Perfluoroalkanosulfonyl fluoride-assisted Atherton–Todd-like reaction of diphenylphosphine oxide with alcohols under air generating diphenylphosphinate esters

Article abstract of DOI:10.1016/j.tetlet.2017.07.052

An efficient method for the synthesis of diphenylphosphinate esters via the Atherton–Todd-like reaction of diphenylphosphine oxide with alcohols assisted by perfluoroalkanosulfonyl fluoride in the presence of triethylamine under air is achieved affording the corresponding diphenylphosphinate esters in moderate to good yields of 52–78%. The protocol features the use of non-toxic and stable perfluoroalkanosulfonyl fluoride and metal-free reaction conditions.

Full text of DOI:10.1016/j.tetlet.2017.07.052

Accepted Manuscript
Perfluoroalkanosulfonyl Fluoride-Assisted Atherton–Todd-like Reaction of Di-
phenylphosphine Oxide with Alcohols Under Air Generating Diphenylphos-
phinate Esters
Wangyang Wang, Hongai Jin, Zhaohua Yan, Mingchuang He, Sen Lin,
Weisheng Tian
PII:
S0040-4039(17)30908-5
DOI:
http://dx.doi.org/10.1016/j.tetlet.2017.07.052
TETL 49134
Reference:
Tetrahedron Letters
To appear in:
Received Date:
Revised Date:
Accepted Date:
2 June 2017
13 July 2017
14 July 2017
Please cite this article as: Wang, W., Jin, H., Yan, Z., He, M., Lin, S., Tian, W., Perfluoroalkanosulfonyl Fluoride-
Assisted Atherton–Todd-like Reaction of Diphenylphosphine Oxide with Alcohols Under Air Generating
Diphenylphosphinate Esters, Tetrahedron Letters (2017), doi: http://dx.doi.org/10.1016/j.tetlet.2017.07.052
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Perfluoroalkanosulfonyl Fluoride-Assisted Atherton-Todd-like Reaction of Diphenylphosphine
Oxide with Alcohols Under Air Generating Diphenylphosphinate Esters
Wangyang Wanga, Hongai Jina, Zhaohua Yana, *, Mingchuang Hea, Sen Lina, Weisheng Tianb, *
n-C4F9SO2F
O
O
Et3N
ROH
+
H
P
Ph
R
O
P
Ph
CH3CN, air
25oC, 0.5h
Ph
Ph
in 52-78% yields
15 examples
R=primary or secondary alcohols
Fonts or abstract dimensions should not be changed or altered.

1
Tetrahedron Letters
Perfluoroalkanosulfonyl Fluoride-Assisted Atherton–Todd-like Reaction of
Diphenylphosphine Oxide with Alcohols Under Air Generating Diphenylphosphinate
Esters
Wangyang Wanga, Hongai Jina, Zhaohua Yana,*, Mingchuang Hea, Sen Lina, Weisheng Tianb,*
a College of Chemistry, Nanchang University, Nanchang 330031, P. R. China
b Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, P. R. China
ARTICLE INFO
ABSTRACT
Article history:
Received
Received in revised form
Accepted
An efficient method for the synthesis of diphenylphosphinate esters via the Atherton–Todd-like
reaction of diphenylphosphine oxide with alcohols assisted by perfluoroalkanosulfonyl fluoride
in the presence of triethylamine under air is achieved affording the corresponding
diphenylphosphinate esters in moderate to good yields of 52-78%. The protocol features the use
of non-toxic and stable perfluoroalkanosulfonyl fluoride and metal-free reaction conditions.
Available online
2017 Elsevier Ltd. All rights reserved.
Keywords:
Perfluoroalkanosulfonyl Fluoride
alcohols
diphenylphosphine oxide
Phosphinate esters
Introduction
phosphoric fluorides, diphenylphosphinate esters and S-phenyl
diphenylphosphinothioate esters.9 Prabhu disclosed a I2/H2O2-
Over the past decades, organophosphorus compounds have
found widespread applications in medicinal chemistry1, organic
catalysis2 and material sciences3. The conventional method for
the preparation of organophosphorus compounds is the
substitution reaction of phosphorus chlorides with a wide range
of nucleophiles. The Atherton-Todd reaction provides a more
efficient way to make phosphoramidates, phosphonate esters and
other phosphorus-containing products, and it avoids the
employment of moisture-sensitive and toxic phosphorus
chlorides.4 Recently, Zhao and Han systematically studied the
stereochemistry at the phosphorus center under the Atherton-
Todd reaction conditions leading to the smooth synthesis of
optically active organophosphorus compounds.5 However, the
Atherton-Todd reaction requires the use of highly toxic carbon
tetrachloride or bromotrichloromethane. To overcome this
shortcoming, alternative methods have been recently developed
to make organophosphorus products. In 2008, Hackenberger
published a Lewis acid-catalyzed phosphorimidate rearrangement
yielding secondary phosphoramidates,6 which was subsequently
applied in the site-specific PEGylation of proteins.7 Hayes
disclosed a straightforward synthesis of phosphoramidate starting
from easily available amines and H-phosphonates using CuI as
the catalyst and O2 as the oxidant.8 Yang also reported a copper-
catalyzed oxidative reaction of hydrophosphine oxide with
nucleophiles such as NaF, ROH and RSH for the synthesis of
promoted phosphorylation of acohols and amines to synthesize
phosphoramidates and phosphorus triesters.10 In 2014, Yin
reported Cs2CO3-promoted O-deprotonation/alkylation of
diphenyl phosphinic acid with alkyl halides.11 Generally speaking,
the direct phosphorylation of hydrophosphine oxides or H-
phosphonates with nucleophiles (such as alcohols and amines)
possesses advantage of easily availability of substrates. In view
that organophosphorus compounds play more and more
important roles in both academic and industrial fields, the search
for more convenient, straightforward and effective approaches to
make them (such as phosphonate esters and phosphoramidates,
etc) is still in highly demand.
Perfluoroalkanosulfonyl fluoride (RfSO2F, such as n-C4F9SO2F
and n-C8F17SO2F) is a kind of commercially available and cost
effective reagent. RfSO2F is non-toxic and moisture-tolerant
compound. In industry, they have been widely applied as
precusors for the synthesis of highly valued surfactants
-
perfluoroalkanesulfonic acid salt RfSO3 M+ . On the basis of the
-
excellent leaving ability of perfluorosulfonate anion (RfSO3 ),12
RfSO2F has been explored and used as an excellent hydroxyl
group-activating reagent for fluorination of alcohols to synthesize
fluorides,13 and for cyclodehydration of chiral vicinal diols,14 N-
acylamino alcohols, β-hydroxy sulfonamides and β-hydroxy
thioamides15 for the synthesis of epoxides and other heterocyclic

2
Tetrahedron
compounds. When perfluoroalkanosulfonyl fluoride was used
nitrobenzyl alcohol (3.0 mmol), diphenylphosphine oxide (3.0
mmol), n-C4F9SO2F (18.0 mmol), Et3N (18.0 mmol), 25oC,
CH3CN as solvent and under air.
to activate hydroxyl group of α,β-unsaturated ketoximes,
Beckmann rearrangement occurred leading to the smooth
formation of acid-sensitive enamides.16 The dehydration of
aldoximes to nitriles17 and esterification, amidation and
anhydridization of carboxylic acids18 induced by RfSO2F as an
efficient condensing reagent have been achieved. RfSO2F shows
its unique property in mediating the homoallylic carbocation
rearrangement of 19-hydroxymethyl steroid19 leading to the novel
total synthesis of a naturally occurring (±)-Spiniferin.20 However,
to the best of our knowledge, the use of perfluoroalkanosulfonyl
fluoride in the phosphorylation of alcohols with hydrophosphine
oxides or H-phosphonates has not been investigated yet. In this
work, we wish to report the Atherton–Todd-like reaction of
diphenylphosphine oxide with alcohols under air assisted by
perfluoroalkanosulfonyl fluoride resulting in the formation of
diphenylphosphinate esters in moderate to good yields.
Table 1 Optimization of reaction conditionsa
RfSO2F
O
base
O
P
OH
solvent
O
P
Ph
+
H
Ph
temperature
air
Ph
O2N
Ph
2
O2N
1a
3a
Entry Solvent
Temp. (oC)
Base
Yieldb
(%)
0
1c
2
CH2Cl2
CH2Cl2
CHCl3
25
25
25
Et3N
Et3N
20
5
3
Et3N
4
CH3COCH3 25
Et3N
57
40
45
23
78
30
0
5
PhCH3
THF
25
25
25
25
25
25
25
25
25
25
25
25
0
Et3N
6
Et3N
7
DMF
Et3N
8
CH3CN
EtOAc
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
Et3N
Results and discussion
9
Et3N
10
11
12
13
14
15
16
17
18
19d
20e
Pyridine
i-Pr2NEt
DBU
NaH
Initially we chose p-nitrobenzyl alcohol (1a) as a model
substrate and studied phosphorylation of 1a (3.0 mmol) with
diphenylphosphine oxide (2, 3.0 mmol) under air. The reaction
was carried out in CH2Cl2 (10 mL) at 25oC using n-C4F9SO2F
(6.0 mmol) as RfSO2F and Et3N (9.0 mmol) as a base.
0
76
trace
43
58
0
KOH
NaOH
K2CO3
Et3N
Unfortunately,
the
desired
product
p-nitrobenzyl
diphenylphosphinate (3a) was not detected and only p-
nitrobenzyl fluoride was formed in 80% yield. However, when
the amounts of n-C4F9SO2F and Et3N were respectively increased
to 6.0 equiv. and 6.0 equiv., to our delight, 3a was smoothly
obtained although in low yield of 20% (Table 1, entry 2). Thus
optimization of reaction conditions was next undertaken. Solvent
screening reactions revealed that CH3CN was the best choice of
solvent generating 3a in 78% yield and the employment of THF,
CH3COCH3, CH3COOEt, CHCl3, PhMe and DMF as solvents
only resulted in the formation of 3a in lower 5-57% yields (Table
1, entries 3-9). Among the different bases examined, Et3N gave
the best result (Table 1, entries 10-16). Then, the effect of
reaction temperature was explored. The results showed that the
incomplete reaction was observed at 0oC and p-nitrobenzyl
fluoride was the major product at 50oC (Table 1, entries 17 and
18). When n-C4F9SO2F was replaced by a longer carbon-chain n-
C8F17SO2F, 3a was produced in a slightly lower 73% yield (Table
1, entry 19). Finally, when the reaction of 1a with 2 was run
under nitrogen atmosphere, only trace of 3a was detected (Table
1, entry 20), and this result disclosed that oxygen plays an
important role in this phosphorylation. Further experiments
confirmed that the amount of air has effects on yield of 3a. The
limited amount of air only resulted in the low yield of 3a. when
the reaction 1a with 2 was run at 25oC for 30 min under air, the
highest yield of 3a was obtained, and longer reaction time or
even bubbling of air into the reaction system did not improve the
yield of 3a. Therefore, the optimized reaction conditions are: p-
40
16
73
trace
50
25
25
Et3N
Et3N
Et3N
aReaction conditions: 1a (3.0 mmol),
2 (3.0 mmol), RfSO2F (18.0
mmol), base (18.0 mmol), solvent (20 mL), 25oC, 0.5-2 h, under air.
bIsolated yields. c6.0 mmol of n-C4F9SO2F and 9.0 mmol of Et3N were
used. d18.0 mmol of n-C8F17SO2F was used. eThe reaction was run
under nitrogen atmosphere.
With the optimized conditions in hand, we continued to
investigate the scope and generality of alcohol substrates for the
phosphorylation with 2. The results were summarized in Table 2.
We are pleased to find that a wide range of alcohols underwent
phosphorylation efficiently. The reactions of benzyl alcohols
bearing electron-withdrawing groups on the benzene ring with 2
afford the corresponding esters in good yields of 78% and 65%
(Table 2, 3a and 3b). However, for benzyl alcohol with electron-
donating methyl group on the benzene ring, the corresponding
product was obtained only in moderate 52% yield (Table 2, 3c).
2-Phenylethanol and 4-phenylbutanol are suitable substrates
giving 3e and 3f in 68% and 76% yields respectively (Table 2, 3e
and 3f). For secondary benzylic alcohol substrates, the
phosphorylation with 2 works well (Table2, 3g and 3h). In
addition, when 1-hydroxymethylnaphthalene and cinnamyl
alcohol were used as nucleophiles, the expected products were
obtained in 60% and 65% yields (Table2, 3i and 3j). It is worth
mentioning that when aliphatic primary and secondary alcohols,

3
such as isopropanol, n-butanol, n-heptanol, n-decanol, and
cyclohexanol were subjected to phosphorylation with 2 under the
optimized conditions, the corresponding products were offered in
58-76% yields (Table 2, 3k-3o). However, when methanol,
ethanol and tert-butyl alcohol were tested for the phosphorylation
with 2, only trace of diphenylphosphinate esters were detected.
That the low sterically hindrance caused methanol and ethanol
rather than 2 to prefer to directly react with n-C4F9SO2F
generating the volatile fluorides can probably explain this result.
On the contrary, the high sterically hindrance of tert-butyl
alcohol might be the major reason that its phosphorylation with 2
almost did not work.
Additionally, when the reactions of p-nitrobenzyl alcohol
(1a) with two H-phosphonates (dimethyl phosphite and diethyl
phosphite) instead of diphenylphosphine oxide (2) were
evaluated, likewise, no desired phosphonate triesters products
were detected.
Therefore, perfluoroalkanosulfonyl fluoride can neither be
used to assist the phosphorylation of phenols and amines with
hydrophosphine oxides or H-phosphonates, nor the
phosphorylation of alcohols with H-phosphonates.
In order to put forward to a possible mechanism to interpret
the phosphorylation of alcohols with diphenylphosphine oxide, a
few of control experiments were conducted using p-nitrobenzyl
alcohol (1a) as a model substrate (Scheme 2). When 1a and
diphenylphosphine oxide (2) were mixed in CH3CN at room
temperature in the presence of Et3N without n-C4F9SO2F, 1a was
found to keep unreacted accompanied by the formation of
unidentified species probably originating from the oxidative
dimerization of 2 (Scheme 2, Equation a). The oxidative
dimerization of hydrophosphine oxides or H-phosphonate in the
presence of organic base (such as Et3N) and/or copper catalyst
has been reported.8,21 In the absence of 2, the reaction of 1a with
n-C4F9SO2F/Et3N in CH3CN gave the corresponding p-
nitrobenzyl fluoride 8 which did not react with 1a to give 3a
under the above optimized conditions (Scheme 2, Equation b).
Without 1a, the reaction of 2 with n-C4F9SO2F/Et3N in CH3CN
gave an unstable species A or B which was hard to isolate and
not identified at this time and the subsequent reaction of species
B with 1a smoothly offered 3a in 75% yield (Scheme 2, Equation
c).
Table 2 Phosphorylation of different alcohols with 2a,b
n-C4F9SO2F
Et3N
O
O
+
R
OH
H
P
Ph
R
O
P
Ph
CH3CN
25oC, air
Ph
2
Ph
1
3
O
O
O
O P Ph
O P Ph
O P Ph
Ph
Ph
Ph
O2N
H3C
F
3b (65%)
3c (52%)
3a (78%)
O
O
O
O P Ph
O P Ph
O P Ph
Ph
Ph
Ph
3d (63%)
3e (68%)
3f (76%)
O
O P Ph
O
O
O P Ph
Ph
O P Ph
Ph
Ph
O2N
3g (55%)
3i (60%)
3h (70%)
O
O
O
O P Ph
O P Ph
O P Ph
Ph
Ph
3k (76%)Ph
3j (65%)
3l (70%)
Et3N
CH3CN
25oC, 24 h
air
O
OH
O
O
O
1a
+
+ unidentified species (a)
H
P
Ph
O P Ph
O P Ph
O P Ph
O2N
Ph
2
Ph
Ph
Ph
1a
3n (68%)
3m (64%)
3o(58%)
O
n-C4F9SO2F
Et3N
CH2F
2
×
O
P
Ph
O
O
O
(b)
1a
CH3CN
25oC, 24h
83%
Et3N, CH3CN
25oC, 24 h
air
O P Ph
Ph
C2H5 O P Ph
H3C O P Ph
O2N
O2N
8
3a
Ph
Ph
Ph
3p (Trace)
3q (Trace)
3r (Trace)
n-C4F9SO2F
Et3N
O
O
O
S
O
O2
aThe reaction conditions: alcohol (3.0 mmol), diphenylphosphine oxide (3.0
mmol), n-C4F9SO2F (18.0 mmol) and Et3N (18.0 mmol), CH3CN (20 mL),
under air, 25oC, 0.5 h; bisolated yield.
H
P
Ph
Ph
P
O
C4F9
Ph
P
O
S
C4F9
CH3CN
25oC, 0.5h
air
Ph
2
Ph
O
Ph
O
A
B
O
1a
O
P
Ph
(c)
Next, we explored the reactions of two other nucleophiles,
phenol and morpholine, with diphenylphosphine oxide 2 under
the above optimized conditions. Both reactions only provide
undesired products 4 and 5 other than desired ones 6 and 7, and
the reason is due to the fact that the stronger nucleophilicity of
phenol and morpholine results in their direct attack on RfSO2F
preferentially (Scheme 1).
Et3N, CH3CN
25oC, 0.5h
Ph
O2N
3a
Scheme 2. Control experiments.
The results from the above control experiments and
descriptions in literatures21,22 bring us to propose a plausible
mechanism for the phosphorylation of alcohols with
diphenylphosphine oxide (Scheme 3). First, the reaction of 2 with
Et3N generated anion D. The subsequent attack of D on n-
C4F9SO2F affords species A which was oxidized by oxygen
providing unstable species B. Next, substitution of alkoxyl anion
RO- with B furnished product 3. Meanwhile, species A may first
react with alkoxyl anion RO- to give species E which was
subsequently oxidized by oxygen yielding 3. However, at this
time the exact structure of active and unstable species A, B and E
n-C4F9SO2F
n-C4F9SO2F
O
OSO2C4F9
OH
O
Et3N
Et3
N
P
Ph
O
+
╳
Ph
H
P
CH3CN
CH3CN
Ph
Ph
25℃, air
25℃, air
4
6
n-C4F9SO2F
Et3N
n-C4F9SO2F
Et3N
O
SO2C4F9
O
NH
N
N
P
Ph
+
H
P
Ph
╳
O
O
CH3CN
CH3CN
O
Ph
Ph
25℃, air
25℃, air
7
5
Scheme 1. The reactions of phenol and morpholine

4
Tetrahedron
have not acturally confirmed yet, and further work is now
5 (a) Xiong, B.; Zhou, Y.; Zhao, C.; Goto, M.; Yin, S.-F.; Han, L.-B.
Tetrahedron 2013, 69, 9373-9380; (b) Wang, G.; Shen, R.; Xu,
Q.; Goto, M.; Zhao, Y.; Han, L.-B. J. Org. Chem. 2010, 75, 3890-
3892; (c) Zhou, Y.; Wang, G.; saga, Y.; Shen, R.; Goto, M.; Zhao,
Y.; Han, L.-B. J. Org. Chem. 2010, 75, 7924-7927.
6 Wilkening, I.; Signore, G. D.; Hackenberger, C. P. R. Chem.
Commun. 2008, 596-602.
underway in our laboratory.
Et3N
ROH
RO
Ph
O
O
P
Et3N
n-C4F9SO2F
Ph
P
P
O
Ph
H
Ph
Ph
Ph
D
2
C
7 (a) Serwa, R.; Majkut, P.; Horstmann, B.; Swiecicki, J.-M.;
Gerrits, M.; Krause, E.; Hackenberger, C. P. R. Chem. Sci. 2010,
1, 596-602; (b) Serwa, R.; Wilkening, I.; Signore, G. D.;
Mühlberg, M.; Clauβnitzer, I.; Weise, C.; Gerrits, M.;
Hackenberger, C. P. R. Angew. Chem. Int. Ed. 2009, 48, 8234-
8239. (c) J. P. Krise and V. J. Stella, Adv. Drug Delivery Rev.,
1996, 19, 287–310.
O
S
O
O
S
O
O2
RO
R
Ph
P
O
C4F9
Ph
P
O
C4F9
O
P
Ph
Ph
O
Ph
O
Ph
A
B
3
Ph
RO
O2
P
O
R
Ph
E
8 Fraser, J.; Wilson, L. J.; Blundell, R. K.; Hayes, C. J. Chem.
Commun. 2013, 49, 8919-8921.
Scheme3. The Plausible mechanism.
9 Liu, N.; Mao, L.-L.; Yang, B.; Yang, S.-D. Chem. Commun. 2014
50, 10879 - 10882.
10 Dhineshkumar, J.; Prabhu, K. R. Org. Lett. 2013, 15, 6062 -
6065.
,
Conclusions
I
n summary, an efficient and convenient approach for the
11 Xiong, B.; Ye, Q.; Feng, X.; Zhu, L.; Chen, T.; Zhou, Y.; Au, C.-T.;
Yin, S.-F. Tetrahedron 2014, 70, 9057-9063.
12 Hansen, R. L. J. Org. Chem. 1965, 29, 4322-4326.
13 Vorbruggen, H. Synthesis 2008, 40, 1165-1174.
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15 Yan, Z.; Guan, C.; Yu, Z.; Tian, W. Tetrahedron Lett. 2013, 54,
5788-5790.
16 Yan, Z.; Xu, Y.; Tian, W. Tetrahedron Lett. 2014, 55, 7186-
7189.
synthesis of diphenylphosphinate esters via the Atherton–Todd-
like reaction of diphenylphosphine oxide with alcohols assisted
by perfluoroalkanosulfonyl fluoride in the presence of
triethylamine under air has been developed. The protocol features
the use of non-toxic and stable perfluoroalkanosulfonyl fluoride
and
metal-free
reaction
conditions.
The
use
of
perfluoroalkanosulfonyl fluoride in organic synthesis has been
further extended.
17 Yan, Z.-H.; Tian, H.; Zhao, D.-D.; Jin, H.-A.; Tian, W.-S. Chin.
Chem. Lett. 2016, 27, 96-98.
18 Yan, Z.; Tian, W.; Zeng, F.; Dai, Y. Tetrahedron Lett. 2009, 50,
2727-2729.
19 Tian, W. S.; Lei, Z.; Chen, L.; Huang, Y. J. Fluorine Chem. 2000
101, 305-308.
Acknowledgements
We thank the National Natural Science Foundation of China
(21362022) for the financial support.
,
20 Sun, Y. S.; Ding, K.; Tian, W. S. Chem. Commun. 2011, 47,
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Notes and references
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Bolletta, F.; Manet, I.; Ziessel, R. Angew. Chem. Int. Ed. Engl.
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file. That file can then be transformed into PDF format and
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appropriate editorial office.
3 (a) Granzow, A. Acc. Chem. Soc. 1978, 11, 177-183; (b) Nguyen,
T.-M. D.; Chang, S. C.; Condon, B.; Uchimiya, M.; Fortier, C.
Polym. Adv. Technol. 2012, 23, 1555-1563.
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4 Le Corre, S. S.; Berchel, M.; Couthon-Gourvès, H.; Haelters, J.-P.;
Jaffrès, P.-A. Beilstein J. Org. Chem. 2014, 10, 1166-1196.

5
Highlights:
• The use of non-toxic and stable reagent
perfluoroalkanosulfonyl fluoride reagent.
• Mild and metal-free reaction conditions for
synthesis of diphenylphosphinate ester.
• Perfluoroalkanosulfonyl fluoride-promoted
formation of cationic phosphorus species.