Bu4NI-catalyzed construction of tert-butyl peresters from alcohols

Article abstract of DOI:10.1039/c5ra27500h

A new method for the synthesis of tert-butyl peresters directly from available alcohols catalyzed by Bu₄NI at room temperature in an aqueous system was developed. Additionally, allylic esters could also be obtained by combing this method and Kharasch-Sosnovsky reaction via a two-step one-pot procedure.

Full text of DOI:10.1039/c5ra27500h

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Bu4NI-catalyzed construction of tert-butyl peresters from alcohols
Hui Zhang,a1 Dao-Qing Dong,a1 Shuang-Hong Haoa and Zu-Li Wanga*
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
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A new method for the synthesis of tert-butyl peresters directly toluene, CH3OH etc. showed lower yields (table 1, entries 3-6).
from available alcohols catalyzed by Bu4NI at room temperature in Further study indicated that other catalysts including KI, CuI,
aqueous system was developed. Additionally, allylic esters could FeCl2 etc. lead to relatively low yields. (table 1, entries 7-14).
also be obtained by combing this method and Kharasch– When the reaction time was reduced to 12h, a lower yield of
Sosnovsky reaction via a two-step one-pot procedure.
the product was obtained (table 1, entry 15). However,
prolonging the reaction time showed almost the same yield
(table 1, entry 16). The effect of the temperature on the
reaction was also investigated. Decreasing the reaction
temperature to RT led to a slightly lower yield (table 1, entry
17). But there was no significant changes on the yield when
The synthesis of tert-butyl peresters is an important task to the
research community due to their importance as core structure
in organic chemistry.1 However, the method for the synthesis
of tert-butyl peresters are limited. Traditionally method for the
synthesis of tert-butyl peresters relied on the reaction of
carboxylic acid and its derivative with tert-butyl
hydroperoxide.2 In 2011, an alternative method for the
synthesis of tert-butyl peresters from aldehydes was disclosed
Wan etc.3 However, versatile and practical methods for the
synthesis of tert-butyl peresters are still desirable.
Table 1. Optimization of the Reaction Conditionsa
O
O
Bu4NI (0.2equiv)
solvent, 16h
OH
O
+
H O O
2
1a
3
Tetrabutylammonium Iodide (TBAI) in combination with tert-
butyl hydroperoxide (TBHP) has been recognized as high
effective and environmentally begin catalyst in most coupling
and radical reactions in recent years.4 For example,
construction of C-O,5 C-N,6 C-C7,4f bonds through cross-
dehydrogenation coupling (CDC) reaction catalysed by TBAI
have been well established. In continuation of our interests in
green chemistry,8 herein, we disclose the synthesis of tert-
butyl peresters from the reaction of alcohols with TBHP using
Bu4NI as the catalyst.
Entry Catalysts
Solvent
H2O
t (h)
16
16
16
16
16
16
16
16
16
16
16
16
16
16
12
24
16
16
T (℃)
Yield (%)
98
1
Bu4NI
Bu4NI
Bu4NI
Bu4NI
Bu4NI
Bu4NI
KI
40
40
40
40
40
40
40
40
40
40
40
40
40
40
40
40
RT
60
2
DMF
DMSO
CH3OH
Toluene
EG
83
3
40
4
39
5
64
6
50
7
H2O
68
At the beginning of our studies,
a model reaction of
8
CuI
H2O
67
phenylmethanol and TBHP was chosen for optimization of the
reaction conditions. It was found that the solvent can greatly
effect the yield of the reaction. When water was used as
solvent, the highest yield of the desired product was obtained
(table 1, entry 1). High yield was also obtained when DMF was
used (table 1, entry 2). However, other solvents such as DMSO,
9
CuCl2
FeCl2
FeCl3
I2
H2O
30
10
11
12
13
14
15
16
17
18
H2O
32
H2O
31
H2O
40
Bu4NCl
CuBr
Bu4NI
Bu4NI
Bu4NI
Bu4NI
H2O
35
H2O
28
H2O
80
H2O
97
H2O
95
H2O
97
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a
Reaction conditions: 1a (0.5 mmol), 2 (2.5 mmol), TBAI (0.25 mmol), phenylmethanol and 3-substituted phenylmethanol gave a
solvent (2 mL), 16 h. Isolated yields. EG: ethylene glycol
higher yield than that of 2-substituted phenylmethanol (table
2, 3d-3l). Additionally, naphthalen-1-ylmethanol and
the reaction temperature was elevated to 60℃(table 1, entry naphthalen-2-ylmethanol were also good substrates in this
18).
reaction affording the desired products in high yield (table 2,
After completion of the search for the optimized reaction 3p
conditions, we chose variety of structurally diverse providing the corresponding product in high yields (table 2, 3q).
phenylmethanol possessing a wide range of functional groups It is interesting to note that when aliphatic alcohols 2-(4-
, 3r). Heteroarenes, thiophen-2-ylmethanol could also
a
to understand the scope and generality of the reaction. It
methoxyphenyl)ethanol was subjected to this reaction, tert-
butyl 4-methoxybenzoperoxoate(3s) was obtained in 36%
yield(Scheme 1). A decarbonylation process may occurred in
this reaction. However, other aliphatic alcohols such as 2-(4-
chlorophenyl)ethanol, 2-phenylethanol were not suitable for
this reaction. The same excellent results were also obtained
when this method was performed at a gram scale using (4-
chlorophenyl)methanol as substrate (Scheme 2). This example
clearly demonstrates the preparative utility of this newly
developed method.
Table 2 Synthesis of tert-butyl peresters catalysed by Bu4NIa
To investigate the synthetic application of the methodology in
organic synthsis. The Kharasch–Sosnovsky reaction between
the tert-butyl peresters and cyclohexene was conducted in
two-step one-pot process. As it was shown in table 3, both
electron-withdrawing groups (F, Br, Cl) (table 3, 4a, 4b, 4g) and
electron-donating groups (CH3S, PhO) (table 3, 4c, 4e) are all
well tolerated in this system. Besides substituted
phenylmethanol, thiophen-2-ylmethanol and naphthalen-2-
ylmethanol (table 3, 4d, 4f) also worked well in this system.
3c, 90%
3a, 95%
3b, 86%
3e, 70%
3f, 83%
3i, 87%
3d, 78%
3g, 76%
Table 3 Synthesis of allylic ester in two-step one-pot processa
3h, 82%
3k, 90%
Entry
1
Substrate
1
Product
4
Yield (%)
80
3j, 83%
3l, 92%
4a
4b
O
O
O
2
3
76
73
S
3n, 73%
3m, 70%
3p, 92%
3o, 95%
3r, 90%
O
O
O
4c
3q, 89%
a
Reaction conditions:
1
(0.5 mmol),
2
(2.5 mmol), Bu4NI (20 mol%),
4
5
85
79
water (2mL), RT, 16 h. Isolated yield.
4d
should be noted that a variety of functional groups, including
methyl, ether, sulfide, halide and ester ran well in this reaction.
Because of smaller hindrance of 4-substituted phenylmethanol
and 3-substituted phenylmethanol compared with its
analogues 2-substituted phenylmethanol, 4-substituted
4e
2 | J. Name., 2012, 00, 1-3
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6
60
4f
7
82
4g
(2.5 mmol), Bu4NI (20 mol%), CH2Cl2 (2mL), RT,
16 h.; step 2: CuBr (5mol%), cyclohexene(10 equiv.), 40 °C for 36 h.
a Step 1:
1 (0.5 mmol), 2
Scheme
1
Reactions
between
aliphatic
alcohol
2-(4-
methoxyphenyl)ethanol and TBHP under standard conditions.
Scheme 4 Possible reaction pathways.
Conclusions
In summary, we have discovered a new method for the
synthesis of tert-butyl peresters catalysed by TBAI directly
from commercially available and low-cost acohols and TBHP at
room temperature in aqueous system. This method and it
combination with Kharasch-Sosnovsky reaction have good
potential in synthetic chemistry. Mechanism investigation
indicated that a radical process probably included. The further
investigation of the reaction mechanism and its applications
are underway in our lab.
Scheme
2 A Gram-Scale Preparation of cyclohex-2-en-1-yl 4-
chlorobenzoate via Kharasch–Sosnovsky reaction.
Financial support from the National Natural Science Foundation of
China (21402103), the China Postdoctoral Science Foundation
(150030), the Scientific Research Foundation of Shandong Province
Outstanding Young Scientist Award (BS2013YY024) and the research
fund of Qingdao Agricultural University’s High-level Person (631303)
were gratefully acknowledged.
Scheme 3 Investigation of the reaction mechanism.
In order to elucidate the mechanism of this reaction, control
experimental was carried out. When radical scavengers like
TEMPO was added to the reaction, the yield of the product
was decreased dramatically (Scheme 3). This suggested that
the transformation probably proceeded through a radical
progress.
Notes and references
‡ Footnotes relating to the main text should appear here. These
might include comments relevant to but not central to the
matter under discussion, limited experimental and spectral data,
and crystallographic data.
§
§§
etc.
According to the above results as well as the known
literature,3,5 a plausible reaction mechanism of the reaction
which is similar with the catalytic cycle proprosed by Wan etc.3
is proposed in Scheme 4. Firstly, the tert-butoxyl
butylperoxy radicals were generated from the reaction
between TBHP and TBAI. Then aldehyde which is generated
the oxidation of alcohol reacted with tert-butoxyl to afford
the acyl radical . Finally, the desired perester were formed
from the reaction between the acyl radical and the tert-
butylperoxy
B and tert-
1
(a) W. Ando, Organic Peroxides, Wiley-Interscience,
New York, 1992;(b) S. N. Gupta, I. Gupta and D. C.
Neckers, J. Polym. Sci. Polym. Chem. Ed. 1981, 19, 103;
A
D
C
B
(c) L. Wang, X. Liu and Y. Li, Macromolecules, 1998, 31
3446. (a) P. C. Montevecchi, A. Manetto, M. L.
Navacchia and C. Chatgilialoglu, Tetrahedron. 2004, 60
,
E
E
,
4303; (b) S. Antonello, M. Crisma, F. Formaggio, A.
Moretto, F. Taddei, C. Toniolo and F. Maran, J. Am.
Chem. Soc., 2002, 124, 11503; (c) B. K. Shah and D. C.
Neckers, J. Am. Chem. Soc., 2004, 126, 1830. (a) F.
Formaggio, M. Crisma, L. Scipionato, S. Antonello, F.
A
.
Maran and C. Toniolo, Org. Lett., 2004, 6, 2753; (b) Y. Li,
S. Niu, B. Sun, S. Liu, X. Liu and Y. Che, Org. Lett., 2010,
This journal is © The Royal Society of Chemistry 20xx
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12, 3144. (a) D. A. Powell and H. Fan, J. Org. Chem.,
2010, 75, 2726; (b) G. Pelletier and D. A. Powell, Org.
Lett., 2006, , 6031. (a) M. S. Kharasch, G. Sosnovsky
and N. C. Yang, J. Am. Chem., Soc. 1959, 81, 5819; (b)
M. B. Andrus and J. C. Lashley, Tetrahedron, 2002, 58
8
,
845; (c) J. Eames and M. Watkinson, Angew. Chem. Int.
Ed., 2001, 40, 3567; (d) A. V. Malkov, M. Bella, V.
Langer and P. Koc , Org. Lett., 2000, 2, 3047; (e) M. B.
Andrus and Z. Zhou, J. Am. Chem. Soc., 2002, 124, 8806;
(f) A. S. Gokhale, A. B. E. Minidis and A. Pfaltz,
Tetrahedron Lett., 1995, 36, 1831; (g) M. T. Rispens, C.
Zondercu and B. L. Feringa, Tetrahedron, Asymmetry,
1995, 6, 661; (h) Y. Kohmura and T. Katsuki,
Tetrahedron Lett., 2000, 41, 3941.
2
(a) N. Milas and D. M. Surgenor, J. Am. Chem. Soc.,
1946, 68, 642; (b) S. L. Silbert and D. Swern, J. Am.
Chem. Soc., 1959, 81, 2364; (c) N. A. Milas, D. G.
Orphanos and R. J. Klein, J. Org. Chem., 1964, 29, 3099;
(d) M. Y. Lu, R. Bao, W. Liu and Y. Li, J. Org. Chem.,
1995, 60, 5341; (e) Y. Hamada, A. Mizuno, T. Ohno and
T. Shioiri, Chem. Pharm. Bull., 1984, 32, 3683.
3
4
W. Wei, C. Zhang, Y. Xu and X. Wan, Chem. Commun.,
2011, 47, 10827.
(a) M. Kirihara, Y. Asai, S. Ogawa, T. Noguchi, A. Hatano
and Y. Hirai, Synthesis, 2007, 3286; (b) P. Finkbeiner
and B. J. Nachtsheim, Synthesis. 2013, 979. (a) M.
Uyanik, H. Okamoto, T. Yasui and K. Ishihara, Science,
2010, 328, 1376; (c) T. Froehr, C. P. Sindlinger, U.
Kloeckner, P. Finkbeiner, B. J. Nachtsheim, Org. Lett.,
2011, 13, 3754; (d) M. Lamani and K. R. J. Prabhu, J.
Org. Chem., 2011, 76, 9552; (e) Z. J. Liu, J. Zhang, S.
Chen, E. Shi, Y. Xu and X. B. Wan, Angew. Chem. Int.
Ed., 2012, 51, 1; (f) L.-T. Li, J. Huang, H.-Y. Li, L.-J. Wen,
P. Wang and B. Wang, Chem. Commun., 2012, 48,
5187; (g) J. Feng, S. Liang, S.-Y. Chen, J. Zhang, S.-S. Fu
and X.-Q. Yu, Adv. Synth. Catal., 2012, 354, 1287; (h) M.
Uyanik and K. Ishihara, ChemCatChem., 2012, 4, 177; (i)
J. A. Souto, D. Zian and K. J. Muniz, Am. Chem. Soc.,
2012, 134, 7242; (j) E. Shi, Y. Shao, S. Chen, H. Y. Hu, Z.
J. Liu, J. Zhang and X. B. Wan, Org. Lett., 2012, 14
2936.
,
5
6
(a) L. Chen, E. Shi, Z. Liu, S. Chen, W. Wei, H. Li, K. Xu
and X. Wan, Chem. Eur. J., 2011, 17, 4085; (b) B. Tan, N.
Toda and C. F. Barbas III, Angew. Chem. Int. Ed., 2012,
51, 12538.
(a) C. Zhu and Y. Wei, ChemSusChem., 2011,
(b) T. Froehr, C. P. Sindlinger, U. Kloeckner, P.
Finkbeiner and B. J. Nachtsheim, Org. Lett., 2011, 13
4, 1082;
,
3754; (c) L. Ma, X. Wang, W. Yu and B. Han, Chem.
Commun., 2011, 11333;(d) U. Kloeckner, N. M.
Weckenmann and B. J. Nachtsheim, Synlett, 2012, 23
,
97–100; (e) S. Chen, Y. Xu, X. Wan, Org. Lett., 2011, 13
,
6152; (f) J. Xie, H. Jiang, Y. Cheng and C. Zhu, Chem.
Commun., 2012, 979; (g) Z. Liu, J. Zhang, S. Chen, E. Shi,
Y. Xu and X. Wan, Angew. Chem. Int. Ed. , 2012, 51
,
3231; (h)W. Mai, H. Wang, Z. Li, J. Yuan, Y. Xiao, L.
Yang, P. Mao and L. Qu, Chem. Commun., 2012, 10117;
(i) H. Li, J. Xie, Q. Xue, Y. Cheng and C. Zhu, Tetrahedron
Lett., 2012, 53, 6479. (j) X. Zhang and L. Wang, Green
Chem., 2012, 14, 2141.
7
(a) A. Rodriguez and W. J. Moran, Org. Lett., 2011, 13
2220;
,
4 | J. Name., 2012, 00, 1-3
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DOI: 10.1039/C5RA27500H
A new method for the synthesis of tert-butyl peresters directly from available alcohols catalyzed
by Bu4NI in aqueous system was developed.