Sodium Perborate: A Facile Catalyst for Allylation of Active Centers

Article abstract of DOI:10.1080/00397911.2014.963874

An efficient and ecofriendly allylation of O-H, N-H, and C-H groups has been achieved successfully with the reaction of allyl bromide by using sodium perborate as a new catalyst in aqueous media. The advantage of this method is operationally simple, short reaction time, good yield, and simple workup conditions over the previously reported conventional methods such as amination, oxyalkylation reactions of allyl bromide, and Friedel-Crafts allylation chemistry.

Full text of DOI:10.1080/00397911.2014.963874

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Sodium Perborate: A Facile Catalyst for Allylation of
Active Centers
Soora Harinath Jayaprakasha, Balam Satheesh Krishnaa, Sthanikam Siva Prasada, Sarva Santhi
Sudhaa & Cirandur Suresh Reddya
a Department of Chemistry, Sri Venkateswara University, Tirupati, India
Accepted author version posted online: 10 Oct 2014.
To cite this article: Soora Harinath Jayaprakash, Balam Satheesh Krishna, Sthanikam Siva Prasad, Sarva Santhi
Sudha & Cirandur Suresh Reddy (2014): Sodium Perborate: A Facile Catalyst for Allylation of Active Centers,
Synthetic Communications: An International Journal for Rapid Communication of Synthetic Organic Chemistry, DOI:
10.1080/00397911.2014.963874
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Sodium Perborate: A Facile Catalyst for Allylation of Active Centers
Soora Harinath Jayaprakash1, Balam Satheesh Krishna1, Sthanikam Siva Prasad1, Sarva
Santhi Sudha1, Cirandur Suresh Reddy1
1Department of Chemistry, Sri Venkateswara University, Tirupati, India
Corresponding Author: E-mail: csrsvu@gmail.com
Abstract
An efficient and eco-friendly allylation of O-H, N-H and C-H groups has been achieved
successfully with the reaction of allyl bromide by using sodium perborate as a new
catalyst in aqueous media. The advantage of this method is operationally simple, short
reaction time, high yield and simple work-up conditions over the previously reported
conventional methods such as amination, oxyalkylation reactions of allyl bromide and
Friedel-Crafts allylation chemistry.
KEYWORDS: Allylation; Aqueous Medium; Sodium perborate
INTRODUCTION
1

The green chemical approach reinforces the scope of designing new synthetic
methodologies in organic chemistry with clean and environmentally benign strategies.[1]
In such, conceiving new organic reactions in aqueous medium is considered as the first
and foremost choice for the researchers. Though the aid of microwave[2] and sonication[3]
energies accelerates the aqueous mediated organic reactions, identification of new and
efficient green catalysts remains as an eternal challenge for the researchers. Thus, our
interest to develop effective methodology for allylation reaction has emerged as a novel
accomplishment in catalysis and was inspired us to report herewith.
Allylation is an important organic reaction used in the synthesis of new compounds that
could be further converted into polymers, spiro compounds, resins and natural products.[4-
10] This aspect provoked researchers to develop new synthetic precursors, catalysts and
methodologies for allylation of organic molecules. In such endeavors, allylation reaction
received the great attention due to the universal superior properties in aqueous medium
over other solvents.[11] This highly impacted the designing of aqueous organic reactions
by the use of synergetic and potential catalysts and promoters.[12]
One of the methods for allylation of alkyl/ aryl/ hetero arylated compounds containing -
OH, -NH & -CH groups is with allyl halides in the presence of K2CO3,[13] tetra (n-butyl)
ammonium hydroxide,[14] NaOH,[15] gallium,[16] Cs2CO3,[17] NaH,[18] and Cu/ CuCl2[19] as
catalysts. But all these reactions needed elevated temperatures, dry organic solvents and
moisture sensitive catalysts. As a consequence, development of an environmentally
benign practical synthetic route under neutral conditions for accessing these allylated
2

compounds remains as a major goal.
Herein, we reported sodium perborate (PBS), an efficient catalyst for a facile allylation
reaction in aqueous medium. Also, the catalyst PBS is an inexpensive, stable, innocuous,
easily handled and extensively used ingredient in detergents as a bleaching agent.
However, the main advantage of this catalyst is that it generates nontoxic boric acid and
water in these reactions which facilitates product separation easier. Thus PBS has
emerged as an efficient catalyst source for various chemical transformations.[20-24]
RESULTS AND DISCUSSION
Allyl bromide is a highly active reagent and its amination, oxyalkylation reactions to
electron rich aromatic ring are very conventional and involves organic solvent mediation
and high temperature conditions. But the aqueous mediated allylation of compounds
containing OH, NH or CH with allyl bromide in presence of PBS at room temperature
has been proved as an an effective, practical green approach. Accordingly some mono/ di
hydric alcohols & phenolic compounds, and aryl, alkyl amines and aromatic compounds
were allylated at O, N and CH successfully (Scheme 1).
Preparation of compound 4d was selected as a model reaction for optimizing the
experimental conditions of the present methodology. Initially, we screened the reaction
conditions with and without the catalyst to optimize the reaction and found that best
yields were achieved with 0.4 equiv. of catalyst loading and use of higher catalyst
concentrations has not effectively improved the product yields (Figure 1).
3

After optimizing the catalyst quantity requirements, the generality of this method was
tested on aliphatic alcohols, substituted phenolic compounds, secondary amines and on
aromatic CH group. All reactions proceeded smoothly at room temperature and afforded
corresponding allylated products exclusively with moderate to good yields. Sensitive
substituted functionalities such as -OMe, -CHO -Br and -Cl were unaffected under the
established conditions during this allylation. This method is also successful with low
reactive aliphatic diols, where both the hydroxy groups got allylated simultaneously.
Further, the present method does not require any additives to promote the reaction.[25]
Results are incorporated in Table 1.
PBS (3), a dimeric crystalline, non-toxic inorganic reagent releases highly reactive
hydrogen peroxide (3a) and sodium borate (3b) in dilute aqueous conditions (0.1 M)
which in turn generates sodium peroxoborate (3c) at equilibrium. Formation of 3a, 3b
and 3c in this reaction is confirmed by NMR and Raman spectroscopy.[25] It is also
reported that, the lower pH conditions more favorably shifts the equilibrium towards the
sodiumborate (3b) rather than sodiumperoxoborate (3c).[20] The hydrogenperoxide
associated with sodiumborate will react with reactants (1a-j & 2) and generates the
allylated products by releasing hypobromous acid (HOBr, 3d). The released HOBr, a
mild acid renders the more acidic compared to H2O2 [HOBr (Ka = 2.5 X 10-9; pKa for is
8.70) H2O2 (Ka = 2.4 x 10-12; pKa = 11.62)] and strengthens the shifting of the same
dynamic equilibrium towards the formation of more hydrogen peroxide (3a) along with
sodium borate (3b).[26] Such that these reaction parameters fortify the plausible key role
of sodium perborate with good catalytic behavior and potentially energizes the
4

electrophilic allylation of active nucleophilic centers. Though Tsuji-Trost methodology[27,
28] the facilitates electrophilic allylation of nucleophilic centers in the presence of
palladium-catalyst by allyl halides, the present methodology itself enables it to report as
an interesting and mild alternative catalyst with eco-friendly advantages for the existing
ones.
To explore the scope of this methodology in to pharmaceuticals and medicinal chemistry
of interest on heterocyclic compounds, the same reaction is performed between simple
indole and allyl bromide (Scheme 2) where we get 3-allyl indole (4j) and are very
important molecules due to their numerous biological activities[29] and also serves as
useful intermediates in the synthesis furo[3,4-b]indoles,[30] (-)-physovenine[31] & many
other naturally occurring indole alkaloids.[32] Literature scan reveals that, preparation of
3-allyl indoles was achieved by the reaction of indole with allyl bromide using Zinc,[33]
Gallium,[34]etc., as catalysts in organic solvents. The present method is more attractive in
terms of product yields and green chemistry involved when compared to those reported
earlier.
Finally, the catalytic efficiency of PBS was compared with the reported catalysts in the
literature for synthesis of allylated compound 4d (Table 2). As shown in Table 2, PBS
was proved to be more efficient catalyst than previously reported ones related to reaction
conditions.
EXPERIMENTAL SECTION GENERAL
5

Solvents and reagents were procured from Sigma-Aldrich & Merck and are used as such
without further purification. IR spectra of samples were recorded as potassium bromide
pellet on a Bruker Vector 21 FT-IR spectrophotometer. 1H and 13C NMR spectra were
recorded as solutions in CDCl3 on a Bruker AMX 500 MHz spectrometer operating at
300 MHz for 1H, and 75.4 MHz for 13C using tetra methyl silane (TMS) as an internal
standard. ESI mass spectra were recorded on a Micromass Quattro LC instrument.
Elemental analysis was performed on Thermo Finnigan Instrument.
Typical Protocol For The Reaction
To the 25 mL round bottomed flask containing 5 mL of water, were added β-Naphthol
(1d, 0.50 g, 1 equiv.), sodium perborate (3, 0.214 g, 0.4 equiv.), and allyl bromide (2,
0.462 g, 1.1 equiv.) and reaction mixture was stirred at room temperature as given time.
Progress of the reaction was monitored by TLC. After completion of the reaction (6.5h),
the product was extracted with ethyl acetate (3x15 mL) and combined organic layers
were dried over anhydrous sodium sulfate and concentrated under reduced pressure. The
crude residue thus obtained was purified by silica gel column chromatography (100-200
mesh) using 5% ethyl acetate in hexane as eluent to afford pure compound 4d. Similar
procedure was adopted for the compounds 4a-c, and 4e-j (Table 1).
2-(allyloxy) naphthalene (4d): Yield 96%, Yellow oily liquid, 1H NMR (300 MHz,
CDCl3) δ (ppm): 4.65-4.66 (d, 2H, J = 5.18 Hz), 5.31-5.33 (dd, 1H, J = 10.52 Hz), 5.45-
5.49 (dd, 1H, J = 17.24 Hz), 6.09-6.16 (m, 1H), 7.14-7.77 (m, 7H, Ar-H); 13C NMR (75
MHz, CDCl3) δ (ppm): 68.7, 106.9, 117.8, 118.9, 123.6, 126.3, 126.7, 127.6, 129.3
6

133.1; IR (KBr, ν, cm-1): 3033, 1654, 1092; MS (ESI): m/z 185 [M+H]+; Anal. Calc. for
C13H12O: C, 84.75; H, 6.57; O, 8.68, Found: C, 84.68; H, 6.48; O, 8.61.
CONCLUSION
Sodium perborate has been reported as an efficient catalyst for the allylation of alcohols,
phenols and secondary amines with good to excellent product yields under aqueous
conditions at room temperature. The noteworthy advantages of the methodology are
operational simplicity, green chemical approach, ecofriendly catalysis, simple work-up
procedure and higher product yields. Further, the reaction is applicable to wide spectrum
of aromatic and aliphatic alcohols/ amine substrates and the reaction conditions are
tolerant to a variety of sensitive functional groups. All the merits qualify this as the
method of choice for large scale procedure of the title compounds.
CONFLICT OF INTEREST
We state that none of the authors have any conflict of interest in the context of this
communication.
ACKNOWLEDGMENTS
We thank Professor C.D. Reddy, Department of Chemistry, Sri Venkateswara University,
Tirupati, for his helpful Discussions, University Grants Commission (UGC), New Delhi
for providing Senior Research Fellowship to one of the author Mr. S.H. Jayaprakash and
for funding a major research project (F. No.: 42-281/2013 (SR), dated: 12-03-2013).
7

SUPPLEMENTAL MATERIAL
Supplemental data for this article can be accessed on the publisher’s website.
REFERENCES
1.
Rao, V. K.; Reddy, S. S.; Krishna, B. S.; Naidu, K. R. M.; Raju, C. N.; Ghosh, S.
K. Synthesis of Schiff’s bases in aqueous medium: a green alternative approach with
effective mass yield and high reaction rates, Green Chemistry Letters and Reviews. 2010,
3, 217.
2.
Wiley-VCH, Weinheim, 2013, Chap. 4, pp. 127-208.
3. Rao, V. K.; Babu, B. H.; Babu, K. R.; Srinivasulu, D.; Raju, C. N. Ecofriendly
Perreux, L.; Loupy, A.; Petit, A. Microwaves in Organic Synthesis; 3rd ed.,
synthesis of tetrahydropyrimidine derivatives in aqueous medium under ultrasonic
irradiation. Synth. Commun. 2012, 42, 3368.
4.
Bodwell, G. J.; Li, J. Concise synthesis and trans annular inverse electron demand
Diels-Alder reaction of [3](3,6)pyridazino[3](1,3)indolophane. Rapid access to a penta
cyclic indoloid system. Org. Lett. 2002, 4, 4127.
5.
Chen, W.; Yang, X.D.; Li, Y.; Yang, L. J.; Wang, X. Q.; Zhang, G. L.; Zhang, H.
B. Design, synthesis and cytotoxic activities of novel hybrid compounds between di
hydro benzofuran and imidazole. Org. Biomol. Chem. 2011, 9, 4250.
6.
Enrique, L. L.; Teodoro, S. K. A combined RCM-Bischler-Napieralski strategy
towards the synthesis of the carbon skeleton of excentricine and related stephaoxocanes.
Tetrahedron 2008, 64, 9921.
8

7.
Ding, L.; Xie, M.; Yang, D.; Song, C. Efficient Synthesis of Long-Chain Highly
Branched Polymers via One-Pot Tandem Ring-Opening Metathesis Polymerization and
Acyclic Diene Metathesis Polymerization. Macromolecules 2010, 43, 10336.
8.
Kit, Y. T.; Margaret, A. B. Synthesis of aromatic spiro acetals related to γ-
rubromycin based on a 3H-spiro[1-benzofuran-2,2’-chromane] skeleton. Tetrahedron
2007, 63, 6015.
9.
peptide synthesis. Org. Lett. 2003, 5, 415.
10. Charles de Koning, B.; Joseph Michael, P.; William van Otterlo, A. L.; Syntheses
Gu, W.; Silverman, R. B. New stable backbone linker resins for solid-phase
of isochromane analogues of the michellamines and korupensamines. J. Chem. Soc.,
Perkin Trans.1. 2000, 1, 799.
11.
12.
13.
Okuhara, T. Water-tolerant solid acid catalysts. Chem Rev. 2002, 102, 3641.
Philip, G. J. Searching for green solvents. Green Chem. 2011, 13, 1391.
White, W. N.; Slater, C. D. The ortho-Claisen Rearrangement. V. The Products of
Rearrangement of Allyl m-X-Phenyl Ethers. J. Org. Chem. 1961, 26, 3631.
14. Delaine, T.; Bernardes-Génisson, V.; Quémard, A.; Constant, P.; Meunier, B.;
Bernadou, J. Development of isoniazid-NAD truncated adducts embedding a lipophilic
fragment as potential bi-substrate InhA inhibitors and antimycobacterial agents. Eur. J.
Med. Chem. 2010, 45, 4554.
15.
Borgulya, J.; Madeja, R.; Fahrni1, P.; Hansen, H. J.; Schmid, H.; Barner, R.
Umlagerung von Allyl-aryläthern und Allyl-cyclohexadienonen mittels Bortrichlorid.
HeIv. Chim. Acta. 1973, 56, 14.
9

16.
Gogoi, B. J.; Gohain, M.; Prajapati, D. Novel gallium-mediated C-3 allylation of
indoles and pyrroles in aqueous media promoted by Bu4NBr. Tetrahedron Lett. 2006, 47,
3535.
17.
Cesium Carbonate. Synth. Commun. 1995, 25, 1367.
18. Miguel, Y.; Rosa, O.; Fernando, F. H. Intramolecular carbolithiation promoted by
a DTBB-catalysed chlorine–lithium exchange. Tetrahedron 2003, 59, 8525.
19. Zadmard, R.; Aghapoor, K.; Bolourtchian, M.; Saidi, M. R. Solid Composite
Lee, J. C.; Yuka, J. Y.; Cho, S. H. Facile Synthesis of Alkyl Phenyl Ethers Using
Copper-Copper Chloride Assisted Alkylation of Naphthols Promoted by Microwave
Irradiation. Synth. Commun. 1998, 28, 4495.
20.
McKillop, A.; Tarbin, J. A. Functional group oxidation using sodium perborate
Tetrahedron 1987, 43, 1753.
21.
Firouzabadi, H.; Iranpoor, N.; Amani, K. Tungstophosphoric acid catalyzed
oxidation of aromatic amines to nitro compounds with sodium perborate in micellar
media. Green Chem. 2001, 3, 131.
22.
23.
Safaiee, M. sodium perborate (PBS). Synlett. 2006, 15, 2513.
Sharifi, A.; Mohsenzadeh, F.; Mojtahedi, M. M.; Saidi, M. R.; Balalaie, S.
Microwave-Promoted Transformation Of Nitriles To Amides With Aqueous Sodium
Perborate. Synth. Commun. 2001, 31, 431.
24.
Yuan, J.; Zhao, Z.; Zhu, W.; Li, H.; Qian, X.; Xu, Y. New strategy for the
synthesis of 2-phenylbenzimidazole derivatives with sodium perborate (PBS) as oxidant.
Tetrahedron. 2013, 69, 7026.
10

25.
aryl alkane nitrile carbanions to substituted propenylarenes. Synthesis 1993, 8, 780.
26. Flanagan, J.; Griffith, W. P.; Powell, R. D.; West, A. P. Nature of peroxoborate
Wojciech, L.; Mieczysław, M. Phase-transfer catalyzed nucleophilic addition of
species in aqueous solution: a study by boron-11 nuclear magnetic resonance and Raman
spectroscopy. J. Chem. Soc. Dalton Trans. 1989, 1651.
27.
peroxide in aqueous solution. Inorg. Chem. 1987, 26, 3639.
28. Tsuji, J.; Takahashi, H.; Morikawa, M. Organic syntheses by means of noble
Pizer, R.; Tihal, C. Peroxoborates. Interaction of boric acid and hydrogen
metal compounds XVII. Reaction of π-allyl palladium chloride with nucleophiles.
Tetrahedron Lett. 1965, 49, 4387.
29.
Mori, M.; Nakanishi, M.; Kajishima, D.; Sato, Y. A new and general synthetic
pathway to strychnos indole alkaloids: total syntheses of (-)-dehydrotubifoline and (-)-
tubifoline by palladium-catalyzed asymmetric allylic substitution. Org. Lett. 2001, 14,
1913.
30.
Zhang, J.; Chen, Z.; Wu, H. H.; Zhang, J. Ni(ClO4)2-catalysed regio and
diastereoselective [3+2] cycloaddition of indoles and aryl oxiranyl-dicarboxylates/
diketones: a facile access to furo[3,4-b]indoles. Chem. Commun. 2012, 48, 1817.
31.
Sunazuka, T.; Yoshida, K.; Kojima, N.; Shirahata, T.; Hirose, T.; Handa, M.;
Yamamoto, D.; Harigaya, Y.; Kuwajima, I.; Omura, S. Total synthesis of (−)-
physovenine from (−)-3a-hydroxyfuroindoline. Tetrahedron Lett. 2005, 46, 1459.
32.
Nishibayashi, Y.; Yoshikawa, M.; Inada, Y.; Hidai, M.; Uemura, S. Ruthenium-
catalyzed propargylation of aromatic compounds with propargylic alcohols. J. Am. Chem.
Soc. 2002, 124, 11846.
11

33.
Yadav, J.S.; Reddy, B.V.S.; Muralikrishna Reddy, P.; Srinivas, Ch. Zinc-
mediated Barbier reactions of pyrrole and indoles: a new method for the alkylation of
pyrrole and indoles. Tetrahedron Lett. 2002, 43, 5185.
34.
Dipak, P.; Mukut, G.; Baikuntha, J. G. Novel gallium-mediated C3-allylation of
indoles and pyrroles in aqueous media promoted by Bu4NBr. Tetrahedron Lett. 2006, 47,
3535.
35.
Chen, J.; Chen, L.; Jie, S.; Li, S.; Liang, X.; Luo, Y.; Ma, L.; Peng, A.; Peng, M.;
Wang, T.; Wang, X.; Wei, Y.; Zhu, W. Structural Modification of Honokiol, a Biphenyl
Occurring in Magnolia officinalis: the Evaluation of Honokiol Analogues as Inhibitors of
Angiogenesis and for Their Cytotoxicity and Structure–Activity Relationship. J. Med.
Chem. 2011, 54, 6469.
36.
Alcaide, B.; Alonso, J. M.; Almendros, P. Ruthenium-Catalyzed Chemoselective
N-Allyl Cleavage: Novel Grubbs Carbene Mediated Deprotection of Allylic Amines.
Chem.-Eur. J. 2003, 9, 5793.
37.
Hoveyda, A. H.; Li, B.; Malcolmson, S. J.; Meek, S. J.; Schrock, R. R. The
Significance of Degenerate Processes to Enantioselective Olefin Metathesis Reactions
Promoted by Stereogenic-at-Mo Complexes. J. Am. Chem. Soc. 2009, 131, 16407.
12

Table 1. Synthesis of compounds 4a-i
13

Table 2. Comparison of our results with previously reported data for synthesis of 4d
Entry Catalyst
Reaction conditions
Acetone/ heating
Time
19h
Yield (%)a
99[5]
1
2
3
4
K2CO3
CS2CO3
Cu, CuCl2
Acetonitrile/ heating 5h
MW irradiation
98[14]
0.025h 72[16]
NaBO3.4H2O Water/ rt
6.5h
98[b]
aIsolated yield
bPresent work
14

Scheme 1. PBS catalyzed synthesis of allylated compounds (4a-i)
15

Scheme 2. Reaction of Indole with ally bromide
16

Figure 1. Optimization of catalyst loading on model reaction of 4d
17

Figure 2. Plausible mechanism for the PBS catalysed allylation reaction
18