, 22.0, 20.9, 20.7, 15.6, 15.5; IR (KBr) 3064, 2951, 1740,
1583, 1217, 1167, 1080, 1065, 616, 581cm-1; HRMS-(DART) (m/z): (M + NH4)+ calcd for
C30H39N2O6S2, 587.2250; found 587.2244.
Ethyl 2-(4-fluorophenyl)-2-(N-(phenylsulfonyl)phenylsulfonamido)acetate(3e)
Compound 3e was obtained as a white solid in 78% yield, 111 mg, Rf = 0.25 (petroleum ether :
ethyl acetate = 10 : 1); mp 120-121 oC; 1H NMR (400 MHz, CDCl3, 7.26) δ 7.71 (d, J = 7.6 Hz, 4H),
7.68-7.65 (m, 2H), 7.58 (t, J = 7.2 Hz, 2H), 7.43 (t, J = 8.0 Hz, 4H), 7.04 (t, J = 8.4 Hz, 2H), 6.07 (s,
1H), 4.17-4.09 (m, 1H), 3.89-3.81 (m, 1H), 0.96 (t, J = 7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ
166.9, 162.7 (d, JC-F = 247.7 Hz), 139.7, 133.7, 133.2 (d, JC-F = 8.2 Hz), 129.0 (d, JC-F = 3.4 Hz), 128.6,
128.5, 115.0 (d, JC-F = 21.4 Hz), 63.4, 62.0, 13.5; IR (KBr) 3066, 2996, 2899, 1733, 1381, 1354, 1289,
1224, 1022, 616, 544 cm-1; HRMS-(DART) (m/z): (M + NH4)+ calcd for C22H24FN2O6S2, 495.1060;
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ethyl acetate = 5 : 1); mp 137-138 C; H NMR (400MHz, CDCl3, 7.26) δ 7.71 (d, J = 8.0 Hz, 4H),
7.61-7.57 (m, 4H), 7.43 (t, J = 8.0 Hz, 4H), 7.31 (d, J = 8.8 Hz, 2H), 6.05 (s, 1H), 4.17-4.09 (m, 1H),
3.89-3.81 (m, 1H), 0.96 (t, J = 7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ 166.7, 139.7 134.7, 133.7,
132.5, 131.6, 128.6, 128.5, 128.2, 63.4, 62.1, 13.5; IR (KBr) 3066, 2984, 1488, 1374, 1214, 1169,
1090, 1012, 614, 579, 546 cm-1; HRMS-(DART) (m/z): (M + NH4)+ calcd for C22H24ClN2O6S2,
511.0764; found 511.0759.
Ethyl 2-(4-bromophenyl)-2-(N-(phenylsulfonyl)phenylsulfonamido)acetate (3g)
Compound 3g was obtained as a white solid in 83% yield, 134 mg, Rf = 0.34 (petroleum ether :
ethyl acetate = 10 : 1); mp 144-145 oC; 1H NMR (400 MHz, CDCl3, 7.26) δ 7.71 (d, J = 7.6 Hz, 4H),
7.59 (t, J = 7.2 Hz, 2H), 7.53 (d, J = 8.4 Hz, 2H), 7.48-7.42 (m, 6H), 6.03 (s, 1H), 4.17-4.09 (m, 1H),
3.89-3.81 (m, 1H), 0.96 (t, J = 7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ 166.7, 139.6, 133.7, 132.8,
132.1, 131.2, 128.6, 128.5, 123.0, 63.4, 62.1, 13.5; IR (KBr) 3064, 2986, 1740, 1586, 1488, 1351,
1209, 1167, 683, 616, 544 cm-1; HRMS-(EI) (m/z): (M + NH4)+ calcd for C22H24BrN2O6S2, 555.0259;
found 555.0254.
Ethyl 2-(3-chlorophenyl)-2-(N-(phenylsulfonyl)phenylsulfonamido)acetate (3h)
Compound 3h was obtained as a white solid in 64% yield, 95 mg, Rf = 0.29 (petroleum ether :
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ethyl acetate = 10 : 1); mp 86-87 C; H NMR (400 MHz, CDCl3, 7.26) δ 7.70 (d, J = 7.6 Hz, 4H),
7.60-7.55 (m, 3H), 7.51 (d, J = 7.6 Hz, 1H), 7.42 (t, J = 8.0 Hz, 4H), 7.32 (d, J = 8.0 Hz, 1H),
7.24-7.22 (m, 1H), 6.01 (s, 1H), 4.15-4.07 (m, 1H), 3.88-3.80 (m, 1H), 0.95 (t, J = 7.2 Hz, 3H); 13C
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NMR (100 MHz, CDCl3) δ 166.6, 139.7, 134.9, 134.0, 133.8, 131.2, 129.4, 129.2, 128.8, 128.63,
128.58, 63.5, 62.2, 13.6; IR (KBr) 3064, 2981, 1738, 1583, 1491, 1356, 1217, 1060, 683, 541 cm-1;
HRMS-(DART) (m/z): (M + H)+ calcd for C22H21ClNO6S2, 494.0499; found 494.0493.
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Ethyl 2-(3,4-dichlorophenyl)-2-(N-(phenylsulfonyl)phenylsulfonamido)acetate (3i)
Compound 3i was obtained as a white solid in 56% yield, 88 mg, Rf = 0.32 (petroleum ether : ethyl
acetate = 5 : 1); mp 102-103 oC; 1H NMR (400 MHz, CDCl3, 7.26) δ 7.76 (d, J = 7.6 Hz, 4H), 7.72 (d,
J = 1.6 Hz, 1H), 7.61 (t, J = 7.6 Hz, 2H), 7.50 (d, J = 1.6 Hz, 1H), 7.45 (t, J = 8.0 Hz, 4H), 7.38 (d, J =
8.4 Hz, 1H), 6.00 (s, 1H), 4.17-4.09 (m, 1H), 3.91-3.83 (m, 1H), 0.97 (t, J = 7.2 Hz, 3H); 13C NMR
(100 MHz, CDCl3) δ 166.4, 139.5, 133.9, 133.1, 132.99, 132.97, 132.2, 130.3, 130.0, 128.7, 128.5,
62.8, 62.3, 13.5. IR (KBr) 3101, 3063, 2981, 1583, 1464, 1381, 1214, 1167, 681, 576, 549 cm-1;
HRMS-(DART) (m/z): (M + NH4)+ calcd for C22H23Cl2N2O6S2, 545.0375; found 545.0369.
Ethyl 2-(N-(phenylsulfonyl)phenylsulfonamido)-2-(4-(tosyloxy)phenyl)acetate (3j)
Compound 3j was obtained as a white solid in 64% yield, 121 mg, Rf = 0.15 (petroleum ether :
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ethyl acetate = 5 : 1); mp 99-100oC; H NMR (400 MHz, CDCl3, TMS) δ 7.78 (d, J = 8.0 Hz, 2H),
7.68-7.58 (m, 8H), 7.46 (t, J = 7.6 Hz, 4H), 7.34 (d, J = 8.0 Hz, 2H), 6.99 (d, J = 8.8 Hz, 2H), 6.02 (s,
1H), 4.15-4.07 (m, 1H), 3.86-3.78 (m, 1H), 2.46 (s, 3H), 0.95 (t, J = 7.2 Hz, 3H); 13C NMR (100 MHz,
CDCl3) δ 166.8, 149.6, 145.6, 139.6, 133.8, 132.7, 132.2, 129.8, 128.7, 128.5, 128.4, 122.1, 63.3,
62.1, 21.7, 13.5; IR (KBr) 3071, 2986, 1728, 1498, 1376, 1239, 1172, 1092, 1015, 661, 584, 556
cm-1; HRMS-(DART) (m/z): (M + NH4)+ calcd for C29H31N2O9S3, 647.1192; found 647.1186.
Ethyl 2-(4-(benzyloxy)phenyl)-2-(N-(phenylsulfonyl)phenylsulfonamido)acetate (3k)
Compound 3k was obtained as a white solid in 83% yield, 141 mg, Rf = 0.26 (petroleum ether :
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7.60-7.54 (m, 4H), 7.48 (d, J = 7.2 Hz, 2H), 7.45-7.37 (m, 7H), 6.96 (d, J = 8.4 Hz, 2H), 6.09 (s, 1H),
5.13 (s, 2H), 4.18-4.10 (m, 1H), 3.91-3.83 (m, 1H), 0.98 (t, J = 7.2 Hz, 3H); 13C NMR (100 MHz,
CDCl3) δ 167.2, 158.8, 139.9, 136.7, 133.5, 132.5, 128.6, 128.5, 128.4, 128.0, 127.3, 125.3, 114.4,
69.9, 63.9, 61.9, 13.5; IR (KBr) 3066, 2925, 2876, 1734, 1069, 1380, 1355, 1220, 1170, 754, 682,
582, 552 cm-1; HRMS-(DART) (m/z): (M + NH4)+ calcd for C29H31N2O7S2, 583.1573; found 583.1567.
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Ethyl 2-(4-methoxyphenyl)-2-(N-(phenylsulfonyl)phenylsulfonamido)acetate (3l)
Compound 3l was obtained as a white solid in 64% yield, 94 mg, Rf = 0.25 (petroleum ether : ethyl
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acetate = 5 : 1); mp 105-106 C; H NMR (400 MHz, CDCl3, 7.26) δ 7.71 (d, J = 7.6 Hz, 4H),
7.58-7.56 (m, 4H ), 7.42 (t, J = 7.6 Hz, 4H), 6.87 (d, J = 8.8 Hz, 2H), 6.07 (s, 1H), 4.17-4.09 (m, 1H),
3.90-3.82 (m, 1H), 3.84 (s, 3H), 0.97 (t, J = 7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ 167.3, 159.8,
140.0, 133.5, 132.6, 128.5, 125.1, 113.5, 64.0, 61.9, 55.4, 13.6; IR (KBr) 3064, 2989, 2847, 1730,
1611, 1578, 1376, 1171, 1082, 616, 539 cm-1; HRMS-(DART) (m/z): (M + H)+ calcd for C23H24NO7S2,
490.0994; found 490.0989.
Ethyl 2-(4-(methylthio)phenyl)-2-(N-(phenylsulfonyl)phenylsulfonamido)acetate (3m)
Compound 3m was obtained as a white solid in 83% yield, 126 mg, Rf = 0.25 (petroleum ether :
o
ethyl acetate = 5 : 1); mp 125-126 C;1H NMR (400 MHz, CDCl3, 7.26) δ 7.71 (d, J = 7.6 Hz, 4H),
7.59-7.54 (m, 4H), 7.42 (t, J = 8.0 Hz, 4H), 7.20 (d, J = 8.4 Hz, 2H), 6.06 (s, 1H), 4.17-4.09 (m, 1H),
3.91-3.83 (m, 1H), 2.51 (s, 3H), 0.97 (t, J = 7.2 Hz, 3H); 13C NMR(100 MHz, CDCl3) δ 167.0, 139.8,
139.7, 133.6, 131.5, 129.5, 128.53, 128.51, 125.6, 63.9, 62.0, 15.5, 13.6; IR (KBr) 3064, 2991,
2852, 1733, 1583, 1376, 1302, 1167, 1025, 681, 584, 549cm-1; HRMS-(DART) (m/z): (M + NH4)+
calcd for C23H27N2O6S3, 523.1031; found 523.1026.
Ethyl 2-(N-(phenylsulfonyl)phenylsulfonamido)-2-(p-tolyl)acetate (3n)
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Compound 3n was obtained as a white solid in 70% yield, 99 mg, Rf =0.32 (petroleum ether : ethyl
acetate = 5 : 1); mp 120-121 oC; 1H NMR (400 MHz, CDCl3) δ 7.69 (d, J = 8.0 Hz, 4H), 7.56 (t, J = 7.6
Hz, 2H), 7.51 (d, J = 8.0 Hz, 2H), 7.41 (t, J = 7.6 Hz, 4H), 7.15 (d, J = 8.0 Hz, 2H), 6.09 (s, 1H),
4.17-4.09 (m, 1H), 3.91-3.83 (m, 1H), 2.39 (s, 3H), 0.99 (t, J = 7.2 Hz, 3H); 13C NMR (100 MHz,
CDCl3) δ 167.2, 140.0, 138.6, 133.5, 131.1, 130.0, 128.8, 128.54, 128.48, 64.2, 61.9, 21.1, 13.6; IR
(KBr) 3074, 2989, 1733, 1513, 1379, 1302, 1169, 1061, 616, 586, 551 cm-1; HRMS-(DART) (m/z):
(M + NH4)+ calcd for C23H27N2O6S2, 491.1311; found 491.1305.
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Ethyl 2-(N-(phenylsulfonyl)phenylsulfonamido)-2-(o-tolyl)acetate (3o)
Compound 3o was obtained as a white solid in 82% yield, 92 mg, Rf = 0.40 (petroleum ether :
o
ethyl acetate = 5 : 1); mp 131-132 C; 1H NMR (400 MHz, CDCl3, TMS) δ 7.71 (d, J = 8.0 Hz, 4H),
7.54 (t, J = 7.6 Hz, 2H), 7.38 (t, J = 7.6 Hz, 4H), 7.34-7.32 (m, 1H), 7.22-7.19 (m, 2H), 6.85-6.83 (m,
1H), 6.46 (s, 1H), 4.30-4.22 (m, 1H), 4.09-4.01 (m, 1H), 2.05 (s, 3H), 1.16 (t, J = 7.2Hz, 3H); 13C
NMR (100 MHz, CDCl3) δ 168.5, 140.0, 139.3, 133.4, 132.7, 130.3, 129.4, 129.1, 128.5, 128.3,
125.6, 63.4, 62.1, 19.5, 13.9; IR (KBr) 3076, 2989, 1730, 1581, 1496, 1384, 1169, 1082, 1020, 606,
544 cm-1; HRMS-(DART) (m/z): (M + NH4)+ calcd for C23H27N2O6S2, 491.1311; found 491.1305.
Ethyl 2-(3,4-dimethoxyphenyl)-2-(N-(phenylsulfonyl)phenylsulfonamido)acetate (3p)
Compound 3pwas obtained as a white solid in 37% yield, 58 mg, Rf =0.14 (petroleum ether : thyl
acetate = 5 : 1); mp 153-154 oC ; 1H NMR (400MHz, CDCl3) δ 7.73 (d, J = 7.6 Hz, 4H), 7.57 (t, J = 7.6
Hz, 2H), 7.43 (t, J =7.6 Hz, 4H), 7.23 (dd, J1 = 8.4 Hz, J2 = 1.6 Hz, 1H), 7.14 (d, J = 1.6 Hz, 1H), 6.84
(d, J = 8.4 Hz, 1H), 6.06 (s, 1H), 4.17-4.09 (m, 1H), 3.92-3.84 (m, 1H), 3.92 (s, 3H), 3.76 (s, 1H), 0.98
(t, J = 7.2 Hz, 3H); 13C NMR (100MHz, CDCl3) δ 167.2, 149.3, 148.4, 140.0, 133.6, 128.5, 125.2,
124.0, 114.2, 110.4, 64.2, 61.9, 56.0, 55.9, 13.6; IR (KBr) 3061, 2959, 2842, 1739, 1445, 1380,
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1173, 1143, 683, 599, 552 cm-1; HRMS-(DART) (m/z): (M + NH4)+ calcd for C24H29N2O8S2, 537.1365;
found 537.1369.
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Ethyl 2-(naphthalen-2-yl)-2-(N-(phenylsulfonyl)phenylsulfonamido)acetate (3q)
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Compound 3q was obtained as a white solid in 90% yield, 137 mg, Rf = 0.18 (petroleum ether :
ethyl acetate = 10 : 1); mp 143-144 oC; 1H NMR (400 MHz, CDCl3) δ 8.17 (s, 1H), 7.88-7.79 (m, 3H),
7.74-7.69 (m, 5H), 7.59-7.48 (m, 4H), 7.30 (t, J = 7.6 Hz, 4H), 6.35 (s, 1H), 4.26-4.18 (m, 1H),
4.00-3.92 (m, 1H), 1.04 (t, J = 7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ 167.3, 158.9, 140.0, 136.8,
133.5, 132.6, 128.6, 128.5, 128.0, 127.4, 125.3, 114.4, 69.9, 64.0, 61.9, 13.6; IR (KBr) 3061, 2954,
1743, 1381, 1354, 1272, 1125, 1082, 616, 549 cm-1; HRMS-(DART) (m/z): (M + NH4)+ calcd for
C26H27N2O6S2, 527.1311; found 527.1305.
N-(2-oxo-1-phenylhex-5-en-1-yl)-N-(phenylsulfonyl)benzenesulfonamide (3r)
Compound 3r was obtained as a white solid in 69% yield, 97 mg, Rf = 0.13 (petroleum ether :
ethyl acetate = 10 : 1); mp 122-123 oC; 1H NMR (400 MHz, CDCl3) δ 7.67 (d, J = 7.6 Hz, 4H), 7.62 (d,
J = 6.8 Hz, 2H), 7.56 (t, J = 7.2 Hz, 2H), 7.42-7.33 (m, 7H), 6.15 (s, 1H), 5.67-5.58 (m, 1H), 5.20-5.13
(m, 2H), 4.60-4.55 (m, 1H), 4.36-4.31 (m, 1H); 13C NMR (100 MHz, CDCl3) δ 166.9, 139.8, 133.6,
132.9, 131.2, 131.0, 128.7, 128.6, 128.2, 119.1, 66.7, 64.3; IR (KBr) 3064, 2924, 1735, 1496, 1446,
1217, 1167, 1080, 683, 599, 541 cm-1; HRMS-(DART) (m/z): (M + NH4)+ calcd for C23H25N2O6S2,
489.1154; found 489.1149.
Ethyl 2-(4-(phenylethynyl)phenyl)-2-(N-(phenylsulfonyl)phenylsulfonamido)aceate (3s)
Compound 3s was obtained as a white solid in 62% yield, 104 mg, Rf = 0.29 (petroleum ether :
o
ethyl acetate = 10 : 1); mp 168-169 C; 1H NMR (400 MHz, CDCl3, 7.26) δ 7.72 (d, J = 7.6 Hz, 4H),
7.64 (d, J = 8.4 Hz, 2H), 7.59 (t, J = 7.2 Hz, 4H), 7.51 (d, J = 8.4 Hz, 2H), 7.45 (t, J = 8.0 Hz, 4H), 7.38
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(d, J = 3.2 Hz, 3H), 6.10 (s, 1H), 4.19-4.11 (m, 1H), 3.91-3.83 (m, 1H), 0.99 (t, J = 7.2 Hz, 3H); 13C
NMR (100 MHz, CDCl3) δ 166.8, 139.7, 133.7, 133.0, 131.7, 131.2, 131.1, 128.6, 128.56, 128.49,
128.4, 123.8, 123.0, 90.4, 88.8, 63.8, 62.1, 13.6; IR (KBr) 3066, 2924, 1738, 1513, 1446, 1381,
1167, 1027, 683, 616, 549 cm-1; HRMS-(DART) (m/z): (M + NH4)+ calcd for C30H29N2O6S2, 577.1467;
found 577.1462.
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Ethyl
2-(N-(phenylsulfonyl)phenylsulfonamido)-2-(4-(((2,5,7,8-tetramethyl-2-(4,8,12trimethyltridecyl)
chroman-6-yl)oxy)methyl)phenyl)acetate (3t)
Compound 3t was obtained as a colorless oil in 76% yield, 205 mg, Rf = 0.31 (petroleum ether :
ethyl acetate = 10 : 1); 1H NMR (400 MHz, CDCl3) δ 7.72-7.69 (m, 6H), 7.57 (t, J = 7.6 Hz, 2H), 7.51
(d, J = 8.4 Hz, 2H) 7.43 (t, J = 7.6 Hz, 4H), 6.18 (s, 1H), 4.74 (s, 2H), 4.21-4.13 (m, 1H), 3.95-3.87 (m,
1H), 2.64 (t, J = 6.4 Hz, 2H), 2.28 (s, 3H), 2.24 (s, 3H), 2.15 (s, 3H), 1.90-1.77 (m, 2H), 1.62-1.51 (m,
3H), 1.48-1.42 (m, 3H), 1.35-1.23 (m, 11H), 1.19-1.10 (m, 6H), 1.01 (t, J = 7.2 Hz, 3H), 0.90-0.86
(m, 13H); 13C NMR (100 MHz, CDCl3) δ 167.1, 148.1, 148.0, 139.9, 138.8, 133.6, 132.4, 131.3,
128.6, 128.6, 127.8, 127.4, 125.8, 123.0, 117.7, 74.8, 74.1, 64.1, 62.0, 40.0, 39.3, 37.6-37.3(m),
37.3, 32.8, 32.7, 31.3, 31.2, 27.9, 24.8, 24.4, 23.9, 22.7, 22.6, 21.0, 20.7, 19.7, 19.7-19.6(m), 13.6,
12.9, 12.0, 11.8; IR (KBr) 2951, 2852, 2363, 1750, 1653, 1538, 1459, 1381, 1274, 1169, 1087, 763,
751, 686, 544, cm-1; HRMS-(DART) (m/z): (M + H)+ calcd for C52H72NO8S2, 902.4699; found
902.4694.
Ethyl 2-(4-methyl-N-((4-nitrophenyl)sulfonyl)phenylsulfonamido)-2-phenylacet-ate (3ab)
Compound 3ab was obtained as a white solid in 81% yield, 126 mg, Rf = 0.26 (petroleum ether :
o
1
ethyl acetate = 5 : 1); mp 178-179 C; H NMR (400 MHz, CDCl3, TMS) δ 8.15 (d, J = 8.8 Hz, 2H),
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7.71 (d, J = 8.0 Hz, 2H), 7.65-7.61 (m, 4H), 7.44-7.36 (m, 3H), 7.28 (d, J = 8.0 Hz, 2H), 6.15 (s, 1H),
4.20-4.12 (m, 1H), 4.00-3.92 (m, 1H), 2.44 (s, 3H), 1.03 (t, J = 6.8 Hz, 3H); 13C NMR (100 MHz,
CDCl3) δ 166.8, 150.2, 145.6, 145.4, 136.0, 132.8, 131.2, 129.8, 129.4, 129.0, 128.8, 128.3, 123.5,
64.5, 62.2, 21.6, 13.6; IR (KBr) 3101, 3071, 2986, 1743, 1596, 1376, 1222, 1167, 1045, 943, 815,
776, 663, 546 cm-1; HRMS-(DART) (m/z): (M + NH4)+ calcd for C23H26N3O8S2, 536.1161; found
536.1156.
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Ethyl 2-(4-methylphenylsulfonamido)-2-phenylacetate (4a)17
Compound 4a was obtained as a white solid in 81% yield, 81 mg, Rf = 0.10 (petroleum ether :
o
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ethyl acetate = 5 : 1); mp 74-75 C; H NMR (400 MHz, CDCl3, TMS) δ 7.63 (d, J = 8.0 Hz, 2H),
7.25-7.19 (m, 7H), 5.76 (d, J = 8.0 Hz, 1H), 5.04 (d, J = 8.0 Hz, 1H), 4.08-3.93 (m, 2H), 2.38 (s, 3H),
1.09 (t, J = 7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ 170.0, 143.5, 136.9, 135.4, 129.4, 128.7,
128.4, 127.2, 127.0, 62.2, 59.3, 21.4, 13.8; IR (KBr) 3263, 3243, 2924, 2849, 1725, 1596, 1339,
1162, 1012, 920, 818, 534, 417 cm-1.
ASSOCIATED CONTENT
Supporting Information
The Supporting Information is available free of charge on the ACS Publications website.
Mechanistic experiments, 1H and 13C NMR spectra for all described compounds (PDF)
AUTHOR INFORMATION
Corresponding Author
helin@shzu.edu.cn;
huangxl@fjirsm.ac.cn
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Author Contributions
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‡ X.L. and G.C. contributed equally to this work.
Notes
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The authors declare no competing financial interest.
ACKNOWLEDGMENT
We thank NSFC (Grant No. 21402197, 21502190), NSF of Fujian (Grant No. 2015J05043) and
Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences,
Hundred-Talent Program (Chinese Academy of Sciences) for financial support.
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