TBAI/TBHP mediated oxidative cross coupling of aryl alkyl ketones with H-phosphonates and H-phosphine oxides in water: Facile access to ketol phosphates and phosphinates

Article abstract of DOI:10.1016/j.tetlet.2016.02.095

A metal free cross coupling of aryl alkyl ketones with alkyl/aryl H-phosphonates and H-phosphine oxides using tetrabutylammonium iodide (TBAI) catalyst in the presence of tert-butyl hydroperoxide (TBHP) as terminal oxidant in aqueous media is developed. T

Full text of DOI:10.1016/j.tetlet.2016.02.095

Accepted Manuscript
TBAI/TBHP mediated oxidative cross coupling of aryl alkyl ketones with H-
phosphonates and H-phosphine oxides in water:facileaccess to ketolphosphates
and phosphinates
G. Saidulu, R. Arun Kumar, T. Anitha, P. Santhosh Kumar, K. Rajender Reddy
PII:
S0040-4039(16)30204-0
DOI:
http://dx.doi.org/10.1016/j.tetlet.2016.02.095
TETL 47370
Reference:
Tetrahedron Letters
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Received Date:
Revised Date:
Accepted Date:
21 December 2015
22 February 2016
25 February 2016
Please cite this article as: Saidulu, G., Arun Kumar, R., Anitha, T., Santhosh Kumar, P., Rajender Reddy, K., TBAI/
TBHP mediated oxidative cross coupling of aryl alkyl ketones with H-phosphonates and H-phosphine oxides in
water: facile access to ketol phosphates and phosphinates, Tetrahedron Letters (2016), doi: http://dx.doi.org/
10.1016/j.tetlet.2016.02.095
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1
Tetrahedron Letters
TBAI/TBHP mediated oxidative cross coupling of aryl alkyl ketones with H-
phosphonates and H-phosphine oxides in water: facile access to ketol phosphates and
phosphinates
G. Saidulu, R. Arun Kumar, T. Anitha, P. Santhosh Kumar and K. Rajender Reddy*
Inorganic and Physical Chemistry Division, CSIR-Indian Institute of Chemical Technology, Tarnaka, Telangana State, Hyderabad – 500 007, India.
ARTICLE INFO
ABSTRACT
Article history:
Received
Received in revised form
Accepted
A metal free cross coupling of aryl alkyl ketones with alkyl/aryl H-phosphonates and H-
phosphine oxides using tetrabutylammonium iodide (TBAI) catalyst in presence of tert-butyl
hydroperoxide (TBHP) as terminal oxidant in aqueous media is developed. This new approach
offers a direct and convenient route to access a wide range of ketol phosphates and phosphinates
in moderate to good yields.
Available online
Keywords:
Tetrabutylammonium iodide,
Oxidative coupling,
Phosphonate,
2009 Elsevier Ltd. All rights reserved.
Aryl alkyl ketone,
Ketol phosphate.
Direct activation of C-H bonds and subsequent coupling
with carbon and heteroatom based pro-nucleophiles to generate
new carbon-carbon (C-C) and carbon-heteroatom (X= N, O, P)
bonds under oxidative conditions have emerged as one of the
most reliable and robust tools in modern synthetic organic
chemistry. Since, this approach avoids the pre-formed precursors
and thus provides a direct, atom-economical and environmentally
benign route to synthesize biologically relevant organic
molecules. Over the past decade, tremendous progress has been
made on oxidative cross coupling methodology using variety of
coupling partners and catalytic systems.1 Generally, these
reactions are furnished using transition metal catalysts and
oxidants such as molecular oxygen (O2), hydrogen peroxides and
organic peroxides). Moreover, numerous transition-metal free
oxidative coupling methods have also been reported using
stoichiometric oxidants such as hypervalent iodine reagents,2 2,3-
dichloro-5,6-dicyanohydroquinone (DDQ),3 benzoylperoxide
(BPO)4 and others.5 However, the problems associated with the
above methods are use of expensive metals, tedious procedures to
remove metal impurities and most importantly, the release of
large amount of undesired by-product by the high mass
stoichiometric oxidants.
In particular, ketol phosphates are well-known
biologically relevant organic compounds which are used as sugar
analogues and important precursor for the synthesis of
phospholipids and nucleotides.7 Several synthetic methods are
documented in the literature for the preparation of this moiety.8-12
However, most of the methods are devoted to the oxidative
coupling strategy involving pre-formed or in situ generated
organo hypervalent iodine reagents (Scheme 1).9-12
In recent years, iodine or iodide salts are recognized as an
ideal substitute to transition metal catalysts and organo
hypervalent iodine reagents. Notably, the combination of
tetrabutylammonium iodide (TBAI) and tert-butyl hydroperoxide
(TBHP) has found to be an attractive metal-free catalytic system,
especially in oxidative cross coupling reactions owing to its mild,
easy removable, high efficient and eco-friendly characteristics.6
 Corresponding author. Tel.: +91-040-2719-1532; fax: +91-040-
27160921; e-mail: rajender@iict.res.in; rajenderkallu@yahoo.com.
Scheme 1 Different approaches to prepare ketol phosphates.

2
Table 1 Optimization of reaction conditionsa
Koser and co-workers demonstrated the pre-formed iodine
(III) phosphate promoted α-phosphoryloxylation of ketones10a and
they have also described the regio-specific conversion of terminal
alkynes to ketol phosphates using iodine (III) phosphate reagent
(Scheme 1, a).10b Recently, Zhang developed the p-iodotoluene
difluoride (p-Tol-IF2) mediated α-phosphoryloxylation of 1,3-
dicarbonyl compounds with diphenylphosphate (Scheme 1, b).11
Yan’s group reported an efficient α-phosphoryloxylation of
ketones with phosphates to generate ketol phosphates (Scheme 1,
c) in the presence of (diacetoxyiodo)benzene.12a Very recently,
the same group also developed an effective catalytic method for
the oxidative coupling between ketones and phosphates using
iodobenzene (PhI) as catalyst and meta-chloroperbenzoic acid
(m-CPBA) as terminal oxidant (Scheme 1, c).12b However, most
of these methods have certain drawbacks such us limited
substrate scope and release of massive by-product from the pre-
formed hypervalent iodine compounds at the end of the reaction,
thus limiting its practical application. Therefore, still there is a
demand for the development of efficient and environmentally
benign methods to access ketol phosphate.
Over the past few years, our group has been focusing on the
synthetic usefulness of transition-metal free catalysts particularly
iodine or iodide salt for various organic transformations.13 In
continuation of our efforts, herein we wish to describe a simple,
convenient and direct method for the synthesis of ketol
phosphates through oxidative coupling of aryl methyl ketones
with H-phosphonates and H-phosphine oxides using TBAI as a
catalyst and TBHP as an oxidant in aqueous media.
Recent literature data reveals that there is renewed interest
on H-phosphonates in cross coupling chemistry.14 Very recently
we have shown application of H-phosphonates as a cross-
coupling partners in the synthesis of substituted 3,4-
dihydroquinazolines.15 To extend the scope of H-phosphonates, it
was originally intended to look at the feasibility of cross coupling
between acetophenone (1a) with H-phospahonate (2a) i.e diethyl
phosphite to generate β-keto phosphonate (3aa) under metal and
metal-free conditions (Table 1). No product was observed with I2,
KI, copper and iron catalysts (Table 1, entries 1-5). To our
surprise, unexpected ketol phosphate was selectively formed in
less than 10% isolated yield with TBAI and the desired β-keto
phosphonate (3aa) could not observe under this condition (Table
1, entry 6). Furthermore, the formation of 3a was confirmed by
spectral analysis (H1, P31 NMR and LC-MS) and spectral datas
were consistent with reported one.
Encouraged by this preliminary result, we did further
investigation to achieve optimal reaction conditions for the
formation of ketol phosphate selectively and the results are
summarized in table 1. Among different solvents tested, water
(H2O) was best solvent media for this reaction (Table 1, entries
7-9). Other oxidants such hydrogen peroxide (H2O2), potassium
persulfate (K2S2O8) and di-tert-butyl peroxide (DTBP) could not
improve the efficiency of the reaction (Table 1, entries 11-13).
Control experiments clearly reveal that both the catalyst (TBAI)
and oxidant (TBHP) play crucial role in this oxidative
transformation (Table 1, entries 14 and 15). The yield of the
desired product 3a was 17%, when the reaction performed in 50
oC (Table 1, entry 16). Similarly, the isolated yield of 3a was
decreased to 38% when amount of TBHP reduced from 3
equivalents to 1.5 equivalents (Table 1, entry17). Finally,
treatment of 2 equivalents acetophenone (1a) with 1 equivalent of
diethyl phosphonate (2a) in the presence 20 mol% of TBAI and 3
equivalents of TBHP in 2 mL of water at 75 oC for 24 hours was
found to be the best conditions for this oxidative transformation
(Table 1, entry 9).
Entry
Catalyst
Oxidant
Solvent
Yield(%)b
3a
1
2
3
4
5
6
7
8
9
I2
TBHP in H2O
TBHP in H2O
TBHP in H2O
TBHP in H2O
TBHP in H2O
TBHP in H2O
TBHP in H2O
TBHP in H2O
TBHP in H2O
DCE
N.D
N.D
N.D
N.D
N.D
<10
<10
<10
56
KI
DCE
CuI
DCE
Cu(OAc)2
FeCl2
TBAI
TBAI
TBAI
TBAI
DCE
DCE
DCE
CH3CN
EtOAc
H2O
10
11
12
13
14
15
16
17
TBAI
TBAI
TBAI
TBAI
TBAI
-
TBHP in H2O
H2O2
H2O
H2O
H2O
H2O
H2O
H2O
H2O
H2O
13
36
K2S2O8
N.D
N.D
N.D
N.D
17c
38d
DTBP
-
TBHP in H2O
TBHP in H2O
TBHP in H2O
TBAI
TBAI
aReaction conditions: (i) Acetophenone 1 (2 mmol), diethylphosphite 2 (1
mmol), TBAI (20 mol%), 70 wt% TBHP in H2O (3 equiv.), H2O (2 mL), 75
oC, 24 h.
bIsolated yield of 3a after SiO2 column chromatography,
creaction performed at 50 oC.
d1.5 equivalents TBHP used.
After establishing the optimal reaction conditions, the scope
of the substituted acetophenones and H-phosphonates were
studied and the results are summarized in table 2. Acetophenone
(1a) was reacted with other aliphatic H-phosphonates such as di-
isopropyl and di-butyl phosphonates and afforded the
corresponding products 3b and 3c in 70% and 58% isolate yields
respectively. Under this standard condition, 1a could not react
with di-tert-butyl phosphonate, which may be because of steric
influence of phosphonate (Table 2, 3d). Whereas diaryl H-
phosphine oxides i.e. diphenyl and di-p-tolyl H-phosphine oxides
provided the corresponding ketol phosphinate products 3e and 3f
in lower yields. Aryl group of acetophenone containing electron
donating groups (methyl and methoxy) coupled with dialkyl
phosphonates and afforded the corresponding products in
moderate to good isolated yields (Table 2, 3g-3i).
Gratifyingly, halogenated acetophenones such as fluro,
bromo and iodo acetophenones worked well under this standard
condition and gave the desired ketol phosphates 3j, 3k, 3l and
3m in satisfactory yields (Table 2, 3j-3m). Reaction of 5-methyl-
2-hydroxy acetophenone with diethyl phosphonate afforded the
product 3n in 33% isolated yield. In addition, propiophenones
were also examined to react with dialkyl phosphonates under this

3
Table 3 Scope of heteroaryl methyl ketonesa,b
standard condition and the representative products were afforded
in moderate yields (Table 2, 3o and 3p). In addition, H-
phosphine oxides were tried to couple with p-chloro-
acetophenone and propiophenone and the corresponding ketol
phosphinates 3q and 3r were obtained in satisfactory isolated
yields (Table 2, 3q and 3r). .
Table 2 Scope of aryl alkyl ketones couplinf reaction with H-
phosphonates and H-phosphine oxidesa
aReaction conditions: (i) Heteroaryl methyl ketone
4
(2 mmol),
dialkylphosphonate 2 (1 mmol), TBAI (20 mol%), 70 wt% TBHP in H2O (3
equiv.), H2O (2 mL), 75 oC, 24 h.
bNumbers in parentheses are isolated yields of the products after SiO2 column
chromatography.
To gain mechanistic insight of this oxidative transformation
four observations were made experimentally as shown in scheme
2: (i) Only trace amount of product 3a formed in the presence of
radical scavenger 5,5-dimethyl-1-pyrroline N-oxide (DMPO). (ii)
Formation of small amount of α-iodoacephenone by GC-MS
analysis of crude reaction mixture. (iii) Formation of product
with pre-synthesized α-iodoacetophenone. (iv) Formation of
corresponding product with dibenzyl hydrogen phosphate
(Bn2PO(OH) (see supporting information).
aReaction conditions: (i) Aryl alkyl ketone 1 (2 mmol), dialkyl H-
phosphonates or diaryl H-phosphine oxide 2 (1 mmol), TBAI (20 mol%), 70
wt% TBHP in H2O (3 equiv.), H2O (2 mL), 75 oC, 24 h. bNumbers in
parentheses are isolated yields of the products after SiO2 column
chromatography.
Scheme 2 Experiments for the mechanistic study.
The exact mechanism for the product formation is not clear
at present stage. However, based on the above observations as
well as from the previous reports,16 a plausible mechanism for
this oxidative transformation is illustrated in scheme 3. Initially,
TBHP is converted into tertiary butoxide radical catalytically
with an aid of iodide anion and this radical trap the hydrogen (H)
from the acetophenone and generates radical cation A.16a
Subsequently, the hypothetic radical cation A is converted into
Furthermore, scope of the reaction was extended to
heteroaryl methyl ketones and the representative results are
shown in table 3. Thiophene methyl ketone coupled smoothly
with di-isopropyl and di-butyl phosphonates under this optimized
reaction conditions and the products 5a and 5b were obtained in
moderate to good isolated yields (Table 3, 5a, 5b). Furyl methyl
ketone was also oxidatively coupled with dibutyl phosphonate to
accomplish ketol phosphate 5c in 55% isolated yield (Table 3,
5c). The isolated yield of the ketol phosphate was very low, when
the reaction was performed between pyridyl methyl ketone and
di-butyl phosphonate (Table 3, 5d).
carbocation intermediate
B via oxidative single electron
transformation (SET).16b After that there are two possible ways
for the conversion of carbocation into final product 3a: (i) The
carbocation B can directly undergo nuclephilic addition reaction
with diethyl hydrogen phosphate C, which is formed in situ by
the direct oxidation of diethyl phosphite with TBHP.16c (ii) The
carbocation B can be also attacked with iodide anion to form α-
iodo acetophenone (D) and subsequently iodide is substituted by
the diethyl hydrogen phosphate to yield the final product 3a.

4
References and Notes
1. Selected reviews on C-C and C-X (X=N, O, P and S) bond formation
through oxidative cross coupling reaction: (a) Murahashi, S.-I.; Zhang,
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42, 335; (c) Scheuermann, C. J. Chem. Asian J. 2010, 5, 436; (d)
Klussmann, M.; Sureshkumar, D. Synthesis, 2011, 353; (e) Zhang, S.-
Y.; Zhang, F.-M.; Tu, Y.-Q. Chem. Soc. Rev. 2011, 40, 1937; (f)
Wendlandt, A. E.; Suess, A. M.; Stahl, S. S. Angew. Chem. Int. Ed.
2011, 50, 11062; (g) Kuhl, N.; Hopkinson, M. N.; Delord, J. W.;
Glorius, F. Angew. Chem. Int. Ed. 2012, 51, 10236; (h) Arockiam, P.
B.; Bruneau, C.; Dixneuf, P. H. Chem. Rev. 2012, 112, 5879. (i) Song,
G.; Wang, F.; Li, X. Chem. Soc. Rev. 2012, 41, 3651; (j) Zhang, C.;
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Chatani,N. Angew. Chem. Int. Ed. 2013, 52, 11726; (l) Girard, S. A.;
Knauber, T.; Li, C.-J. Angew. Chem. Int. Ed. 2014, 53, 74.
Scheme 3 Plausible mechanism.
2. (a) Magnus, P.; Lacour, J.; Weber, W. J. Am. Chem. Soc. 1993, 115,
9347; (b) Zhdankin, V. V.; Kuehl, C. J.; Krasutsky, A. P.; Bolz, J. T.;
Mismash, B.; Woodward, J. K.; Simonsea, A. J. Tetrahedron Lett.
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X.-Y.; Liang,Y.–M.; J. Org. Chem. 2009, 74, 7464.
In conclusion, we have demonstrated a metal-free and
environmentally benign route for the synthesis of ketol
phosphates and phosphinates via direct oxidative cross coupling
between aryl alkyl ketones and H-phosphonates/H-phosphine
oxides. Importantly, this method exhibits good compatibility with
various phosphonates/phosphine oxides and avoids the use of
hazardous reagents. It is worth noting that the reaction proceeds
in water under mild conditions using commercially available
catalyst (TBAI) and oxidant (TBHP). Furthermore, investigations
on the reaction mechanism and to expand the scope of these
reactions are underway in our laboratory.
3. Tsang, A. S. K.; Todd, M. H. Tetrahedron Lett. 2009, 50, 1199.
4. Chua, L.; Qing, F.-L. Chem. Commun. 2010, 46, 6285.
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Chem. 2014, 12, 5807 and references are therein.
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6935; (b) Ramirez, F.; Narecek, J. F. Synthesis, 1985, 449.
General procedure of Ketol Phosphates
A 70 wt% tert-butyl hydroperoxide solution in H2O (TBHP,
3.0 mmol), was added dropwise for 15 minutes into the mixture
of acetophenone derivatives (2.0 mmol), TBAI (20 mol%) and
dialkyl or diaryl phosphite or H-phosphine oxide (1.0 mmol) in
water (H2O, 2.0 mL). The resulting mixture was stirred at 75 °C
for 24 hours. The progress of the reaction was monitored by thin
layer chromatography (TLC). After completion of the reaction,
the resulting solution was cooled to room temperature. After
cooling to room temperature, the reaction mixture was extracted
with ethyl acetate and dried over anhydrous Na2SO4 and
concentrated under reduced pressure. The crude product was
purified by column chromatography on silica gel using petroleum
ether/ethylacetate as an eluent and the products were
charecterised by 1H, 13C, 31P NMR, IR, ESI and HRMS analysis.
3a (153 mg, 56%) Diethyl 2-oxo-2-phenylethyl phosphate: IR
2983, 2928, 2858, 1708, 1598, 1449, 1373, 1265, 1116, 1029,
975, 855, 756, 690 cm-1; 1H NMR (300 MHz, CDCl3)  δ 7.90 (d,
J = 7.5 Hz, 2H), 7.61 (t, J = 7.5 Hz, 1H), 7.49 (t, J = 7.5 Hz, 2H),
5.33 (d, J = 9.8 Hz, 2H), 4.25-4.18 (m, 4H), 1.37 (t, J = 6.0 Hz,
6H); 13C NMR (125 MHz, CDCl3)  192.1, 133.8, 128.8, 127.6,
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P
NMR (202 MHz, CDCl3) δ -0.75; MS (ESI) m/z = 295 (M+Na)+;
(ESI-HRMS) calculated for C12H17O5NaP (M+Na)+: 295.07058,
found: 295.07059.
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Acknowledgements
G. S., T. A. and P. S. thank University Grants Commission
(UGC) and R. A. K thanks Council of Scientific and Industrial
Research (CSIR) for the award of Research Fellowships. K. R. R.
thanks CSIR, India, for financial support under network project
CSC-0123.
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5
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Highlights
 Transition metal free oxidative cross coupling reaction is demonstrated.
 The present protocol offers direct and facile access to ketol-phosphates and phosphinates.
 Performing the reactions in aqueous media make this methodology greener.

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TBAI/TBHP mediated oxidative cross coupling of aryl alkyl ketones with H-phosphonates and
H-phosphine oxides in water: facile access to ketol phosphates and phosphinates.
G. Saidulu, R. Arun Kumar, T. Anitha, P. Santhosh Kumar and K. Rajender Reddy*
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