TBAI/K2S2O8 Initiated Radical Cyclization to Synthesize β- Arylsulfonyl Naphthalenes from Homopropargylic Alcohols and Sulfonyl Hydrazides

Article abstract of DOI:10.1002/adsc.201700634

A metal-free radical addition method for the synthesis of β-arylsulfonyl naphthalenes with homopropargylic alcohols and sulfonyl hydrazides has been developed. In this reaction, sulfonyl hydrazide is employed as the source of sulfonyl radical to produce the desired sulfone directly. There is the first example for homopropargylic alcohol through direct intramolecular addition of vinyl radical to arenes with sulfonyl radical, which is initiated by the TBAI/K₂S₂O₈ reaction system and generates the desired products in moderate yields. (Figure presented.).

Full text of DOI:10.1002/adsc.201700634

Title: TBAI/K2S2O8 Initiated Radical Cyclization to Synthesize β-
Arylsulfonyl Naphthalenes from Homopropargylic Alcohols and
Sulfonyl Hydrazides
Authors: xiaodong yang, lianbiao zhao, bingxiang yuan, zhenjie qi, and
Ru-Long Yan
This manuscript has been accepted after peer review and appears as an
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To be cited as: Adv. Synth. Catal. 10.1002/adsc.201700634
Link to VoR: http://dx.doi.org/10.1002/adsc.201700634

10.1002/adsc.201700634
Advanced Synthesis & Catalysis
UPDATE
DOI: 10.1002/adsc.201((will be filled in by the editorial staff))
Xiaodong Yang,† Lianbiao Zhao,‡ Bingxiang Yuan,† Zhenjie Qi,† Rulong Yan*†
† State Key Laboratory of Applied Organic Chemistry, Key laboratory of Nonferrous Metal Chemistry and Resources
Utilization of Gansu Province, Department of Chemistry, Lanzhou University, Lanzhou, Gansu, China
‡ College of Chemical Engineering, Northwest University for Nationalities, Lanzhou, Gansu, China
Fax: 0931-8912596 E-mail: yanrl@lzu.edu.cn
Received: ((will be filled in by the editorial staff))
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201######.((Please
delete if not appropriate))
Abstract. A metal-free radical addition method for the
synthesis of β-arylsulfonyl naphthalenes with
alkynes has drawn more attentions for its offering
straightforward approaches to synthesize sulfones.
Several elegant and significant works about sulfonyl
radical addition to alkynes have been reported by
the group of Tian, Tu, Li, Breit, Wang and so on.[7]
Due to the wide applications of sulfone, it is of great
interest to develop efficient and direct method for
the construction of sulfone.
homopropargylic alcohols and sulfonyl hydrazides has been
developed. In this reaction, sulfonyl hydrazide is employed
as the source of sulfonyl radical to produce the desired
sulfone directly. There is the first example for
homopropargylic alcohol through direct intramolecular
addition of vinyl radical to arenes with sulfonyl radical,
which is initiated by the TBAI/K2S2O8 reaction system and
generates the desired products in moderate yields.
Keywords: β- arylsulfonyl naphthalenes; homopropargylic
alcohols; sulfonyl hydrazides
Organosulfones motifs represent as privileged
structure in the fields of organic synthesis,
pharmaceutical industry, agrochemicals as well as
materials science.[1] Particularly, the sulfones have
been used as drug candidates for anticancer, HIV
and Parkinson’s diseases for its significant
biological activities.[2] On the other hand,
desulfonylation reactions have also been flourished
in the total synthesis through functional group
transformations (FGTs) because the sulfonyl is a
good leaving group.[3] Common strategies for
sulfones preparation mainly include the introduction
sulfonyl group with sulfonylating reagents and
oxidation of the sulfide.[4] Compared to the
traditional sulfonylating reagents, such as sodium
sulfinate, arylsulfinic acids, sulfonyl halides,[5]
sulfonyl hydrazides have emerged as ideal
sulfonylating agents because of its commercial
availability, stability and high reactivity.[6] Recently,
radical-triggered addition of sulfonyl radical to
Scheme 1. The reactions of homopropargylic alcohols
The homopropargylic alcohols, interesting and
useful substrates, have been heavily studied recent
years.[8] The radical rearrangement and nucleophilic
addition methods empolying homopropargylic
alcohol as substrate had been well developed in the
past several years. In the field of nucleophilic
1
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10.1002/adsc.201700634
Advanced Synthesis & Catalysis
Table 1. Optimization of reaction conditions a
Scheme 2. The scope of substituted sulfonyl
hydrazides
entr
y
catalyst(20
mol %)
oxidant
(equiv)
additives
solvent
yield
(%)b
(20 mol %)
1
TBAI
TBAI
TBAI
TBAI
TBAI
TBAI
TBAI
TBAI
TBAI
TBAI
TBAI
TBAI
TBAI
TBAI
TBAI
TBAI
KI
K2S2O8 (3)
K2S2O8 (3)
K2S2O8 (3)
K2S2O8 (3)
K2S2O8 (3)
K2S2O8 (3)
K2S2O8 (4)
TBHP (4)
TBP (4)
Oxone® (4)
K2S2O8 (4)
K2S2O8 (4)
K2S2O8 (4)
K2S2O8 (4)
K2S2O8 (4)
K2S2O8 (4)
K2S2O8 (4)
K2S2O8 (4)
K2S2O8 (4)
-
DCE
45
53
trace
trace
36
-
2
-
CH3NO2
DMF
3
-
4
-
DMSO
CH3CN
EtOH
5
-
6
-
7
-
CH3NO2
CH3NO2
CH3NO2
CH3NO2
CH3NO2
CH3NO2
CH3NO2
CH3NO2
CH3NO2
61
41
-
8
-
9
-
10
11
12
13
14
15
16
17
18
19
-
-
PivOH
CF3COOH
TMEDA
Et3N
43
37
55
62
59
HMPA
DMEDA
DMEDA
DMEDA
DMEDA
Reaction conditions: 1a (0.3 mmol), 2 (0.45 mmol), TBAI (20 mol %),
CH3NO2 69
K2S2O8 (1.2 mmol), DMEDA (20 mol %), CH3NO2 (2 mL), 100 oC.
CH3NO2
CH3NO2
CH3NO2
49
35
13
NH4I
Initially, 1,4-diphenylbut-3-yn-1-ol (1a) and p-
toluenesulfonyl hydrazide (2b) were chose as the
model substrates to optimize reaction conditions.
While TBAI (20 mol %) and K2S2O8 (3 equiv) were
used in this reaction, radical cyclization occurred to
give the desired product 1-phenyl-2-tosylnaphthalene
(3ab) in 45% yield with DCE as solvent (Table 1,
entry 1). After confirming the structure of compound
3ab by the single crystal X-ray analysis (Figure 1),[13]
different solvents were evaluated and CH3NO2 was
found to be the most efficient solvent for this
transformation (Table 1, entry 1-6). The yield of 3ab
was slightly improved when K2S2O8 was increased to
4 equiv for this reaction (Table 1, entry 7). Then
various oxidants, such as TBHP, TBP, Oxone® were
also tested, no better results were obtained (Table 1,
entries 8-11). Further investigation was focused on
introducing the acids or bases to this reaction system.
The yields of 3ab were decreased when acids were
added (Table 1, entries 11, 12). To our delight, the
base DMEDA promoted the reaction and the yield
I2
b
a Reaction conditions: 1a (0.3 mmol), 2b (0.45 mmol), solvent (2 mL).
Yields of isolated products. Entry in bold highlights optimized reaction
conditions, and the reaction time was monitored by TLC. TBAI =
Tetrabutylammonium iodide, TBP = Ditertbutyl peroxide, DMEDA =
N,N-Dimethylethanediamine, TMEDA
HMPA = Hexamethylphosphoric triamide, DCE = Dichloroethane.
= Tetramethylethylenediamine,
addition, Liu's group had reported the approach for
the synthesis SCF3-substituted dihydrofurans with
homopropargylic
alcohols
and
trifluoromethanesulfenamide (Scheme 1).[9] Our
group also had developed two methods for the
construction sulfanylfurans and 3-methylthiofurans
with homopropargylic alcohols and sulfonyl
hydrazides/DMSO (Scheme 1).[10] In the field of
radical rearrangement, great progress had been
achieved by the group of liang (Scheme 1). In 2014,
Liang' group developed an unprecedented one pot
reaction of homopropargylic alcohols that involved
copper-catalyzed
migration, and formation of a carbonyl group.
trifluoromethylation,
1,4-aryl
[11]
To
our best knowledge, the formation of β-arylsulfonyl
naphthalenes from homopropargylic alcohols and
sulfonyl hydrazides through direct radical addition
has not been explored. Intrigued by the utilization of
arylsulfonohydrazides for the formation of the S-
containing molecules,[12] herein, we developed a
metal-free approach to synthesize β-arylsulfonyl
naphthalenes from homopropargylic alcohols and
sulfonyl hydrazides via direct radical addition.
Figure 1. The X-ray Structure of 3ab.
2
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10.1002/adsc.201700634
Advanced Synthesis & Catalysis
benzene ring were transformed well under the
optimized conditions and gave the corresponding β-
arylsulfonyl naphthalenes in 52-73% yields (Scheme
Scheme 4. Control experiments
Scheme 3. The scope of substituted homopropargylic
alcohols and sulfonyl hydrazides
3). Moreover, more challenging substrates 1m, 1n,
and 1o were also tolerated well and generated the
desired products 3mb, 3lb, and 3ob in 83%, 89%,
76% yields respectively. Unfortunately, the
homopropargylic alcohols with alkyl group
performed unsuccessfully in this process and no
desired product was obtained.
To gain some mechanistic insights, several
control experiments were carried out and the results
are shown in Scheme 4. The reaction was
significantly inhibited when 2.0 equiv of 2,2,6,6-
tetramethylpiperidine-1-oxyl
(TEMPO)
was
Reaction conditions: 1 (0.3 mmol), 2b (0.45 mmol), TBAI (20 mol %),
K2S2O8 (1.2 mmol), DMEDA (20 mol %), CH3NO2 (2 mL), 100 oC.
employed. When the radical scavenger of 2,6-di-
tert-butyl-4-methyl-phenol (BHT) was used for this
reaction, the product 3ab was almost not detected
and a product 2,6-di-tert-butyl-4-methylphenyl-4-
methylbenzene sulfonate 4 was isolated in 89%
yield, which was confirmed by NMR and HMRS
spectroscopy (Scheme 4, entry 2). This result
suggested that sulfonyl radical should be the
was improved to 69% (Table 1, entries 13-19).
Finally, different iodine sources were also
investigated and TBAI was proved to be the best
catalyst for this reaction (Table 1, entries 17-19).
After screening other reaction parameters, the
optimized reaction system was established as Table 1,
entry 16.
important
radical
intermediate
for
this
With the optimized conditions in hand, the scope
of substituted sulfonyl hydrazides was examined and
the results are illustrated in Scheme 2.
Arylsulfonohydrazides with various the m-, o-, p-
substituents reacted with substrate 1a smoothly,
generating the desired substituted β-arylsulfonyl
naphthalenes in moderate yields. Substituted sulfonyl
hydrazides with both electron-withdrawing and
electron-donating groups, such as alkyl, methoxyl,
fluoro, chloro, bromo and trifluoromethyl all survived
in this process and the reactions were less affected by
the nature of groups on the benzene ring of sulfonyl
hydrazides. When methanesulfonyl hydrazide 2l was
subjected to the standard condition, no desired
product was detected, probably due to the instability
of methanesulfonyl radicals. It is known that
generation of methanesulfonyl radicals is often
followed by beta-scission to yield a methyl radical.
After successfully evaluating the various sulfonyl
hydrazides, we next extended our investigation to the
scope of substituted homopropargylic alcohols. As
conceived, various homopropargylic alcohols with
Me, MeO, tBu, F, Cl, Br and CN groups on the
transformation. Furthermore, no desired product 5
was detected without substrate 2b under the
standard conditions.
Scheme 5. Proposed mechanism
Based on these experimental results and previous
mechanistic studies, a plausible mechanism is
proposed in Scheme 5. Firstly, a sulfonyl radical A
is generated from sulfonyl hydrazides 2 by
3
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10.1002/adsc.201700634
Advanced Synthesis & Catalysis
Fundamental Research Funds for the Central Universities
(lzujbky-2016-39).
TBAI/K2S2O8 with releasing N2. Next, the vinyl
radical intermediate B is obtained from the the
sulfonyl radical A addition to homopropargylic
alcohol 1.[6a-f] Furthermore, the vinyl radical B
undergoes intramolecular cyclization to synthesis
new radical intermediate C.[3a, 6e, 6l, 6t, 6z] Then the
intermediate D is produced via losing hydrogen
radical directly. Finally, the desired naphthalene 3 is
afforded through water elimination.
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General procedure for synthesis of β-Arylsulfonyl
naphthalenes with homopropargylic alcohols and
sulfonylhydrazines:
The homopropargylic alcohols (1a, 0.3 mmol),
sulfonylhydrazines (2b, 0.45 mmol), TBAI (20 mol %),
K2S2O8 (4 equiv), DMEDA (20 mol %) were mixed in
CH3NO2 (2 mL) and this mixture was carried out under N2
o
at 100 C for 12 h. Then the reaction mixture was cooled
to room temperature, and then extracted with ethyl acetate
(15 ml×3). The combined organic phase was dried over
anhydrous Na2SO4. The solvent was evaporated in vacuo
and the crude product was purified by column
chromatography, eluting with petroleum ether/EtOAc
(10:1) to afford the desired β-arylsulfonyl naphthalenes
3ab (74.1 mg, 69% yield).
Acknowledgements
This work was supported by National Natural Science
Foundation of China (21672086, 21462035), Gansu Province
Science Foundation for Youths (1606RJYA260) and the
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10.1002/adsc.201700634
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10.1002/adsc.201700634
Advanced Synthesis & Catalysis
UPDATE
TBAI/K2S2O8 Initiated Radical Cyclization to
Synthesize β- Arylsulfonyl Naphthalenes from
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Adv. Synth. Catal. Year, Volume, Page – Page
Xiaodong Yang,† Lianbiao Zhao,‡ Bingxiang
Yuan,† Zhenjie Qi,† Rulong Yan*†
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