Synthesis of Allenyl Sulfones via a TBHP/TBAI-Mediated Reaction of Propargyl Alcohols with Sulfonyl Hydrazides

Article abstract of DOI:10.1021/acs.joc.5b01684

A new TBHP/TBAI-mediated reaction of propargyl alcohols with sulfonyl hydrazides in the presence of HOAc has been established, in which a wide variety of allenyl sulfones were obtained in moderate to excellent yields. Mechanistic studies indicate that thi

Full text of DOI:10.1021/acs.joc.5b01684

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Article
Synthesis of Allenyl Sulfones via a TBHP/TBAI-Mediated
Reaction of Propargyl Alcohols with Sulfonyl Hydrazides
Zheng Yang, Wen-Juan Hao, Shu-Liang Wang, Jin-Peng Zhang, Bo Jiang, Guigen Li, and Shu-Jiang Tu
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.5b01684 • Publication Date (Web): 17 Aug 2015
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The Journal of Organic Chemistry
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Synthesis of Allenyl Sulfones via a TBHP/TBAIꢀMediated Reaction
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of Propargyl Alcohols with Sulfonyl Hydrazides
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Zheng Yang,a WenꢀJuan Hao,*,a ShuꢀLiang Wang, a JinꢀPeng Zhang,b Bo Jiang,*,a Guigen Li,c,d and
ShuꢀJiang Tu,*,a
a
School of Chemistry and Chemical Engineering, Jiangsu Key Laboratory of Green Synthetic
Chemistry for Functional Materials, Jiangsu Normal University, Xuzhou 221116, P. R. China;
bDepartment of Public Health, Xuzhou Medical College, Jiangsu 221000, People’s Republic of China;
cInstitute of Chemistry & BioMedical Sciences, Collaborative Innovation Center of Chemistry for Life
Sciences, Nanjing University, Nanjing 210093, P. R. China; and dDepartment of Chemistry and
Biochemistry, Texas Tech University, Lubbock, TX 79409ꢀ1061, USA.
Eꢀmail:wjhao@jsnu.edu.cn, jiangchem@jsnu.edu.cn; laotu@jsnu.edu.cn;
RECEIVED DATE
ABSTRACT. A new TBHP/TBAIꢀmediated reaction of propargyl alcohols with sulfonyl hydrazides in
the presence of HOAc has been established, in which a wide variety of allenyl sulfones were obtained in
moderate to excellent yields. Mechanistic studies indicate that this transformation involves HOAcꢀ
promoted sulfonohydrazide intermediate formation, sequential C−O, CꢀN and NꢀS bond cleavage, and
C−S bond formation. Significantly, this sulfonohylation proceeds in a radical process and shows highly
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functional group compatibility and excellent regioselectivity, with a short reaction time and inexpensive
reagents.
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Introduction
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Allenes represent a privileged structural unit in a wide range of nonꢀnaturally and naturally occurring
products.1 Furthermore, allenes serve as an important and useful building block for substrateꢀspecific
domino cyclizations and have been widely utilized for numerous challenging and intriguing syntheses.2,3
They can readily result in various compounds with multifunctionalities via synergistic cascade processes
across C=C bonds system in oneꢀpot fashions.4 So far, enormous efforts have been focused on the highꢀ
efficient synthesis of allenes, which has made it more powerful and applicable.5ꢀ7 Moreover, functional
allenyl sulfones have been extensive applied in conjugate additions and cycloadditions,8 because these
molecules not only behave high and unique reactivity, but also the sulfone functionality can be removed
by various desulfonylation methods.9 The increasing applications of allenyl sulfones have stimulated
investigations on new methodologies for their synthesis.10 For instance, Ma and coꢀworkers developed
Heckꢀtype crossꢀcoupling reaction of allenes with aryl halides, leading to polyꢀsubstituted 1,2ꢀallenyl
sulfones (Scheme 1a).11 Despite these advances, the development of a more flexible protocol toward
allenyl sulfones with broad functional group tolerability is still highly desirable.
In the past decades, propargyl alcohols have proven to be versatile synthons, and have been efficiently
employed in various transformations and the preparation of bioactive molecules.12 Wang, Lv and coꢀ
workers reported the synthesis of allenephosphoramides through Yb(OTf)3ꢀcatalyzed reaction of
propargyl alcohols and diethyl arylphosphoramides.13 However, in sharp contrast, a facile metalꢀfree
sulfonylation of allenes initiated by a sulfonyl radical from propargyl alcohols is virtually unexplored.
Very recently, Zhan and coꢀworkers employed propargylic alcohols to react with pꢀ
tolylsulfonohydrazide to access acrylonitriles using FeCl3 as a catalyst (Scheme 1b).14 Inspired by these
useful transformations and our recent studies on oxidative coupling reactions,15 we envisioned that,
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under the right set of oxidative conditions, the reaction of propargylic alcohols with sulfonyl hydrazides
would proceed in a radical process to form allenyl sulfones. Herein, we report the successful realization
of this concept with the introduction of sulfonyl radicals for the flexible synthesis of polyꢀsubstituted
allenyl sulfones using tetrabutylammonium iodide (TBAI) and tertꢀbutyl hydroperoxide (TBHP)
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(Scheme 1c).
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Ma's work
O
O
O
O
S
H
H
S
Ar
[Pd]
(a)
(b)
Ph
Ph
+
Ar-X
R1
Ar
R1
Zhan's work
R2
R1
R2
CN
R1
FeCl3
Ts
TMS
H2NHN
+
HO
This work
R2
R1
NH2
R1
R2
Ar
R3
TBHP, TBAI
HOAc, CH3CN
Radical process
NH
Ar
+
S
(c)
O
HO
1
O
O
S
O
R3
2
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Scheme 1 Profiling Applications of Propargylic Alcohols
Results and Discussion
Optimization of the reaction conditions was performed by taking 1,1,3ꢀtriphenylpropꢀ2ꢀynꢀ1ꢀol (1a)
and pꢀtoluenesulfonyl hydrazide (2a) as the model substrates. Initially the reaction of 1a with 2a was
performed employing a combination of TBAI (20 mol %) and TBHP (2.0 equiv, 70% in water) in
o
acetonitrile at 40 C, and the desired product 3a was afforded, albeit with a low yield of 26% (Table 1,
entry 1). Other oxidants, such as H2O2 and diꢀtꢀbutyl peroxide (DTBP), were proven to be ineffective
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for this transformation (Table 1, entries 2–3). Increase in reaction temperature to 60 C delivered the
higher yield of 3a (entry 4); however, the higher reaction temperature (80 °C) decrease the chemical
yield (entry 5). A subsequent investigation of other catalysts was conducted in CH3CN. As illustrated in
entries 6−8, different types of catalysts including I2, CuI, and KI were investigated in the model
reaction, and it turned out that these catalysts hardly facilitate the reaction (entries 6ꢀ8). Next, we found
that the use of HOAc (1.0 mL) as an additive delivered 3a in 71% yield (entry 9). Notably, with the use
of TBAI (20 mol %) and TBHP (2.0 equiv), properly increase in the amount of HOAc (2.0 mL) could
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efficiently improve the yield to 84%, and the starting material 1a was completely consumed (entry 10).
Other solvents such as EtOH, tetrahydrofuran (THF), dichloroethane (DCE), 1,4ꢀdioxane, and ethyl
acetate (EA) were inferior to acetonitrile in terms of reaction yields (entries 11−15). Lowering loading
of TBAI or increasing the amount of TBHP all gave unsatisfactory results (31%–56% yields) (entries
16ꢀ18). Using HOAc as a solvent did not improve the yield of 3a (entry 19). Without oxidant, no
product 3a was observed (entry 20).
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Table 1 Optimization of Reaction Conditionsa
entry
1
oxidant (equiv)
TBHP (2.0)
H2O2 (2.0)
DTBP (2.0)
TBHP (2.0)
TBHP (2.0)
TBHP (2.0)
TBHP (2.0)
TBHP (2.0)
TBHP (2.0)
TBHP (2.0)
TBHP (2.0)
TBHP (2.0)
TBHP (2.0)
TBHP (2.0)
TBHP (2.0)
TBHP (2.0)
TBHP (3.0)
TBHP (4.0)
TBHP (2.0)
ꢀ
catalyst (mol %) additives (mL)
TBAI (20)
solvent
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
EtOH
t / oC
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40
40
60
80
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60
60
60
60
60
60
60
yield (%)b
26
2c
3d
4
TBAI (20)
ND
ND
52
TBAI (20)
TBAI (20)
5
TBAI (20)
37
6
I2 (20)
ND
ND
ND
71
7
CuI (20)
8
KI (20)
9
TBAI (20)
TBAI (20)
TBAI (20)
TBAI (20)
TBAI (20)
TBAI (20)
TBAI (20)
TBAI (10)
TBAI (20)
TBAI (20)
TBAI (10)
TBAI (20)
HOAc (1.0)
HOAc (2.0)
HOAc (2.0)
HOAc (2.0)
HOAc (2.0)
HOAc (2.0)
HOAc (2.0)
HOAc (2.0)
HOAc (2.0)
HOAc (2.0)
ꢀ
10
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12
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14
15
16
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18
19
20
84
ND
48
THF
DCE
62
1,4ꢀdioxane 60
59
EA
60
60
60
60
60
60
41
MeCN
MeCN
MeCN
HOAc
MeCN
31
56
41
43
HOAc (2.0)
ND
a Reaction conditions: 1a (1.0 mmol), 2a (2.0 mmol), additive, catalyst (0.2 equiv), oxidant (2.0 equiv) in solvent (4 mL).
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bIsolated yield is based on 1a. ND = No Detected.
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Having identified this acceptable optimization, we next set out to expand the scope of this reaction by
utilizing different sulfonyl hydrazide. First, the influence of substituents in the phenyl ring of sulfonyl
hydrazides 2 was investigated, which found that the sulfonylation reaction tolerated a broad spectrum of
substituted sulfonyl hydrazides carrying either electronꢀdonating, electronꢀneutral, or electronꢀ
withdrawing groups under the optimized conditions (Scheme 2). The variant of substituents resided at
different positions on the phenyl ring, such as Me, MeO, tꢀBu, Cl, and Br, were compatible, giving
access to the expected allenyl sulfones 3a-h with yields ranging from 61% to 84%. Notably, the
sterically more demanding 2ꢀchlorophenyl and 2ꢀnaphthalenyl (2ꢀNp) sulfonyl hydrazide were found to
have no influence on the course of the reaction, with allenyl sulfones 3f and 3k afforded in 74% and
69% yields, respectively. Even for challenging cases in which a strong electronꢀwithdrawing effect
exists on the para position on the aromatic ring (3i and 3j), good yields of 82% and 62% were provided.
Obviously, this sulfonylation can tolerate structurally diverse substrates with steric bulk and a different
electronic nature. Unluckily, aliphatic sulfonyl hydrazide (2l) was not adaptable substrates for this this,
which may be ascribed to the relative instability of the sulfonyl radicals generated in situ from aliphatic
sulfonyl hydrazides.
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Scheme 2. Scope of TBHP/TBAI-Mediated Sulfonylation Reaction.
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Yields of isolated products after column chromatography on silica gel are given. 1a (1.0 mmol) and 2 (2.0 mmol), TBAI (0.2 mmol), TBHP (2.0 mmol, 70%
1
2
in water), HOAc (2.0 mL), MeCN (4.0 mL), under an air atmosphere at 60 oC, 0.5 h.
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Scheme 3. Scope of TBHP/TBAI-Mediated Sulfonylation Reaction.
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Ar1
O
NH2
OH
R3
TBAI, TBHP
R1
S
R3
O
R1
R2
Ar1
NH
+
S
HOAc, MeCN, 60 o
C
O
O
R2
3
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4-ClPh
Ph
4-MePh
O
4-FPh
4-ClPh
O
O
O
Ph
S O
Ph
S
O
Ph
Ph
S
O
Ph
S
O
Ph
PhMe-4
PhMe-4
PhMe-4
Ph
Ph
Ph
3n (56%)
3p (73%)
3o (60%)
3m (75%)
4-ClPh
4-MePh
4-FPh
O
4-MePh
O
O
O
S
Ph
S
O
PhBr-3
Ph
S O
Ph
S
O
O
PhCl-4
PhCl-4
Ph
Ph
3t (68%)
Ph
Ph
3r (66%)
Ph
3s (57%)
4-MePh
3q (72%)
4-ClPh
4-MePh
O
O
O
4-FPh
S O
4-FPh
S
O
4-FPh
S
O
2-ClPh
4-ClPh
4-MePh
4-FPh
3w (72%)
4-FPh
4-FPh
3v (63%)
3u (65%)
4-MePh
4-ClPh
4-ClPh
O
O
O
Me
S O
Ph
S O
Ph
S O
Ph
Ph
Ph
4-ClPh
3z (42%)
4-MeOPh
3y (74%)
4-MePh
3x (76%)
Yields of isolated products after column chromatography on silica gel are given. 1 (1.0 mmol) and 2 (2.0 mmol), TBAI (0.2 mmol), TBHP (2.0 mmol, 70%
in water), HOAc (2.0 mL), MeCN (4.0 mL), under an air atmosphere at 60 oC, 0.5 h.
After the successful utilization of various sulfonyl hydrazides, we next extended our investigation to
the electronic nature of substituents on the phenyl ring of propargyl alcohols. As per our expectation,
propargyl alcohols bearing both electronꢀdonating and electronꢀwithdrawing groups on aromatic alkyne
moiety could take part in these reactions. Functional groups like fluoride, chloride, and methyl were
wellꢀtolerated (Scheme 3, 3m-3t). Likewise, different substituents on the aromatic rings directly
bounded to hydroxyl group can enable the reaction to occur steadily, efficiently converting into the
corresponding products 3u-3y in 63%ꢀ76% yields. Additionally, a significant drop in the yield was
observed for substrate with hydroxyl group linked a methyl group as has been demonstrated with
propargyl alcohol 1i, giving its expected product 3z in a 42% yield. These observations dedicated that
most functionalities of synthetic allenyl sulfones offer a flexible protocol to their further structural
modifications. The structures of products 3 were unambiguously determined by their NMR and HRꢀMS.
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Moreover, the structure of compound 3a was further confirmed by singleꢀcrystal Xꢀray diffraction
analysis. In general, these sulfonylationꢀbased domino reactions provide a new example for forming
richly decorated allenes, which are widespread structural cores in many bioactive compounds and serve
as important synthons for further applications.
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Noteworthily, when using easily prepared propargylic alcohol 1a as the substrate to develop the
efficiency of our method, a gramꢀscale reaction of 1a (50 mmol) with 2a (100 mmol) could be carried
out under the standard conditions to provide in a 68% yield of 3a (Scheme 4), which offered the
potential application in organic synthesis.
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Scheme 4. Scale-up Experiment
Scheme 5. Controlling Reactions
To understand the mechanism, several control experiments were conducted. Treatment of propargyl
alcohols 1a with tosylhydrazide 2a in the presence of 2,2,6,6ꢀtetramethylꢀ1ꢀpiperidinyloxy (TEMPO) or
butylhydroxytoluene (BHT) (2.0 equiv.) under the standard conditions gave complex mixtures without
observation of desired product 3a, which indicates the possible radical mechanism (Scheme 5a). The
preformed propꢀ2ꢀyneꢀ1,1,3ꢀtriyltribenzene 4 was subjected to the reaction with 2a, but no expected
product 3a was observed (Scheme 5b), confirming the hydroxyl group is essential for the success of this
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transformation. The reaction of 1a and sodium benzensulfinate under the standard conditions failed to
access the desired product 3a, indicating that hydrazides may participate in this reaction process
(Scheme 5c). Wihtout TBHP, propargyl alcohols 1a was treated with tosylhydrazide 2a under the
standard conditions at room temperature, providing sulfonohydrazides 5a in 78% yield (Scheme 5d).
Subsequently, the reaction of sulfonohydrazides 5a under the standard conditions generated the
corresponding allenyl sulfones 3a in an 83% chemical yield (Scheme 5c). This observation proves that
the reaction process involved the formation of sulfonohydrazide intermediate.
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On the basis of the above analysis and literature survey,12,13 a reasonable mechanism is outlined in
Scheme 6. Propargyl alcohols 1 is first converted to the allenic carbocation B via a MeyerꢀSchuster
rearrangement.16 Then, B is trapped by 2 to afford the key intermediate allenyl sulfonhydrazides C,
followed by tautomerization to yield sulfonohydrazides 5. The sulfonohydrazides 5 converts into allenyl
t
sulfonyldiazenes D via Hꢀabstractions by tBuO or BuOO radical generated from TBAIꢀaccelerated the
decomposition of TBHP.17,18 Intermediate D undergoes a sequential homolysis and radical coupling
process to afford target products 3. Although the catalytic formation of allenyl sulfones has been
achieved well,10,11 sulfonyl radical initiated functionalization of propargyl alcohols toward allenyl
sulfones is very rare in organic chemistry as mentioned earlier.
Scheme 6. Possible Mechanism
In conclusion, we have successfully developed an interesting method for the construction of polyꢀ
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substituted allenyl sulfones in a highly functionalꢀgroupꢀcompatible manner via TBHP/TBAIꢀmediated
reaction of propargyl alcohols with the commercially available sulfonyl hydrazide in the presence of
HOAc. The reaction pathway may involve a MeyerꢀSchuster rearrangement / key sulfonohydrazide
intermediate formation / Hꢀabstractions / homolysis of sulfonyldiazenes / radical coupling sequence by
the sequential cleavage of C−O, CꢀN and NꢀS bonds. This novel method not only extends the
applications of propargyl alcohols in organic chemistry but also provides an invaluable access to
structurally diverse allenyl sulfones. Moreover, this reaction could be enlarged to gram scale in a
satisfactory yield of 68%, which might display potential application in industrial production.
Experimental Section
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General
All oneꢀpot reactions were carried out in a 25ꢀmL Schlenk tube equipped with a magnetic stir bar under
air. Arylsulfonyl hydrazides 3 were prepared according to the known literatures.19 All other reagents
were obtained from commercial sources and used as received, if not stated otherwise. All melting points
are uncorrected. The NMR spectra were recorded in CDCl3 or DMSOꢀd6 on a 400 MHz instrument with
TMS as internal standard. Chemical shifts (δ) were reported in ppm with respect to TMS. Data are
represented as follows: chemical shift, mutiplicity (s = singlet, d = doublet, t = triplet, m = multiplet),
coupling constant (J, Hz) and integration. HRMS analyses were carried out using a TOFꢀMS instrument
with an ESI source. XꢀRay crystallographic analysis was performed with a SMART CCD and a P4
diffractometer.
General procedure for the synthesis of 3
Example for the synthesis of 3a
1,1,3ꢀTriphenylpropꢀ2ꢀynꢀ1ꢀol (1a, 1.0 mmol, 284 mg) was introduced in a 25ꢀmL Schlenk tube, pꢀ
toluenesulfonyl hydrazide (2a, 2.0 mmol, 372 mg), TBAI (0.2 mmol, 74 mg), tertꢀbutyl hydroperoxide
(2.0 mmol, 70% in water, 257 mg), acetic acid (2.0 mL) and acetonitrile (4.0 mL) were then
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o
successively added and stirred at 60 C. After the completion of the reaction (monitored by TLC), the
solvent was removed under vacuum. The residue was separated by flash column chromatography on
silica gel (eluent, petroleum ether/ethyl acetate 12:1 v/v) to afford the pure product 3a.
(3ꢀTosylpropaꢀ1,2ꢀdieneꢀ1,1,3ꢀtriyl)tribenzene (3a)
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white solid, 354 mg, 84% yield; mp 122ꢀ124 oC.
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1H NMR (400 MHz, CDCl3; δ, ppm) 7.65 (d, J = 8.0 Hz, 2H ), 7.59 (d, J = 9.6 Hz, 2H), 7.39ꢀ7.32 (m,
13H), 7.10 (s, 2H), 2.34 (s, 3H); 13C NMR (100 MHz, CDCl3; δ, ppm) 207.0, 144.3, 137.5, 133.8, 129.9,
129.5, 129.3, 129.0, 128.8, 128.8 128.7, 128.7, 128.1, 118.9, 117.8, 21.6; HRMS (ESIꢀTOF) m/z calcd
for C28H22NaO2S, 445.1233 [M+Na]+; found: 445.1239.
(3ꢀ((4ꢀMethoxyphenyl)sulfonyl)propaꢀ1,2ꢀdieneꢀ1,1,3ꢀtriyl)tribenzene (3b)
white solid, 267 mg, 61% yield; mp 141ꢀ143 oC.
1H NMR (400 MHz, CDCl3; δ, ppm) 7.69 (d, J = 8.8 Hz, 2H), 7.61ꢀ7.59 (m, 2H), 7.38ꢀ7.32 (m, 13H),
6.78 (d, J = 8.8 Hz, 2H), 3.80 (s, 3H); 13C NMR (100 MHz, CDCl3; δ, ppm) 206.6, 163.5, 133.8, 131.9,
130.3, 129.3, 129.0, 128.8, 128.8, 128.7, 128.7, 128.7, 118.8, 118.0, 114.0, 55.6; HRMS (ESIꢀTOF) m/z
calcd for C28H22NaO3S, 461.1182 [M+Na]+; found 461.1178.
(3ꢀ((4ꢀ(Tertꢀbutyl)phenyl)sulfonyl)propaꢀ1,2ꢀdieneꢀ1,1,3ꢀtriyl)tribenzene (3c)
white solid, 348 mg, 75% yield; mp 123ꢀ125 oC.
1H NMR (400 MHz, CDCl3; δ, ppm) 7.89ꢀ7.64 (m, 4H), 7.50ꢀ7.31 (m, 15H), 1.30 (d, J = 15.2 Hz, 9H);
13C NMR (100 MHz, CDCl3; δ, ppm) 206.8, 157.3, 137.4, 133.7, 131.7, 131.0, 129.8, 128.7, 128.6,
128.1, 128.0, 125.8, 124.8, 118.9, 117.9, 35.1, 31.0; HRMS (ESIꢀTOF) m/z calcd for C31H28NaO2S,
487.1703 [M+Na]+; found 487.1706.
(3ꢀ(Phenylsulfonyl)propaꢀ1,2ꢀdieneꢀ1,1,3ꢀtriyl)tribenzene (3d)
white solid, 302 mg, 74% yield; mp 150ꢀ152 oC.
1H NMR (400 MHz, CDCl3; δ, ppm) 7.78ꢀ7.76 (m, 2H), 7.59ꢀ7.57 (m, 2H), 7.50ꢀ7.46 (m, 1H), 7.38ꢀ
7.29 (m, 15H); 13C NMR (100 MHz, CDCl3; δ, ppm) 207.0, 140.3, 133.6, 133.4, 129.1, 128.9, 128.8(5),
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128.8(0), 128.7(8), 128.7(6), 128.7, 128.1, 119.1, 117.5; HRMS (ESIꢀTOF) m/z calcd for C27H20NaO2S,
431.1077 [M+Na]+; found 431.1090.
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(3ꢀ((4ꢀChlorophenyl)sulfonyl)propaꢀ1,2ꢀdieneꢀ1,1,3ꢀtriyl)tribenzene (3e)
white solid, 305 mg, 69% yield; mp 130ꢀ132 oC.
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1H NMR (400 MHz, CDCl3; δ, ppm) 7.69ꢀ7.66 (m, 2H), 7.60ꢀ7.58 (m, 2H), 7.40ꢀ7.32 (m, 13H), 7.28 (m,
2H); 13C NMR (100 MHz, CDCl3; δ, ppm) 207.2, 140.1, 138.9, 133.4, 129.4, 129.3, 129.1(3), 129.0(5),
128.9, 128.8, 128.7, 119.5, 117.5; HRMS (ESIꢀTOF) m/z calcd for C27H19ClNaO2S, 465.0687 [M+Na]+;
found 465.0691.
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(3ꢀ((2ꢀChlorophenyl)sulfonyl)propaꢀ1,2ꢀdieneꢀ1,1,3ꢀtriyl)tribenzene (3f)
white solid, 327 mg, 74% yield; mp 123ꢀ125 oC.
1H NMR (400 MHz, CDCl3; δ, ppm) 8.15ꢀ8.13 (m, 1H), 7.63ꢀ7.61 (m, 2H), 7.38ꢀ7.27 (m, 15H), 7.18ꢀ
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7.16 (m, 1H); C NMR (100 MHz, CDCl3; δ, ppm) 207.1, 137.4, 134.3, 133.5, 133.3, 131.7, 131.6,
129.2, 129.0(5), 129.0(0), 128.8(5), 128.8, 128.7, 126.8, 120.4, 116.5; HRMS (ESIꢀTOF) m/z calcd for
C27H19ClNaO2S, 465.0687 [M+Na]+; found 465.0692.
(3ꢀ((4ꢀBromophenyl)sulfonyl)propaꢀ1,2ꢀdieneꢀ1,1,3ꢀtriyl)tribenzene (3g)
white solid, 335 mg, 69% yield; mp 120ꢀ122 oC.
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1H NMR (400 MHz, CDCl3; δ, ppm) 7.60ꢀ7.57 (m, 4H), 7.44ꢀ7.31 (m, 15H); C NMR (100 MHz,
CDCl3; δ, ppm) 207.3, 139.5, 133.4, 132.1, 129.5, 129.3, 129.1, 128.9, 128.8, 128.7, 128.7, 119.5, 117.4;
HRMS (ESIꢀTOF) m/z calcd for C27H19BrNaO2S, 509.0182 [M+Na]+; found 509.0187.
(3ꢀ((3ꢀBromophenyl)sulfonyl)propaꢀ1,2ꢀdieneꢀ1,1,3ꢀtriyl)tribenzene (3h)
white solid, 389 mg, 80% yield; mp 87ꢀ89 oC.
1H NMR (400 MHz, CDCl3; δ, ppm) 7.93ꢀ7.92 (m, 1H), 7.72 (d, J = 8.4 Hz, 1H), 7.63ꢀ7.60 (m, 3H),
7.43ꢀ7.34 (m, 13H), 7.24ꢀ7.20 (m, 1H); 13C NMR (100 MHz, CDCl3; δ, ppm) 207.3, 142.3, 136.4, 133.3,
130.9, 130.3, 129.3, 129.1, 128.9, 128.9, 128.8, 128.7, 128.6, 126.6, 123.0, 119.6, 117.3; HRMS (ESIꢀ
TOF) m/z calcd for C27H19BrNaO2S, 509.0182 [M+Na]+; found 509.0185.
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(3ꢀ((4ꢀ(Trifluoromethyl)phenyl)sulfonyl)propaꢀ1,2ꢀdieneꢀ1,1,3ꢀtriyl)tribenzene (3i)
white solid, 409 mg, 82% yield; mp 119ꢀ121 oC.
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1H NMR (400 MHz, CDCl3; δ, ppm) 7.86 (d, J = 8.0 Hz, 2H), 7.61ꢀ7.59 (m, , 2H), 7.54 (d, J = 8.0 Hz,
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2H), 7.39ꢀ7.29 (m, 13H); C NMR (100 MHz, CDCl3; δ, ppm) 207.6, 144.1, 135.0 (JCF = 32.9 Hz),
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134.7, 133.2, 129.4, 129.2, 128.9, 128.9, 128.8, 128.6, 128.5, 125.9 (JCF = 3.7 Hz), 123.1 (JCF = 271.3
Hz), 119.8, 117.2; HRMS (ESIꢀTOF) m/z calcd for C28H19F3NaO2S, 499.0951 [M+Na]+; found
499.0965.
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(3ꢀ((4ꢀNitrophenyl)sulfonyl)propaꢀ1,2ꢀdieneꢀ1,1,3ꢀtriyl)tribenzene (3j)
white solid (281 mg, 62% yield) mp 167ꢀ169 oC.
1H NMR (400 MHz, CDCl3; δ, ppm) 8.11ꢀ8.09 (m, 2H), 7.91ꢀ7.88 (m, 2H), 7.60ꢀ7.57 (m, 2H), 7.41ꢀ
7.32 (m, 13H); 13C NMR (100 MHz, CDCl3; δ, ppm) 208.1, 150.4, 146.3, 133.0, 129.6, 129.4, 129.2,
129.0, 129.0, 128.8, 128.6, 128.4, 124.0, 120.2, 117.0; HRMS (ESIꢀTOF) m/z calcd for C27H19NNaO4S,
476.0927 [M+Na]+; found 476.0929.
1ꢀ((1,3,3ꢀTriphenylpropaꢀ1,2ꢀdienꢀ1ꢀyl)sulfonyl)naphthalene (3k)
White solid, 316 mg, 69% yield; mp 134ꢀ136 oC.
1H NMR (400 MHz, CDCl3; δ, ppm) 8.35 (s, 1H), 7.81 (d, J = 8.4 Hz, 1H), 7.73ꢀ7.68 (m, 3H), 7.62ꢀ
7.52 (m, 4H), 7.35ꢀ7.28 (m, 13H); 13C NMR (100 MHz, CDCl3; δ, ppm) 207.5, 137.4, 135.1, 133.6,
132.0, 129.1, 129.4, 129.2, 129.1(1), 129.0(7), 129.0, 128.9, 128.8, 128.8, 128.7(5), 128.6(9), 127.8,
127.4, 122.8, 119.2, 117.6; HRMS (ESIꢀTOF) m/z calcd for C31H22NaO2S, 481.1233 [M+Na]+; found
481.1237.
3ꢀ(4ꢀFluorophenyl)ꢀ3ꢀtosylpropaꢀ1,2ꢀdieneꢀ1,1ꢀdiyl)dibenzene (3m)
white solid, 330 mg, 75% yield; mp 132ꢀ134 oC.
1H NMR (400 MHz, CDCl3; δ, ppm) 7.86 (m, 4H), 7.50ꢀ7.35 (m, 10H), 7.10ꢀ7.05 (m, 4H), 2.38 (s, 3H);
13C NMR (100 MHz, CDCl3; δ, ppm) 215.7, 161.8 (1JCF = 243.4 Hz), 159.7, 144.8, 135.5, 133.8 (3JCF
=
8.5 Hz), 133.1, 131.2, 129.8, 128.7, 128.5, 128.(4)5, 128.2, 118.1, 115.9 (2JCF = 22.1 Hz), 21.7; HRMS
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(ESIꢀTOF) m/z calcd for C28H21FNaO2S, 463.1139 [M+Na]+; found 463.1140.
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White solid, 255 mg, 56% yield; mp 147ꢀ149 oC.
1H NMR (400 MHz, CDCl3; δ, ppm) 7.85ꢀ7.83 (m, 4H), 7.41ꢀ7.37 (m, 4H), 7.37ꢀ7.34 (m, 8H), 7.08 (d,
J = 8.4 Hz, 2H), 2.37 (s, 3H); 13C NMR (100 MHz, CDCl3; δ, ppm) 207.1, 144.8, 135.4, 135.3, 133.1,
133.0, 132.9, 131.1, 129.8, 128.9, 128.7, 128.4, 128.2, 120.5, 21.7; HRMS (ESIꢀTOF) m/z calcd for
C28H21ClNaO2S, 479.0843 [M+Na]+; found 479.0853.
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(3ꢀ(pꢀTolyl)ꢀ3ꢀtosylpropaꢀ1,2ꢀdieneꢀ1,1ꢀdiyl)dibenzene (3o)
white solid, 262 mg, 60% yield; mp 90ꢀ92 oC.
1H NMR (400 MHz, CDCl3; δ, ppm) 7.66 (d, J = 8.0 Hz, 2H), 7.49 (d, J = 8.0 Hz, 2H), 7.38ꢀ7.33 (m,
10H), 7.18ꢀ7.12 (m, 4H), 2.36 (s, 3H), 2.36 (s, 3H); 13C NMR (100 MHz, CDCl3; δ, ppm) 206.9, 144.2,
139.1, 137.6, 133.9, 129.4, 128.7, 128.1, 126.2, 118.7, 117.7, 21.6, 21.3; HRMS (ESIꢀTOF) m/z calcd
for C29H24NaO2S, 459.1390 [M+Na]+; found 459.1409.
(3ꢀ(4ꢀChlorophenyl)ꢀ3ꢀ(phenylsulfonyl)propaꢀ1,2ꢀdieneꢀ1,1ꢀdiyl)dibenzene (3p)
White solid, 323 mg, 73% yield; mp 127ꢀ129 oC.
1H NMR (400 MHz, CDCl3; δ, ppm) 7.77ꢀ7.75 (m, 2H), 7.54ꢀ7.48 (m, 3H), 7.38ꢀ7.28 (m, 14H); 13C
NMR (100 MHz, CDCl3; δ, ppm) 207.0, 140.2, 135.2, 133.5, 133.4, 130.1, 129.0, 128.9, 128.8, 128.7,
128.06, 127.7, 119.5, 116.7; HRMS (ESIꢀTOF) m/z calcd for C27H19ClNaO2S, 465.0687 [M+Na]+;
found 465.0689.
(3ꢀ(Phenylsulfonyl)ꢀ3ꢀ(pꢀtolyl)propaꢀ1,2ꢀdieneꢀ1,1ꢀdiyl)dibenzene (3q)
White solid, 304 mg, 72% yield; mp 130ꢀ132 oC.
1H NMR (400 MHz, CDCl3; δ, ppm) 7.79ꢀ7.77 (m, 2H), 7.51ꢀ7.47 (m, 3H), 7.36ꢀ7.31 (m, 12H), 7.16 (d,
J = 8.0 Hz, 2H), 2.35 (s, 3H); 13C NMR (100 MHz, DMSOꢀd6; δ, ppm) 206.9, 140.5, 139.2, 133.8, 133.3,
129.4, 128.8, 128.7, 128.7, 128.1, 126.1, 118.9, 117.5, 21.3; HRMS (ESIꢀTOF) m/z calcd for
C28H22NaO2S, 445.1233 [M+Na]+; found 445.1245.
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(3ꢀ((4ꢀChlorophenyl)sulfonyl)ꢀ3ꢀ(4ꢀfluorophenyl)propaꢀ1,2ꢀdieneꢀ1,1ꢀdiyl)dibenzene (3r)
white solid, 305 mg, 66% yield; mp 146ꢀ148 oC.
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1H NMR (400 MHz, CDCl3; δ, ppm) 7.66 (d, J = 8.4 Hz, 2H), 7.59ꢀ7.55 (m, 2H), 7.41ꢀ7.39 (m, 6H),
7.32ꢀ7.29 (m, 6H), 7.09ꢀ7.05 (m, 2H); 13C NMR (100 MHz, CDCl3; δ, ppm) 207.0, 163.2 (1JCF = 248.5
Hz), 140.2, 138.7, 133.3, 130.8 (3JCF = 8.4Hz), 129.4, 129.2, 129.1, 128.9, 128.6, 124.8, 119.6, 116.6,
116.0 (2JCF = 21.7); HRMS (ESIꢀTOF) m/z calcd for C27H18ClFNaO2S, 483.0593 [M+Na]+; found
483.0596.
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(3ꢀ((4ꢀChlorophenyl)sulfonyl)ꢀ3ꢀ(pꢀtolyl)propaꢀ1,2ꢀdieneꢀ1,1ꢀdiyl)dibenzene (3s)
white solid, 260 mg, 57% yield; mp 102ꢀ104 oC.
1H NMR (400 MHz, CDCl3; δ, ppm) 7.69 (d, J = 8.4 Hz, 2H), 7.49 (d, J = 8.0 Hz, 2H), 7.42ꢀ7.33 (m,
10H), 7.30ꢀ7.28 (m, 2H), 7.19 (d, J = 8.0 Hz, 2H), 2.37 (s, 3H); 13C NMR (100 MHz, DMSOꢀd6; δ, ppm)
207.1, 140.0, 139.4, 139.0, 133.6, 129.5, 129.4, 129.1, 129.0, 128.8, 128.7, 128.6, 125.8, 119.2, 117.4,
21.3; HRMS (ESIꢀTOF) m/z calcd for C28H21ClNaO2S, 479.0843 [M+Na]+; found 479.0850.
(3ꢀ((3ꢀBromophenyl)sulfonyl)ꢀ3ꢀ(4ꢀchlorophenyl)propaꢀ1,2ꢀdieneꢀ1,1ꢀdiyl)dibenzene (3t)
white solid, 353 mg, 68% yield; mp 105ꢀ107 oC.
1H NMR (400 MHz, CDCl3; δ, ppm) 7.90 (s, 1H), 7.69 (d, J = 8.0 Hz, 1H), 7.62 (d, J = 8.0 Hz, 1H),
7.54 (d, J = 8.4 Hz, 2H), 7.41ꢀ7.29 (m, 12H), 7.24ꢀ7.20 (m, 1H); 13C NMR (100 MHz, CDCl3; δ, ppm)
207.3, 142.0, 136.6, 135.5, 133.1, 130.9, 130.4, 130.0, 129.2(4), 129.1(5), 129.0, 128.6, 127.3, 126.5,
123.1, 120.0, 116.5; HRMS (ESIꢀTOF) m/z calcd for C27H18BrClNaO2S, 544.9766 [M+Na]+; found
544.9775.
4,4'ꢀ(3ꢀ(Pꢀtolyl)ꢀ3ꢀtosylpropaꢀ1,2ꢀdieneꢀ1,1ꢀdiyl)bis(fluorobenzene) (3u)
white solid (307 mg, 65% yield; mp 108ꢀ110 oC.
1H NMR (400 MHz, CDCl3; δ, ppm) 7.62 (d, J = 8.4 Hz, 2H), 7.43 (d, J = 8.4 Hz, 2H), 7.32ꢀ7.27 (m,
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4H), 7.17ꢀ7.13 (m, 4H), 7.09ꢀ7.05 (m, 4H), 2.36 (s, 3H), 2.35 (s, 3H); C NMR (100 MHz, CDCl3; δ,
ppm) 206.6, 164.3, 161.7 (1JCF = 252.0 Hz), 144.4, 139.3, 137.5, 130.4 (3JCF = 8.3 Hz), 129.8, 129.8,
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129.5, 129.5, 128.6, 128.0, 126.0, 117.9, 117.0, 115.9 (2JCF = 22.7 Hz), 21.6, 21.3; HRMS (ESIꢀTOF)
m/z calcd for C29H22F2NaO2S, 495.1201 [M+Na]+; found 495.1205.
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white solid, 307 mg, 65% yield; mp 108ꢀ110 oC.
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1H NMR (400 MHz, CDCl3; δ, ppm) 7.65 (d, J = 8.4 Hz, 2H), 7.42 (d, J = 8.0 Hz, 2H), 7.32ꢀ7.28 (m,
6H), 7.19ꢀ7.07 (m, 6H), 2.40 (s, 3H); 13C NMR (100 MHz, CDCl3; δ, ppm) 206.8, 163.2 (1JCF = 248.2
Hz), 140.2, 139.7, 138.9, 130.4, (3JCF = 8.4Hz), 129.6, 129.5 (4JCF = 3.0 Hz), 129.4, 129.2, 128.7, 125.6,
117.6, 117.5, 116.0 (2JCF = 21.7), 21.3; HRMS (ESIꢀTOF) m/z calcd for C28H19ClF2NaO2S, 515.0655
[M+Na]+; found 515.0660.
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4,4'ꢀ(3ꢀ(4ꢀChlorophenyl)ꢀ3ꢀ((2ꢀchlorophenyl)sulfonyl)propaꢀ1,2ꢀdieneꢀ1,1ꢀdiyl)bis(fluorobenzene) (3w)
white solid, 369 mg, 72% yield; mp 151ꢀ153 oC.
1H NMR (400 MHz, CDCl3; δ, ppm) 8.13ꢀ8.11 (m, 1H), 7.51 (d, J = 8.4 Hz, 2H), 7.42ꢀ7.29 (m, 8H),
7.24 (d, J = 8.0 Hz, 1H), 7.10ꢀ7.06 (m, 4H); 13C NMR (100 MHz, DMSOꢀd6; δ, ppm) 206.9, 163.3 (1JCF
= 248.2 Hz), 137.2, 135.5, 134.5, 133.1, 131.7, 131.6, 130.7 (3JCF = 8.4Hz), 130.1, 129.2 (4JCF = 3.3 Hz),
129.1, 127.3, 127.0, 119.0, 115.9 (2JCF = 21.7); HRMS (ESIꢀTOF) m/z calcd for C27H16Cl2F2NaO2S,
535.0109 [M+Na]+; found 535.0111.
1ꢀChloroꢀ4ꢀ(3ꢀphenylꢀ1ꢀ(phenylsulfonyl)ꢀ3ꢀ(pꢀtolyl)propaꢀ1,2ꢀdienꢀ1ꢀyl)benzene (3x)
white solid, 347 mg, 76% yield; mp 98ꢀ100 oC.
1H NMR (400 MHz, CDCl3; δ, ppm) 7.77 (d, J = 7.2 Hz, 2H), 7.54ꢀ7.51 (m, 3H), 7.38ꢀ7.31 (m, 9H),
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7.19 (s, 4H), 2.40 (s, 3H); C NMR (100 MHz, DMSOꢀd6; δ, ppm) 207.0, 140.2, 139.1, 135.2, 133.6,
133.5, 130.3, 130.0, 129.5, 129.0, 128.9, 128.9, 128.8, 128.7, 128.6, 128.1, 127.8, 119.5, 116.5, 100.0,
21.3; HRMS (ESIꢀTOF) m/z calcd for C28H21ClNaO2S, 479.0843 [M+Na]+; found 479.0854.
1ꢀChloroꢀ4ꢀ(3ꢀ(4ꢀmethoxyphenyl)ꢀ3ꢀphenylꢀ1ꢀ(phenylsulfonyl)propaꢀ1,2ꢀdienꢀ1ꢀyl)benzene (3y)
white solid, 349 mg, 74% yield; mp 114ꢀ116 oC.
1H NMR (400 MHz, CDCl3; δ, ppm) 7.77 (d, J = 7.6 Hz, 2H), 7.54ꢀ7.49 (m, 3H), 7.39ꢀ7.28 (m, 9H),
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7.23 (d, J = 8.4 Hz, 2H), 6.91 (d, J = 8.4 Hz, 2H), 3.85 (s, 3H); C NMR (100 MHz, CDCl3; δ, ppm)
207.0, 160.3, 140.2, 135.1, 133.7, 133.5, 130.0(4), 129.9(9), 129.0, 128.9, 128.8, 128.7, 128.0, 127.9,
125.3, 119.3, 116.4, 114.3, 55.4; HRMS (ESIꢀTOF) m/z calcd for C28H21ClNaO2S, 479.0843 [M+Na]+;
found 479.0854.
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1ꢀChloroꢀ4ꢀ(4ꢀ(phenylsulfonyl)ꢀ4ꢀ(pꢀtolyl)butaꢀ2,3ꢀdienꢀ2ꢀyl)benzene (3z)
white solid, 165 mg, 42% yield; mp 102ꢀ104 oC.
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1H NMR (400 MHz, CDCl3; δ, ppm) 7.68ꢀ7.56 (m, 5H), 7.45ꢀ7.41 (m, 2H), 7.36ꢀ7.29 (m, 4H), 7.19 (d,
J = 8.0 Hz, 2H), 2.40 (s, 3H), 2.19 (s, 3H);
13C NMR (100 MHz, CDCl3; δ, ppm) 139.5, 135.3, 134.6, 134.0, 133.1, 131.6, 131.0, 130.5, 129.2,
128.2, 128.2, 118.6, 90.0, 85.2, 22.2, 21.6; HRMS (ESIꢀTOF) m/z calcd for C23H19ClNaO2S, 417.0687
[M+Na]+; found 417.0700.
(3ꢀ(pꢀTolyl)propꢀ2ꢀyneꢀ1,1ꢀdiyl)dibenzene (4)(Known compound)20
white solid, mp 83ꢀ85 oC
1H NMR (400 MHz, CDCl3; δ, ppm) 7.44 (d, J = 7.6 Hz, 4H), 7.38ꢀ7.24 (m, 7H), 7.22 (d, J = 7.2 Hz,
1H), 7.11 (d, J = 8.0 Hz, 2H), 5.20 (s, 1H), 2.34 (s, 3H); 13C NMR (100 MHz, CDCl3; δ, ppm) 141.9,
138.0, 131.6, 129.0, 128.6, 127.9, 126.9, 120.4, 89.4, 85.0, 43.8, 21.5.
1ꢀ(pꢀTolyl)ꢀ2ꢀ(1,3,3ꢀtriphenylallylidene)hydrazine (5a) (Known compound)
white solid, mp 177ꢀ179 oC (Lit. mp 174ꢀ176 oC).21
1H NMR (400 MHz, CDCl3; δ, ppm) 7.85 (s, 1H), 7.62 (d, J = 8.0 Hz, 4H), 7.42ꢀ7.33 (m, 5H), 7.30ꢀ
7.23 (m, 5H), 7.17ꢀ7.12 (m, 1H), 7.05ꢀ6.93 (m, 4H), 6.38 (d, J = 4.8 Hz, 1H), 2.42 (s, 3H).
ASSOCIATED CONTENT
Supporting Information
1H and 13C NMR spectra for all pure products, and Xꢀray crystal data (CIF) for 3a. This material is
available free of charge via the Internet at http://pubs.acs.org.
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Notes
The authors declare no competing financial interest.
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ACKNOWLEDGMENT
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We are grateful for financial support from the NSFC (Nos. 21332005, 21232004, 21272095, and
21472071), PAPD of Jiangsu Higher Education Institutions, the Qing Lan Project (12QLG006), the
Outstanding Youth Fund of JSNU (YQ2015003), Robert A. Welch Foundation (Dꢀ1361, USA), and
NIH (R33DA031860, USA), and the NSF of of JSNU (14XLR005), and the Open Foundation of
Jiangsu Key Laboratory (K201505).
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