Organocatalytic Direct N-Acylation of Amides with Aldehydes under Oxidative Conditions

Article abstract of DOI:10.1021/acs.joc.7b00457

The direct oxidative N-acylation reaction of primary amides with aryl/α,β-unsaturated aldehydes was achieved in the presence of azolium salt C3 and an inorganic base using 3,3′,5,5′-tetra-tert-butyldiphenoquinone as the oxidant, thus providing an efficient approach for the synthesis of three types of imide compounds including N-sulfonylcarboxamides, N-sulfinylcarboxamides, and dicarboxyimides in good yield.

Full text of DOI:10.1021/acs.joc.7b00457

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Note
Organocatalytic Direct N-Acylation of Amides
with Aldehydes under Oxidative Conditions
Chenguang Zheng, Xiang Liu, and Cheng Ma
J. Org. Chem., Just Accepted Manuscript • Publication Date (Web): 08 Jun 2017
Downloaded from http://pubs.acs.org on June 9, 2017
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Organocatalytic Direct N-Acylation of Amides with Aldehydes under Oxidative
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Conditions
Chenguang Zheng,† Xiang Liu,† and Cheng Ma*
Department of Chemistry, Zhejiang University, 20 Yugu Road, Hangzhou 310027, China
mcorg@zju.edu.cn
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†C.G and X. contributed equally
ABSTRACT: The direct oxidative Nꢀacylation reaction of primary amides with aryl/α,βꢀunsaturated
aldehydes was achieved in the presence of azolium salt C3 and an inorganic base using 3,3’,5,5’ꢀtetraꢀ
tertꢀbutyldiphenoquinone (DPQ) as the oxidant, thus providing an efficient approach for the synthesis of
three types of imide compounds including Nꢀsulfonylcarboxamides, Nꢀsulfinylcarboxamides, and
dicarboxyimides in good yield.
The increasing significance of imide motifs in natural products, medical and material molecules1 has
prompted chemists to develop novel methods for their efficient synthesis during the past decades.2 As a
complement alternative to classical methodology focused on the condensation3 of carboxylic acid or its
derivatives with amides to imides, Nꢀacylation of amides using aldehydes as acyl sources possesses
several practical advantages and has attracted the growing interest of specialists in this class of
transformation. The limited successful precedents based on such a crossꢀcoupling strategy were
accomplished mainly via metalꢀcatalyzed oxidative coupling routes (Scheme 1a),4,5 such as Rh(II)ꢀ
catalyzed direct sulfamidation of aldehydes,5a copperꢀ and ironꢀbased C–H functionalization of aldehydes
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with primary or secondary carboxamides assisted by bromineꢀcontaining reagents,5b,c and palladiumꢀ
mediated Nꢀacylation of picolinamides with aldehydes.5d However, these elegant methods appear to be
developed specifically for derivatization of sulfonamides or carboxamides, respectively, giving access to
corresponding imide products.
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On the other hand, significant progress has recently been made in the Nꢀheterocyclic carbene (NHC)ꢀ
catalyzed oxidative conversions of aldehydes to carboxamides,6,7 even though the addition of
nucleophilic additives7dꢀf or a twoꢀstep reaction procedure involving an activated ester intermediate6d,7g
was generally required for simple amines to circumvent problems like competing imine formation and the
weak nucleophilicity of amines.7h Notably, NHCꢀcatalyzed redoxꢀneutral cyclization reactions of imine
compounds with α,βꢀunsaturated aldehydes provide a robust protocol to forge a variety of Nꢀsubstituted
lactams containing tertiary imide scaffolds.8 In this regard, ring expansion of some special formylꢀ
substituted tertiary amides to imides has also been realized upon NHCꢀmediated redox ringꢀopening and
ringꢀclosure cascades (Scheme 1b).9 Despite these advances, to our knowledge, the NHCꢀcatalyzed
intermolecular oxidative coupling of amides and aldehydes has remained elusive in literatures.10 As a
part of our studies on NHCꢀcatalyzed transformation,11 herein we wish to present an organocatalytic
approach for the direct oxidative Nꢀacylation of primary amides with aryl/α,βꢀunsaturated aldehydes to
produce a variety of imide compounds (Scheme 1c).
Scheme 1. Formation of Imides via N-Acylation of Amides with Aldehydes
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a) Metalꢀmediated oxidative coupling of amides and aldehydes
O
O
O
[Cu], [Fe], or [Pd]
R2(H)
R1
N
R3
R2(H)
R1
R'
N
oxidant
H
O
+
H
R3
O
O
O
O
[Rh]
S
H
S
N
R'
N
R3
O
oxidant
H
H
9
b) NHCꢀcatalyzed ringꢀexpansion of formylꢀsubstituted tertiary amides to imides
R2
O
H
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R2
R1
H
R1
O
O
N
N
O
R3
R3
NHC, tertiary amine
or
or
redoxꢀneutral
n
n
R'
O
R'
N
R
N
O
H
R
R = Ts, Boc, Acyl; n = 0, 1
c) This work
O
X
O
O
O
H
NHC, inorganic base
R2
external oxidant
R1
X
N
+
R1
N
R2
H
H
H
X = SO, S or C
The coupling of 4ꢀmethylbenzenesulfonamide (1a) with 4ꢀchlorobenzaldehyde (2a) was initially
explored in the presence of a set of NHC precursors C and bases under oxidative conditions (Table 1).
The treatment of 1a and 2a with triazolium salt C1 and DBU furnished Nꢀtosylcarboxamide 3a in 45%
yield by using PhI(OAc)2 as the oxidant (Table 1, entry 1).12 Further attempts to improve the yield of 3a
by dropping amide 1a slowly to the reaction mixtures or switching C1 to thiazolium salt C2 were
unsuccessful, partially due to the competing oxidation of 1a to PhI=NTs by PhI(OAc)2 (Table 1, entries 2
and 3). When a less acidic triazolium salt C3 and NaH was used to generate the NHC catalyst, a survey
of common quinone compounds (Table 1, entries 4–6) revealed that DPQ was the choice of oxidant to
give 3a in 94% yield. In sharp contrast, neither benzoquinone (BQ) nor 2,3ꢀdichloroꢀ5,6ꢀdicyanoꢀ1,4ꢀ
benzoquinone (DDQ) could conduct this reaction well. Meanwhile the reaction almost did not occur at all
in the absence of C3; and several other azolium salts proved less effective, albeit with DPQ as the
oxidant (Table 1, entries 7–10). It was found that imide 3a was labile in the reaction mixtures and would
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convert to other unidentified byproducts, resulting in a reduced yield (Table 1, entries 4 versus 11). While
an entry of employing tꢀBuOK as the base instead proceeded smoothly in THF to furnish the desired
product 3a in almost quantitative yield, the use of Cs2CO3 led to a moderate product yield (Table 1,
entries 12 and 13). Finally, when the solvent THF was switched to CH2Cl2 or toluene, respectively, 3a
was isolated in 50 and 94% yield after 12 h (Table 1, entries 14 and 15).
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Table 1. Optimization of Reaction Conditionsa
CHO
SO2NH2
O
O
O
C (10 mol %), base
oxidant (1.5 equiv)
S
N
+
solvent, N2, t, 25 o
C
H
Me
Cl
acid workup
Cl
Me
1a
2a
3a
BF4
Cl
N
N
N
Mes
N
Cl
ClO4
N
N
N
N
C6F5
N
Mes
Mes
Mes
S
C1
C2
C3
C4
entry
1c
2c
3c
4
C
oxidant
base (equiv) solvent t (h) yieldb (%)
C1 PhI(OAc)2 DBU (4.0)
C1 PhI(OAc)2 DBU (4.0)
C2 PhI(OAc)2 DBU (4.0)
DCM
DCM
DCM
THF
THF
THF
THF
THF
THF
THF
THF
THF
THF
DCM
16
16
16
45
42
10
C3 DPQ
C3 BQ
NaH
0.5 94
0.5 10
0.5 trace
5
NaH
6
C3 DDQ
NaH
7
–
DPQ
NaH
12
0.5 11
0.5
0.5 25
trace
8
C1 DPQ
C2 DPQ
C4 DPQ
C3 DPQ
C3 DPQ
C3 DPQ
C3 DPQ
NaH
9
NaH
6
10
11
12
13
14
NaH
NaH
2
75
97
45
50
tꢀBuOK
Cs2CO3
tꢀBuOK
1
8
12
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C3 DPQ
tꢀBuOK
PhMe
12
94
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aUnless otherwise noted, reactions were conducted on a 0.4 mmol scale of 1a with 2a (0.6 mmol), catalyst C (10 mol
7
8
9
b
c
%), oxidant (1.5 equiv), and base (2.0 equiv) in solvent (4 mL) under N2. Isolated yield. 4 Å MS (100 mg) was added.
DPQ = 3,3',5,5'ꢀtetraꢀtertꢀbutylꢀ[1,1'ꢀbi(cyclohexylidene)]ꢀ2,2',5,5'ꢀtetraeneꢀ4,4'ꢀdione, DDQ = 2,3ꢀdichloroꢀ5,6ꢀdicyanoꢀ1,4ꢀ
benzoquinone. BQ = benzoquinone.
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Having the optimized reaction conditions established (Table 1, entry 12), the scope of the Nꢀacylation
of primary amides with aldehydes was investigated (Scheme 2). A scope of aryl aldehydes bearing
several substituents (−F, −Cl, –OMe, and –NO2) at different positions (2ꢀ, 3ꢀ, and 4ꢀpositions) of the
benzene ring partook in the reaction with tosylamide (1a) to give the corresponding Nꢀtosylcarboxamides
3a–e in high yields. Both thiopheneꢀ2ꢀcarbaldehyde and 2ꢀnaphthaldehyde carried out this
transformation easily, leading to imides 3f and 3g in 92% and 91% yields, respectively. Moreover, α,βꢀ
unsaturated aldehydes including enals and ynals were also suitable partners in this direct Nꢀacylation of
tosylamide. Whereas ynals were previously employed as suitable substrates in NHCꢀcatalyzed redox
reaction, notably, a wide scope of conjugated ynals no matter containing an aliphatic or an aromatic
substituent underwent this oxidative reaction to produce the desired imides 3i–k in 71–87% yields,
respectively. Unfortunately, simple alkylꢀsubstituted aldehydes could not afford corresponding imide
products under current conditions, probably due to the competing enolization of aldehyde substrates. To
exploit the synthetic feasibility of this protocol, the variation of amide component was tested next.
Electronꢀrich and ꢀpoor aryl sulfonamides reacted with aldehyde 2a readily, giving rise to products 3l–n in
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excellent yields. Methanesulfonamide was also competent partner to furnish Nꢀsulfonylcarboxamide 3o
(92%). In addition, benzamide and 4ꢀnitrobenzamide could be employed with ease for the formation of
dicarboxyimide 3p–r by using NaH (3.0 equiv) as the base instead of tꢀBuOK, owing to the weaker
acidity of carboxamides compared with sulfonylamides. Of particular interest, (S)ꢀtertꢀbutylsulfinamide
(99% ee) accomplished this reaction efficiently and yielded (+)ꢀNꢀ(tertꢀbutylsulfinyl)ꢀ4ꢀchlorobenzamide
(3s) with almost completely retained ee values. These preliminary studies further demonstrated the
versatility of this NHCꢀcatalyzed oxidative Nꢀacylation reaction in secondary imide synthesis.
Scheme 2. Substrate Scopes of the N-Acylation of Primary Amides 1 with Aldehydes 2 to Imides
3a
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10 mol % C3
DPQ (1.5 equiv)
O
X
O
O
X
O
tBuOK or NaH
THF, N2, 25 o
then acid workup
+
R1
NH2
R1
N
R2
C
R2
H
H
1
2
3
X = SO, S, or C
Me
Me
Me
O
O
3a R = 4ꢀCl, 97%
3b R = H, 97%
3c R = 2ꢀF, 94%
3d R = 3ꢀMeO, 90%
3e R = 3ꢀNO2, 87%
O
O
S
S
S
N
N
O
O
H
H
R
3f, 87%
Me
O
O
O
O
S
S
N
N
H
O
O
H
3g, 91%
3h, 82%
Me
Me
O
O
O
O
S
O
S
N
N
O
H
H
3i, 87%
3j, 79%
Me
O
O
O
R
O
Me
O
O
S
S
O
N
N
S
O
H
N
H
O
H
Cl
Ph
Cl
3l R = H, 95%
3m R = 3ꢀNO2, 93%
3n R = 2ꢀCl, 96%
3o, 92%
3k, 71%
O
O
O
O
O
O
N
Ph
Ph
N
H
Ph
N
H
H
O2N
Cl
3p, 91%
3q, 96%
3r, 89%
O
O
O
O
S
S
*
Ph
N
tBu
N
H
H
Cl
3s, 81% (98% ee)
3t, 83%
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aReaction conditions: 1 (0.4 mmol), 2 (0.6 mmol), C3 (10 mol %), DPQ (0.6 mmol), and tꢀBuOK (0.8 mmol) in THF (4 mL)
under N2, 25 oC; quenched by 1M HCl aqueous solution. Isolated yields were given. NaH (1.2 mmol) was used instead of
tꢀBuOK to form 3p–r. The absolute configuration of chiral 3s was not determined, and the ee value was detected by chiral
HPLC analysis.
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The oxidative Nꢀacylation reaction could be easily manipulated on a multigram scale, for example, to
form an antiꢀtumor agent of LY573636 (3u) in 87% yield (eq 1).13 However, the use of 3.5 equiv of tꢀ
BuOK delivered yneꢀimide 3k in 72% yield from the reaction of (Z)ꢀ3ꢀbromoꢀ3ꢀphenylacrylaldehyde and
amide 1a accompanied by the elimination of HBr (eq 2). In addition, a competition experiment using 1a
(1.0 equiv) and 2a (1.5 equiv) in the presence of phenylmethanol (1.0 equiv) still afforded imide 3a in
95% yield (eq 3), indicating that Nꢀacylation is preferred over ester formation under current conditions.14
Based on these results and our previous reports,6,11b a postulated catalytic cycle is depicted in Scheme
3. The nucleophilic addition of in situ generated carbene C3’ to aldehydes 2 initially affords Breslow
intermediates I, which are oxidized to form acylꢀazolium species II upon treatment with DPQ.14 Attacked
by deprotonated amide compounds 1’, presumably via 1,2ꢀadducts III, the azolium intermediates II
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undergo a subsequent fragmentation sequence to give imides 3 along with liberation of the carbene
5
6
7
catalyst.
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Scheme 3. Proposed Catalytic Cycle
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In summary, we have developed an organocatalytic approach for the direct Nꢀacylation reaction of
primary amides with a variety of aromatic or α,βꢀunsaturated aldehydes upon oxidative NHC catalysis
strategy. This study provides a versatile protocol for the efficient construction of several types of imides
including Nꢀsulfonylcarboxamides, Nꢀsulfinylcarboxamides, and dicarboxyimide at room temperature in
good yield.
Experimental Section
General Experimental Methods. All reactions were carried out under N2 atmosphere, with dry, freshly distilled solvents
in anhydrous conditions. Tetrahydrofuran (THF) and toluene were distilled from sodium, while dichloromethane (CH2Cl2)
was distilled from CaH2 immediately prior to use. All chemicals were used without further purification as commercially
available unless otherwise noted. Thinꢀlayer chromatography (TLC) was performed on silica gel plates (60Fꢀ254) using
UVꢀlight (254 and 365 nm). Flash chromatography was conducted on silica gel (300ꢀ400 mesh). Melting points were
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determined on an Xꢀ5 Data microscopic melting point apparatus. NMR (400 MHz for H NMR, 100 for 13C NMR) spectra
were recorded in CDCl3 or acetoneꢀd6 with TMS as the internal standard. High resolution mass spectral (HRMS) analyses
were measured using EI (electron impact) with a QꢀTOF mass analyzer. The enantiomeric excess (ee) of the products
was determined by HPLC using Chiralcel ODꢀH column with isopropanol/hexane = 5/95 as the eluent, UV detection was
monitored at 254 nm.
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General procedure for the synthesis of imides 3. To a suspension of C3 (10.5 mg, 0.04 mmol) in THF (4 mL), tꢀ
o
BuOK (89.1 mg, 0.8 mmol) or NaH (29.0 mg, 1.2 mmol) for 3p–r was added under N2. After stirring at 25 C for 5 min,
aldehyde 2 (0.6 mmol), DPQ (245.2 mg, 0.6 mmol), and amide 1 (0.4 mmol) were added. The resulting mixture was stirred
for 0.5–3 h. After the complete consumption of 1 as detected by TLC, the mixture was quenched with a cold aqueous
solution of HCl (1 M, 10 mL), extracted with CH2Cl2 (10 mL × 3), dried over anhydrous Na2SO4, filtered and concentrated
under vacuum. The residue was purified by flash column chromatography on silica gel with hexane/acetone (v/v = 5:1) as
the eluent to give the product 3.
4ꢀChloroꢀNꢀtosylbenzamide (3a).15 Yield 119.8 mg (97%) from 68.4 mg (0.4 mmol) of amide 1a and 84.1 mg (0.6 mmol)
of aldehyde 2a stirred for 0.5 h as a white soild; mp 172−173 °C; 1H NMR (400 MHz, CDCl3, 25 oC, TMS) δ: 9.17 (s, 1H),
8.04–8.02 (m, 2H), 7.78–7.76 (m, 2H), 7.40–7.35 (m, 4H), 2.44 ppm (s, 3H); HRMS (EI): m/z calcd. for C14H12ClNO3S [M]+
309.0226, found 309.0219.
NꢀTosylbenzamide (3b).15 Yield 106.7 mg (97%) from 68.5 mg (0.4 mmol) of amide 1a and 63.8 mg (0.6 mmol) of
benzaldehyde stirred for 0.5 h as a white soild; mp 125−126 °C; H NMR (400 MHz, CDCl3, 25 oC, TMS) δ 9.03 (s, 1H),
1
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8.06–8.04 (m, 2H), 7.82–7.80 (m, 1H), 7.59–7.53 (m, 1H), 7.37 (d, 2H), 7.28–7.23 (m, 1H), 7.19–7.13 (m, 1H), 2.44 ppm
(s, 3H); HRMS (EI): m/z calcd. for C14H13NO3S [M]+ 275.0616, found 275.0619.
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2ꢀFluoroꢀNꢀtosylbenzamide (3c).16 Yield 110.2 mg (94%) from 68.4 mg (0.4 mmol) of amide 1a and 74.7 mg (0.6 mmol)
of 2ꢀfluorobenzaldehyde stirred for 0.5 h as a white soild; mp 135−136 °C; 1H NMR (400 MHz, CDCl3, 25 oC, TMS) δ 9.03
(s, 1H), 8.06–8.04 (m, 1H), 7.59–7.53 (m, 1H), 7.37 (d, J = 8.0 Hz, 2H), 7.28–7.24 (m, 1H), 7.35 (t, J = 7.8 Hz, 2H), 7.19–
7.13 (m, 1H), 2.44 ppm (s, 3H); HRMS (EI): m/z calcd. for C14H12FNO3S [M]+ 293.0522, found 293.0523.
3ꢀMethoxyꢀNꢀtosylbenzamide (3d).17 Yield 109.8 mg (90%) from 68.4 mg (0.4 mmol) of amide 1a and 81.9 mg (0.6
mmol) of 3ꢀmethoxybenzaldehyde stirred for 2 h as a white soild; mp 131−133 °C; 1H NMR (400 MHz, CDCl3, 25 oC, TMS)
δ 9.52 (s, 1H), 8.05 (d, J = 8.8 Hz, 2H), 7.40–7.28 (m, 5H), 7.08–7.06 (m, 1H), 3.76 (s, 3H), 2.43 ppm (s, 3H); HRMS (EI):
m/z calcd. for C15H15NO4S [M]+ 305.0722, found 305.0729.
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3ꢀNitroꢀNꢀtosylbenzamide (3e).18 Yield 111.3 mg (87%) from 67.4 mg (0.4 mmol) of amide 1a and 90.6 mg (0.6 mmol) of
3ꢀnitrobenzaldehyde stirred for 3 h as a white soild; mp 171−173°C; 1H NMR (400 MHz, acetoneꢀd6, 25 oC, TMS) δ 11.4 (s,
1H), 8.75–8.74 (m, 1H), 8.49–8.48 (m, 1H), 8.47–8.46 (m, 1H), 8.03 (d, J = 8.4 Hz, 2H), 7.85 (t, J = 8.0 Hz, 1H), 7.47 (d, J
= 8.0 Hz, 2H), 2.46 ppm (s, 3H); 13C NMR (100 MHz, acetoneꢀd6, 25 oC, TMS) δ 164.0, 149.2, 145.9, 137.5, 135.1, 134.5,
131.3, 130.4, 129.4, 128.3, 123.9; HRMS (EI): m/z calcd. for C14H12N2O5S [M]+ 320.0467, found 320.0461.
NꢀTosylthiopheneꢀ2ꢀcarboxamide (3f).15 Yield 97.8 mg (87%) from 67.4 mg (0.4 mmol) of amide 1a and 67.9 mg (0.6
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mmol) of thiopheneꢀ2ꢀcarbaldehyde stirred for 2.5 h as a white soild; mp 175−176 °C; H NMR (400 MHz, CDCl3, 25 oC,
TMS) δ 9.52 (s, 1H), 8.08 (d, J = 8.4 Hz, 2H), 7.75–7.74 (m, 1H), 7.62–7.61 (m, 1H), 7.39 (d, J = 8.0 Hz, 2H), 7.10–7.08
(m, 1H), 2.46 ppm (s, 3H); HRMS (EI): m/z calcd. for C12H11NO3S2 [M]+ 281.0180, found 281.0178.
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NꢀTosylꢀ2ꢀnaphthamide (3g).16 Yield 118.2 mg (91%) from 67.9 mg (0.4 mmol) of amide 1a and 93.8 mg (0.6 mmol) of
2ꢀnaphthaldehyde stirred for 1 h as a white soild; mp 164−165 °C; 1H NMR (400 MHz, CDCl3, 25 oC, TMS) δ 9.62 (s, 1H),
8.39 (s, 1H), 8.11 (d, J = 8.4 Hz, 2H), 7.88–7.82 (m, 4H), 7.59–7.52 (m, 2H), 7.35 (d, J = 8.4 Hz, 2H), 2.42 ppm (s, 3H);
HRMS (EI): m/z calcd. for C18H15NO3S [M]+ 325.0773, found 325.0779.
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NꢀTosylcinnamamide (3h).15 Yield 98.8 mg (82%) from 67.8 mg (0.4 mmol) of amide 1a and 79.3 mg (0.6 mmol) of
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cinnamaldehyde stirred for 1 h with hexane/acetone (v/v = 8:1) as a white soild; mp 135−136 °C; H NMR (400 MHz,
CDCl3, 25 oC, TMS) δ 9.22 (s, 1H), 7.96 (d, J = 8.4 Hz, 2H), 7.65 (d, J = 15.6 Hz, 1H), 7.40–7.38 (m, 2H), 7.31–7.19 (m,
4H), 6.42 (d, J = 15.6 Hz, 2H), 2.35 ppm (s, 3H); HRMS (EI): m/z calcd. for C16H15NO3S [M]+ 301.0773, found 301.0770.
NꢀTosyloctꢀ2ꢀynamide (3i). Yield 102.1 mg (87%) from 67.8 mg (0.4 mmol) of amide 1a and 74.5 mg (0.6 mmol) of octꢀ
2ꢀynal stirred for 2 h with hexane/ethyl acetate (v/v = 6:1) as a colorless oil; 1H NMR (400 MHz, acetoneꢀd6, 25 oC, TMS) δ
11.16 (s, 1H), 7.92–7.90 (m, 2H), 7.46–7.44 (m, 2H), 2.45 (s, 3H), 2.35 (t, J = 7.2 Hz, 2H), 1.54–1.50 (m, 2H), 1.37–1.28
(m, 4H), 0.87 ppm (t, J = 7.6 Hz, 3H); 13C NMR (100 MHz, acetoneꢀd6, 25 oC, TMS) δ 150.9, 145.9, 137.5, 130.4, 129.1,
92.9, 74.9, 31.7, 27.9, 22.7, 21.6, 18.9, 14.2 ppm; HRMS (EI): m/z calcd. for C15H19NO3S [M]+ 293.1086, found 293.1092.
3ꢀ(Cyclohexꢀ1ꢀenꢀ1ꢀyl)ꢀNꢀtosylpropiolamide (3j). Yield 95.8 mg (79%) from 67.8 mg (0.4 mmol) of amide 1a and 80.6 mg
(0.6 mmol) of 3ꢀ(cyclohexꢀ1ꢀenꢀ1ꢀyl)propiolaldehyde stirred for 2 h with hexane/ethyl acetate (v/v = 6:1) as a colorless oil;
1H NMR (400 MHz, acetoneꢀd6, 25 oC, TMS) δ 7.93–7.90 (m, 2H), 7.47–7.44 (m, 2H), 2.45 (s, 3H), 2.17–2.13 (m, 2H),
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2.12–2.08 (m, 2H), 1.66–1.56 ppm (m, 4H); 13C NMR (100 MHz, acetoneꢀd6, 25 C, TMS) δ 151.2, 145.9, 143.7, 137.5,
130.4, 129.1, 119.1, 91.1, 80.4, 28.5, 26.6, 22.5, 21.7, 21.6 ppm; HRMS (EI): m/z calcd. for C16H17NO3S [M]+ 303.0929,
found 303.0935.
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3ꢀPhenylꢀNꢀtosylpropiolamide (3k). Yield 84.5 mg (71%) from 67.8 mg (0.4 mmol) of amide 1a and 78.6 mg (0.6 mmol)
of 3ꢀphenylpropiolaldehyde stirred for 2 h with hexane/ethyl acetate (v/v = 7:1) as a colorless oil; 1H NMR (400 MHz,
CDCl3, 25 oC, TMS) δ 7.99 (d, J = 8.4 Hz, 2H), 7.53–7.51 (m, 2H), 7.47–7.45 (m, 1H), 7.39–7.34 (m, 1H), 2.44 ppm (s, 3H);
13C NMR (100 MHz, CDCl3, 25 oC, TMS) δ 149.7, 145.6, 135.2, 133.0, 131.2, 129.7, 128.7, 128.6, 118.8, 81.0, 21.8 ppm;
HRMS (EI): m/z calcd. for C16H13NO3S [M]+ 299.0616, found 299.0622.
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From (Z)ꢀ3ꢀbromoꢀ3ꢀphenylacrylaldehyde (126.7 mg, 0.6 mmol), tꢀBuOK (157.1 mg, 1.4 mmol), and 68.2 mg (0.4 mmol)
of amide 1a, 85.7 mg (72%) of imide 3k was isolated.
4ꢀChloroꢀNꢀ(phenylsulfonyl)benzamide (3l).5a Yield 112.1 mg (95%) from 62.9 mg (0.4 mmol) of benzenesulfonamide
and 84.1 mg (0.6 mmol) of aldehyde 2a stirred for 1.5 h with hexane/acetone (v/v = 4:1) as a white solid; mp 162−164 °C;
1H NMR (400 MHz, acetoneꢀd6, 25 oC, TMS) δ 11.10 (s, 1H), 8.13–8.11 (m, 2H), 7.96–7.94 (m, 2H), 7.76–7.72 (m, 1H),
7.68–7.63 (m, 2H), 7.56–7.53 ppm (m, 2H); HRMS (EI): m/z calcd. for C13H10ClNO3S [M]+ 295.0070, found 295.0077.
4ꢀChloroꢀNꢀ((3ꢀnitrophenyl)sulfonyl)benzamide (3m).19 Yield 103.4 mg (93%) from 80.1 mg (0.4 mmol) of 3ꢀ
nitrobenzenesulfonamide and 84.9 mg (0.6 mmol) of aldehyde 2a stirred for 2.5 h with hexane/acetone (v/v = 2:1) as a
yellow solid; mp 215−216 °C; 1H NMR (400 MHz, acetoneꢀd6, 25 oC, TMS) δ 11.33 (s, 1H), 8.89 (t, J = 1.6 Hz, 1H), 8.61–
8.59 (m, 1H), 8.55–8.52 (m, 1H), 8.03–7.96 (m, 3H), 7.56–7.54 ppm (m, 2H); 13C NMR (100 MHz, acetoneꢀd6, 25 oC, TMS)
δ 165.1, 149.1, 142.0, 140.1, 135.2, 131.8, 131.1, 131.0, 129.8, 129.2, 124.4 ppm; HRMS (EI): m/z calcd. for
C13H9ClN2O5S [M]+ 339.9921, found 339.9917.
4ꢀChloroꢀNꢀ((2ꢀchlorophenyl)sulfonyl)benzamide (3n).5a Yield 126.7 mg (96%) from 84.2 mg (0.4 mmol) of 2ꢀ
chlorobenzenesulfonamide and 84.6 mg (0.6 mmol) of aldehyde 2a stirred for 1 h with hexane/acetone (v/v = 4:1) as a
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white solid; mp 189−191 °C; H NMR (400 MHz, acetoneꢀd6, 25 oC, TMS) δ 11.41 (s, 1H), 8.34–8.31 (m, 1H), 8.01–7.99
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(m, 2H), 7.75–7.71 (m, 1H), 7.67–7.63 (m, 2H), 7.57–7.55 ppm (m, 2H); 13C NMR (100 MHz, acetoneꢀd6, 25 C, TMS) δ
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[M]+ 328.9680, found 328.9686.
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4ꢀChloroꢀNꢀ(methylsulfonyl)benzamide (3o).20 Yield 85.5 mg (92%) from 38.1 mg (0.4 mmol) of methanesulfonamide
and 84.5 mg (0.6 mmol) of aldehyde 2a stirred for 1 h with hexane/acetone (v/v = 3:1) as a white solid; mp 135−136 °C; 1H
NMR (400 MHz, acetoneꢀd6, 25 oC, TMS) δ 10.75 (s, 1H), 8.04–8.03 (m, 2H), 7.60–7.58 (m, 2H), 3.41 ppm (s, 3H); 13
C
NMR (100 MHz, acetoneꢀd6, 25 oC, TMS) δ 166.0, 139.8, 131.7, 131.0, 129.8, 41.7 ppm; HRMS (EI): m/z calcd. for
C8H8ClNO3S [M]+ 232.9913, found 232.9920.
NꢀBenzoylbenzamide (3p).5b Yield 81.9 mg (91%) from 48.6 mg (0.4 mmol) of benzamide and 63.6 mg (0.6 mmol) of
benzaldehyde stirred for 2 h with hexane/acetone (v/v = 6:1) as a white solid; mp 149−150 °C; 1H NMR (400 MHz,
acetoneꢀd6, 25 oC, TMS) δ = 10.4 (s, 1H), 8.00–7.98 (m, 4H), 7.64–7.61 (m, 2H), 7.54–7.50 ppm (m, 4H); 13C NMR (100
MHz, acetoneꢀd6, 25 oC, TMS) δ 167.8, 135.2, 133.4, 129.3, 129.3 ppm; HRMS (EI): m/z calcd. for C14H11NO2 [M]+
225.0790, found 225.0786.
NꢀBenzoylꢀ4ꢀchlorobenzamide (3q).5b Yield 99.9 mg (96%) from 48.5 mg (0.4 mmol) of benzamide and 84.5 mg (0.6
mmol) of aldehyde 2a stirred for 2 h with hexane/acetone (v/v = 6:1) as a white solid; mp 132−134 °C; 1H NMR (400 MHz,
CDCl3, 25 oC, TMS) δ 8.98 (s, 1H), 7.90–7.88 (m, 2H), 7.83–7.81 (m, 2H), 7.66–7.62 (m, 1H), 7.55–7.48 ppm (m, 4H);
HRMS (EI): m/z calcd. for C14H10ClNO2 [M]+ 259.0400, found 259.0405.
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NꢀBenzoylꢀ4ꢀnitrobenzamide (3r).5b Yield 96.1 mg (89%) from 66.5 mg (0.4 mmol) of 4ꢀnitrobenzamide and 64.1 mg (0.6
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mmol) of benzaldehyde stirred for 2 h with hexane/acetone (v/v = 4:1) as a white solid; mp 188−189 °C; H NMR (400
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1H), 7.56–7.52 ppm (m, 2H); 13C NMR (100 MHz, acetoneꢀd6, 25 C, TMS) δ 167.6, 167.4, 150.9, 141.1, 134.5, 133.8,
130.6, 129.4, 129.4, 124.3 ppm; HRMS (EI): m/z calcd. for C14H10N2O4 [M]+ 270.0640, found 270.0641.
(+)ꢀNꢀ(tertꢀButylsulfinyl)ꢀ4ꢀchlorobenzamide (3s). Yield 84.3 mg (81%, 98% ee) from 48.5 mg (0.4 mmol, 99% ee) of (S)ꢀ
2ꢀmethylpropaneꢀ2ꢀsulfinamide and 84.7 mg (0.6 mmol) of aldehyde 2a stirred for 1.5 h as a white soild; mp 149−151 °C;
1H NMR (400 MHz, CDCl3, 25 oC, TMS) δ 8.48 (s, 1H), 7.73 (d, J = 8.4 Hz, 2H), 7.39 (d, J = 8.4 Hz, 2H), 1.19 ppm (s, 9H);
13C NMR (100 MHz, CDCl3, 25 oC, TMS) δ 161.5, 138.7, 132.5, 130.5, 129.3, 57.9, 22.6 ppm; HRMS (EI): m/z calcd. for
C11H14ClNO2S [M]+ 259.0434, found 259.0439. Determined by HPLC with Chiralcel ODꢀH column at 254 nm
(hexane/iPrOH = 95:5, flow rate = 0.8 mL/min), tminor = 11.6 min, tmajor = 7.8 min. [α]20D = + 82.6 (c 0.80, CHCl3).
Nꢀ(Phenylsulfinyl)benzamide (3t).21 Yield 79.4 mg (81%) from 56.4 mg (0.4 mmol) of methanesulfonamide and 63.6 mg
(0.6 mmol) of benzaldehyde stirred for 3 h with hexane/acetone (v/v = 3:1) as a white solid; mp 145−146 °C; 1H NMR (400
MHz, acetoneꢀd6, 25 oC, TMS) δ 10.48 (s, 1H), 7.96–7.95 (m, 2H), 7.84–7.82 (m, 2H), 7.64–7.59 (m, 4H), 7.50–7.47 ppm
(m, 2H); HRMS (EI): m/z calcd. for C13H11NO2S [M]+ 245.0510, found 245.0513.
Synthesis of LY573636 (3u).13b To a suspension of C3 (79.5 mg, 0.3 mmol) in THF (25 mL), tꢀBuOK (673.3 mg, 6.0
mmol) was added under N2. After stirring for 10 min, 2,4ꢀdichlorobenzaldehyde (787.4 mg, 4.5 mmol), DPQ (1.840 g, 4.5
mmol) and 5ꢀbromothiopheneꢀ2ꢀsulfonamide (718.8 mg, 3.0 mmol) was added. The resulting mixture was stirred for 3 h,
quenched a cold aqueous solution of HCl (1 M, 25 mL) at 0–5 oC, extracted with CH2Cl2 (30 mL × 3), and then dried over
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anhydrous Na2SO4, filtered and concentrated under vacuum. Purified by column chromatography on silica gel with
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hexane/acetone (v/v = 4:1) as the eluent to afford 3s (1.081 g, 87%) as as a white solid; mp 168−170 °C; H NMR (400
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MHz, CDCl3, 25 oC, TMS) δ 9.19 (s, 1H), 7.73–7.71 (m, 2H), 7.45 (d, J = 1.6 Hz, 1H), 7.37–7.34 (m, 1H), 7.13 ppm (d, J =
8.0 Hz, 1H); HRMS (EI): m/z calcd. for C11H6BrCl2NO3S2 [M]+ 412.8350, found 412.8357.
Acknowledgments
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We thank the National Natural Science Foundation of China (21372196 and 21572199) for generous
financial support.
Supporting Information
The Supporting Information is available free of charge on the ACS Publications website.
Characterization data of new compounds (PDF)
References
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(3) Bailey, P. D.; Collier, I. D.; Morgan, K. M. In Comprehensive Organic Functional Group Transformations; Katritzky, A.
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