Iodine-Promoted Rapid Construction of Carbamoylphosphonates from Phosphinecarboxamides

Article abstract of DOI:10.1002/adsc.201800303

Organic phosphonates and their derivatives are an important class of compounds in a variety of fields, especially medicinal chemistry, materials chemistry, agrochemistry and catalysis. For example, phosphonate esters and carbamoylphosphonates are matrix m

Full text of DOI:10.1002/adsc.201800303

Title: Iodine-promoted Rapid Construction of Carbamoylphosphonates
from Phosphinecarboxamides
Authors: Yong-Hui Wu, Qiu-Li Wu, Wen-Peng Wang, Xi-Cun Wang,
and Zheng-Jun Quan
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To be cited as: Adv. Synth. Catal. 10.1002/adsc.201800303
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10.1002/adsc.201800303
Advanced Synthesis & Catalysis
UPDATES
DOI: 10.1002/adsc.201((will be filled in by the editorial staff))
Iodine-promoted
Rapid
Construction
of
Carbamoylphosphonates from Phosphinecarboxamides
Yong-Hui Wu,a+ Qiu-Li Wu,a+ Wen-Peng Wang,a Xi-Cun Wang,a Zheng-Jun Quana*
a
Laboratory of Eco-Environment-Related Polymer Materials, Ministry of Education, China. Gansu Key Laboratory of
Polymer Materials, College of Chemistry and Chemical Engineering, Northwest Normal University, Lanzhou, Gansu
730070, People’s Republic of China; Fax: (+86)-931-7972626; quanzhengjun@hotmail.com.
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))
had to be conducted at a high temperature over a longer
reaction time. Because of the harsh conditions, low
efficiency, and substrate limitations of the existing
techniques, it remains necessary to develop a more facile
and mild method for synthesizing phosphonates.
Abstract. A one-step, I2-promoted P−H phosphorylation
and oxygenation of phosphinecarboxamides to give
carbamoylphosphonates was achieved. This transformation
exhibits exceptional substrate generality and functional
group compatibility and affords good to excellent yields of
the
desired
phosphonates.
Notably,
cyclic
carbamoylphosphonates can be obtained from diols. The
1
mechanism was investigated using IR, H and 31P NMR
spectroscopy.
Keywords:
Carbamoylphosphonates;
Phosphinecarboxamides; Organic phosphonates; P−H
phosphorylation; Oxygenation
Organic phosphonates and their derivatives are an
important class of compounds in a variety of fields,
especially medicinal chemistry,[1] materials chemistry,[2]
agrochemistry[3] and catalysis.[4] For example, phosphonate
esters[5] and carbamoylphosphonates[6] are matrix
metalloproteinase (MMP) inhibitors, antimetastatic agents
and antitumor agents. Phosphonate esters are usually
prepared via a multistep transformation from a phenol and
an organohalide and require toxic phosphorus halides and
aryl/alkyl halides.[7,8] Palladium-catalyzed couplings of an
aryl halide (ArX) with a P-H compound, which were
developed by Hirao and co-workers, are now typically
used as efficient and substrate-tolerant methods for
preparing phosphonates (Scheme 1).[9,10] Recently, great
advances were made in the synthesis of phosphonate esters
via metal-catalyzed C-P bonds couplings of H-
phosphonates with C-X compounds (X = B, N, O, S and
Si).[11] Despite these clear advances, metal-catalyzed
coupling reactions of P−H with C-X(H) are still limited by
the need for costly noble metal catalysts.[12]
Scheme 1. Phosphonate-forming reactions.
Alcohols are abundant chemical raw materials. Compared
with organohalides, they are more environmentally
friendly, less expensive and offer more structural diversity.
Polimbetova et al have shown that phosphine (PH3) can be
transformed into phosphoric acid and its esters by
oxidation
with oxygen
in the
presence
of
benzoquinone/iodide ions or copper halides.[14] However,
to the best of our knowledge, the synthesis of a
carbamoylphosphonate via the direct transformation of a
phosphinecarboxamides with an alcohol has never been
achieved. Herein, we have developed an unprecedented, I2-
promoted P−H phosphorylation and oxygenation of
phosphinecarboxamides with alcohols (Scheme 1).
Phosphinecarboxamides, which are available from the
addition of aryl/alkyl primary amines to 2-
phosphaethynolate anion (PCO-),[15,16] are important
scaffolds and ligands in synthetic chemistry.[15b-d] We
initiated our studies by probing various reaction parameters
for the envisioned I2-promoted P−H phosphorylation and
oxygenation of phosphinecarboxamide 1a (Table 1). After
considerable experimentation, we found that the desired
Alternatively, remarkable progress has been made
toward the preparation of carbamoylphosphonates by the
reaction of dialkyl phosphonates with isocyanates and
isothiocyanates.[6,13] Although no metal catalysts were
involved in this synthesis, aromatic isocyanates gave lower
yields, excess isocyanate was required and/or the reaction
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10.1002/adsc.201800303
Advanced Synthesis & Catalysis
P−H phosphorylation and oxygenation was achieved at rt
using 1.5 equivalents of I2 in ethyl acetate giving 3ab in
92% yield (table 1, entry 5). Based on the screening of a
representative set of reaction times, 1 min. was found to be
optimal.
Under the optimized conditions, we investigated the
scope and limitations of the P−H phosphorylation and
oxygenation transformation (Scheme 2). These optimized
P−H transformation conditions provide a more rapid and
efficient
procedure
for
the
synthesis
of
carbamoylphosphonates. Primary and secondary alcohols
(2) all reacted with 1a in the presence of 1.5 eq. of I2 to
exclusively afford the corresponding P−H phosphorylation
and oxygenation products (3aa−3aj) in high yields. In
addition to methanol, ethanol, 2-methylpropan-1-ol,
propan-1-ol, butan-1-ol and hexan-1-ol, a secondary
alcohol, propan-2-ol, was well-tolerated in the reaction and
afforded desired product 3ad. Cyclic alcohols such as
cyclohexanol and tetrahydrofuran-3-ol, were compatible in
the reaction with 1a, and provided product 3ai and 3aj in
82% and 63% yield, respectively.
Table 1. Optimization of the reaction conditions for P−H phosphorylation
and oxygenation with alcohols.a
Temp.[oC]
rt
Entry
Solvent
additive
H SO
Time
/min.
1
Yield
3ab[%]
trace
1
2
3
4
5
EtOH
EtOH
EtOH
EtOH
2
4
I (20%)
rt
rt
rt
rt
1
1
1
1
18
71
91
92
2
I (1.0)
2
I (1.5)
2
MeCO2Et
(EA)
I (1.5)
2
6
7
DMF
I (1.5)
rt
rt
1
1
83
90
2
-
I (1.5)
2
aConditions: 1a (0.5 mmol), 2b (4 eq.), additive, solvent (5 mL). bYield of
isolated.
Scheme 2. Scope of the P−H phosphorylation and oxygenation transformations with respect to both the
phosphinecarboxamide and alcohol substrates.
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10.1002/adsc.201800303
Advanced Synthesis & Catalysis
presence of two different alcohols in ethyl acetate (EA),
and we found that the formation of the corresponding
products was not selective (Scheme 4, Eq. (2)). For
instance, the reaction of 1a in the presence of methanol and
ethanol gave a mixture of products 3aab, 3aa, and 3ab in
an approximately 30% yield of each product. The reaction
of 1a in the presence of two alcohols such as
methanol/hexan-1-ol, or methanol/tetrahydrofuran-3-ol
also resulted in the formation of mixtures of the
corresponding carbamoylphosphonates (3aah, and 3aaj).
The reaction of 1c in the presence of two alcohols such as
methanol/propan-2-ol, or methanol/cyclohexanol also
resulted in the formation of mixtures of the corresponding
carbamoylphosphonates (3cad and 3cai). The structures of
the products exhibit comparable bond strengths and are
closely related to those of N-alkyl phosphinecarboxamides.
Fortunately, we obtained a crystalline sample of 3cr
suitable for crystallographic characterization (Fig. 1).[17]
Scheme 3. P−H phosphorylation and oxygenation
transformations of diols.
The scope of the phosphinecarboxamide component in
this P−H phosphorylation-oxygenation reaction is quite
broad. N-Aryl phosphinecarboxamides with electron-
donating substituents (methyl and methoxyl) (products
3bb-3ce) on the aromatic ring and substrates bearing
electron-withdrawing groups (product 3ea) also performed
well in the reaction. Cyclobutanol, and cyclohexanol are
all well-tolerated and deliver expected products 3ck and
3ci in 54% and 83% yields. 2-Phenylpropan-1-ol and
cyclohexylmethanol gave products 3cl and 3cm in high
yields. Dimethoxy-substituted substrate 1 exhibited good
reactivity (85 and 87% yield of 3db and 3dd). N-
Naphthyl-derived substrate 1 smoothly underwent the
developed reaction to give desired product 3di in 85%
yield.
Fig. 1. Molecular structure of 3cr.
Halide-substituted alcohols can also be efficiently
reacted with phosphinecarboxamides. The reaction of 2-
chloroethan-1-ol with 1c in the presence of 1.5 eq. of I2
yielded corresponding chloro-substituted product 3cn in
71% yield. Remarkably, in the case of more reactive
halogenated alcohols, such as 3-bromopropan-1-ol and
iodoethanol, the P−H phosphorylation and oxygenation
still proceeded, and these substrates afforded
corresponding bromo- and iodo-functionalized products
3co and 3cp, respectively. Notably, this transformation is
tolerant of alkynyl groups (product 3cq), which will allow
the valuable products to be further derivatized using
modern cross-coupling techniques.
In addition to monoalcohols, diols readily participate in
the reaction using DMF as the solvent, providing cyclized
products in good yields (Scheme 3). Propane-1,3-diol and
butane-1,4-diol
afforded
the
corresponding
carbamoylphosphonates (3ar, 3as, 3cr, 3cs, and 3dr). 2-
Methylpropane-1,3-diol and 1-methylpropane-1,3-diol,
which generate products 3at, 3ct, 3au, 3cu, 3av, and 3cv,
provide access to the dioxaphosphinane-2-carboxamide 2-
oxide core in a single step from readily available,
inexpensive materials.
We also conducted the cascade reaction on a gram scale,
which showed potential in the industrial process (Scheme
4, Eq. (1)). Finally, the reaction was carried out in the
Scheme 4. Control experiments.
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10.1002/adsc.201800303
Advanced Synthesis & Catalysis
1
Moreover, IR, H and 31P NMR analysis (Fig. 2 and 3)
of the crude mixture from the reaction of 1c and I2 (1.5 eq.)
revealed the disappearance of substrate 1c and the
formation of P-I species 4 (Scheme 4, Eq. (3)). Compound
4 was unstable and we failed to characterize by HRMS, but
it could be directly reacted with MeOH to give product 3ca
in 83% yield. This result suggested that P-I species 4,
which is likely generated by the reaction of 1c with I2, was
the key intermediate in the P-H phosphorylation step.
Although a P-I intermediate similar to species 4 has been
previously proposed in other reports, its existence has
never been experimentally proven. Substrate 1c reacted
with I2 giving a urea 5 and an aniline hydroiodide 6 in the
absence of an alcohol (Scheme 4, Eq. (4)). The reaction of
1c with MeOH under an argon atmosphere was carried out,
and desired product 3ca was not observed. Then, the result
mixture was treated with aq. Na2SO3 delivering the product
3ca in 83% yield. These results and previous report[14a,b]
indicate that compound 7 is the key intermediate (not
isolated) of this reaction and this P−H oxygenation
transformation may utilize the O2 in air as the oxidant
[Scheme 4, Eq. (5)]. Furthermore, control experiments
show that 1a cannot react with iodomethane under the
optimized conditions (Scheme 4, Eq. (6)). Notably, we
found that this P−H phosphorylation and oxygenation
process did not occur in the reaction of 1a with 2,2,2-
trifluoroethanol or tert-butyl alcohol, probably due to the
strong electron-withdrawing effect or steric effect of the
alcohol.
1
Fig. 2A and 2B respectively show the IR (KBr), and H
NMR (in CDCl3) 31P NMR (in CDCl3) of a) substrate 1c
and b) the mixture of 1c with I2. Fig. 2C. 31P NMR (in
CDCl3) of a) product 3ca b) substrate 1c and c) the mixture
of 1c with I2.
Based on the results described above and previous
reports,[18] we propose the following mechanism (Scheme
5): phosphinecarboxamide 1c reacts with I2 to generate
corresponding I-P-I species 4,[18] which could react with
MeOH to form phosphonite intermediate 7.[14a] Finally,
intermediate 7 could be oxidized to 3ca. On the other hand,
it is possible that species 4 was oxidized by air (O2) to give
intermediate 8 and nucleophilic attack on intermediate 8 by
MeOH gives product 3ca.
In conclusion, we have developed the first one-step, I2-
promoted P−H phosphorylation and oxygenation
procedure. Thus, phosphorylation and oxygenation enabled
the
P−H
functionalization
of
N-substituted
phosphinecarboxamides with high yields, a wide substrate
scope and shorter reaction time under exceedingly mild
conditions at rt. This transformation avoids bases and
metal catalysts by using I2.
Scheme 5. Proposed mechanism.
Experimental Section
General procedure for the synthesis of compound 3ab.
The mixture of 1a (0.40 mmol, 61 mg), ethanol (3.2 mmol,
0.14 g, 8 equiv), I2 (0.6 mmol, 151 mg, 1.5 equiv) and
ethyl acetate (5 mL) was stirred at rt for 1 min under air
atmosphere. After the reaction completing monitored by
TLC analysis, 2.0 mL saturated aqueous Na2SO3 solution
were added to the mixture to quench the reaction and
extracted with ethyl acetate (3×25 mL). The combined
organic layers were washed with aqueous NaHCO3 and
brine, dried over MgSO4, filtered, and the volatiles were
removed in vacuum. The residue was purified by column
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10.1002/adsc.201800303
Advanced Synthesis & Catalysis
chromatography on silica gel (ethyl acetate:petroleum
ether = 1:1) to give the corresponding product 3ab as
colourless oil, (93 mg, 90 % yield); Rf = 0.37. All of the
products (3) were synthesized according to above
described procedure.
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We are thankful for the financial support from the National
Nature Science Foundation of China (No 21562036), and the
Scientific and Technological Innovation Engineering program of
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10.1002/adsc.201800303
Advanced Synthesis & Catalysis
UPDATES
Iodine-promoted Rapid Construction of
Carbamoylphosphonates from
Phosphinecarboxamides
Adv. Synth. Catal. Year, Volume, Page – Page
Yong-Hui Wu,a+ Qiu-Li Wu,a+ Wen-Peng Wang,a
Xi-Cun Wang,a Zheng-Jun Quana*
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