Iodoform, a New Reagent in the Todd-Atherton Reaction

Article abstract of DOI:10.1081/SCC-120026306

An innovative and convenient application of the iodoform (1) as the reagent in the synthesis of phosphoramidates via Todd-Atherton reaction is described. The full stereoselectivity of this transformation using a 4-methyl-1,3,2-dioxaphosphinane model system was demonstrated.

Full text of DOI:10.1081/SCC-120026306

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Iodoform, a New Reagent in the Todd-Atherton
Reaction
a
a
Grażyna Mielniczak & Dr. Andrzej Bopusiński
a
Centre of Molecular and Macromolecular Studies, Polish Academy of Sciences, Łódź,
Poland
Available online: 19 Aug 2006
To cite this article: Grażyna Mielniczak & Dr. Andrzej Bopusiński (2003): Iodoform, a New Reagent in the Todd-Atherton
Reaction, Synthetic Communications: An International Journal for Rapid Communication of Synthetic Organic Chemistry,
33:22, 3851-3859
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Õ
SYNTHETIC COMMUNICATIONS
Vol. 33, No. 22, pp. 3851–3859, 2003
Iodoform, a New Reagent in the
Todd-Atherton Reaction
Gra z_ yna Mielniczak and Andrzej Bopusin
´
ski*
Centre of Molecular and Macromolecular Studies,
Polish Academy of Sciences, Lodz , Poland
´
´
ABSTRACT
An innovative and convenient application of the iodoform (1) as the
reagent in the synthesis of phosphoramidates via Todd-Atherton
reaction is described. The full stereoselectivity of this transformation
using
a
demonstrated.
4-methyl-1,3,2-dioxaphosphinane model system was
Key Words: Iodoform; Todd-Atherton reaction; Iodophosphates.
*
Correspondence: Dr. Andrzej Lopusin
molecular Studies, Polish Academy of Sciences, 90-363 Lo
Poland; Fax: (004842) 684-71-26; E-mail: lopuch@bilbo.cbmm.lodz.pl.
´
ski, Centre of Molecular and Macro-
´
dz´ , Sienkiewicza 112,
3
851
DOI: 10.1081/SCC-120026306
Copyright & 2003 by Marcel Dekker, Inc.
0039-7911 (Print); 1532-2432 (Online)
www.dekker.com

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3
852
Mielniczak and Bopusinski
´
Iodophosphates bearing of alkoxy group at the phosphorus atom,
are unstable compounds and cannot be isolated as the substrates for the
[
1–3]
synthetic purposes.
Irrespective to them, the successful iodine-
[
4–7]
[8]
promoted phosphorylation of amines, nucleoside amines, H- phos-
[
phorothioylation of nucleosides as well the oxidation of nucleoside
phosphonate esters,
9]
[10]
were reported. The formation of the
corresponding iodophosphates, as the reactive intermediates in all of
these transformations is generally accepted, moreover, the synthesis
and characterization of the first stable dialkyl iodophosphates with
[
11]
electronegative fluoro-ester groups, was reported recently.
The
Todd-Atherton reaction is one of the most convenient methods for the
in situ preparation of halophosphates, commonly used substrates for
[
12–13]
organophosphorus synthesis.
method, in which, instead of tetrachloromethane, tetrabromomethane,
Several modifications of this classical
[14]
[15]
bromotrichloromethane,
dibromomethane,
[17,18]
as the sources of the halogens, were
a-chlorophospho-
[16]
nates,
applicated.
and chloroacetates
We wish to report here on modification method of the Todd-
Atherton reaction, in which iodoform (1) as the iodinating agent is used.
RESULTS AND DISCUSSION
The treatment of diethyl phosphite (2a) with a solution of 0.9–0.95
equiv. of iodoform, and gaseous ammonia blowing through the reaction
in chloroform or toluene solution gave diethyl phosphoramidate (3a) in
high yield within few minutes (Sch. 1).
The same amidate 3a is formed, in the reaction between 1 and 2a
performed in liquid ammonia. Reaction of the phosphite 2a with 1 and 2
CHI , NH
3
3
R
NH2
O
P
+ NH I + CH I
4 2 2
CHCl , r.t.
3
R'
3
a-b
CHI , PhNH
R
O
H
3
2
R
NHPh
O
P
P
+ PhNH I + CH I
3 2 2
toluene, r.t.
R'
R'
4
a
2
CHI , Et N/PhNH (1:1)
3
3
2
4
a + Et NHI + CH I
3 2 2
toluene, r.t.
a) R=R'= C H O–
2
5
b) R=R'= CH =CH–CH O–
2
2
Scheme 1.

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Iodoform in Todd-Atherton Reaction
3853
equiv. of dry aniline, in toluene solution, at room temperature is
3
relatively a slow process. As shown by P NMR, after 3 h the formation
1
of only 26% of anilidate 4a took place. After next 8 h the formation
3
1
of 75% of anilidate ( P ꢀ 2.78) was detected. The reaction performed
in the presence of 1:1 equ. mixture of aniline and triethylamine gave
diethyl phenylphosphoramidate (4a) in 80% yield, just after 1 h under
identical reaction conditions. Diallyl phosphite (2b) was also used as the
substrate in the reaction with iodoform (1), and in the presence of
gaseous and/or liquid ammonia diallyl phosphoramidate (4b) was
synthesized in high yield. For comparison, diethyl phosphite (2a) reacts
with tetraiodomethane analogously, and in the presence of two
equivalents of aniline in diethyl ether, the formation of anilidate 4a in
3
1
7
4% yield, was observed after 6 h by P NMR. The work-up of the
reaction mixture and separation of the product is rather a tedious
procedure. The product 4a, separated by crystallization in only 28%
yield, was obtained. Therefore, the procedure with the use of tetraiodo-
methane as an iodinating agent seems to be not very convenient
modification of the reaction. The obtained results demonstrate, that the
action of iodoform (1) on phosphite 2a–b in the presence of amines shows
a typical pattern of the Todd-Atherton reaction, which is known to take
[
19,20]
place under basic conditions.
between 1 and 2a, performed in toluene at room temperature, in the
We have established, that the reaction
presence of triethylamine, results in rapid formation of the product,
3
1
[2,3]
resonating at P NMR: ꢀ ꢀ40.97, which was identified
as diethyl
phosphoroiodidate (5a) (Eq. (1)). This unstable product decomposed
completely in the reaction solution, when stored for 3 h at room
temperature.
C H O
C H O
2 5
2
5
O
H
1, Et
3
N
O
I
P
P
+ other products
ð1Þ
C H O
toluene, r.t.
C H O
2 5
2
5
2
a
5a, (46%)
31
δ
P - 40.97
To examine the stereochemical course of the studied Todd-Atherton
reaction, the cis- and trans-2-hydrogen-2-oxo-4-methyl-1,3,2-dioxa-
phosphinanes (6) were selected as model compounds. The formation of
7
tion of 6 by 1 should be result for this step of the reaction.
with retention of configuration at the phosphorus atom during iodina-
[
21,22]
The
subsequent nucleophilic substitution reaction of intermediate iodo-
phosphates 7 with ammonia proceeds with inversion of configuration

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854
Mielniczak and Bopusinski
´
at phosphorus, and formation of trans- and cis-2-amino-2-oxo-4-methyl-
1,3,2-dioxaphosphinanes (8) is observed. The configurational assignment
for cis- and trans-8 has already been established.
[
23]
Also, the reaction between cis-6 and iodoform (1), performed at the
ꢁ
temperature ꢀ33 C in the liquid ammonia solution, took place with
identical stereochemical result, and the exclusive formation of amidate
trans-8 was observed. Under the same reaction conditions, the less
thermodynamically stable trans phosphonate 6 (76% trans, 24% cis)
gave a mixture of 75% of cis-8 and 25% of trans-8 amidates, as
3
1
calculated from P NMR.
The obtained results show high stereoselectivity of the formation of
the trans- and cis-amidates 8 in the reaction between the corresponding
cis- and trans-6 phosphite with iodoform performed, as well as with
ꢁ
gaseous and liquid ammonia (temp. ꢀ30 C).
The full stereoselectivity of the formation of the trans-2-phenylamino-
-oxo-4-methyl-1,3,2-dioxaphosphinane (9) from cis-phosphonate 6 via
2
classical Todd-Atherton reaction (CCl /NEt /PhNH ) was previously
4
3
2
[21]
reported. The chlorination of the trans-phosphonate 6 with tetrachloro-
methane in the presence of triethylamine, gave a mixture of cis- and
trans-2-chloro-2-oxo-4-methyl-1,3,2-dioxaphosphinanes (10), which is
[
22]
due to the cis-10 ! trans-10 izomerization.
Most probably the
cis-iodophosphate 7 formed as the intermediate product of the reaction
depicted on Sch. 2, is thermodynamically less stable product. However, its
izomerization into the trans-isomer 7 is most probably much slower
process than its reaction with ammonia.
In summary, it has been found that easily available iodoform (1) is
a good iodinating reagent in the synthesis of phosphoramidates via
O
P
H
P
I
1
, NH3(exc.)
P
O
O
O
O
O
O
NH2
O
O
CHCl , r.t.
3
cis-6
trans-7
trans-8
NH2
O
P
O
P
1
, NH3(exc.)
P
O
O
O
O
O
O
O
H
I
CHCl , r.t.
3
trans-6 (90%)
cis-6 (10%)
cis-7
trans-7
cis-8 (89%)
trans-8 (11%)
Scheme 2.

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Iodoform in Todd-Atherton Reaction
3855
the Todd-Atherton reaction. The above procedure can be offered as an
alternative to the known method of the phosphorylation of the amine
functional group by iodophosphates prepared in situ. The known routes
for such phosphorylations are based on the Michaelis-Arbusov type of
[
4–10]
[24–26]
the reaction of variety H-phosphates
as well trialkyl phosphites
with iodine as an electrophile. The procedure could be recommended for
synthesis of diallyl phosphoramidate (3b) in high yield, since it avoids the
use of iodine and subsequent the easily addition reaction of halogens to
[
27]
allyl ester group of the phosphite 2b, as it was reported.
EXPERIMENTAL
The solvents were purified by standard methods and freshly distilled
3
1
prior to use. All reactions were monitored by P NMR spectroscopy
with Brucker AC-200 spectrometer operating at 80.96 MHz.
Chemical shifts are reported using 85% H PO as an external standard.
a
3
4
Positive chemical shifts are downfield from the standard. CI and LSIMS
mass spectra were recorded on a Finnigan MAT 95 spectrometer.
Infrared spectra were recorded using an ATI Matson Infinity FTIR
instrument. Melting points were measured with a Boetius apparatus
and are uncorrected.
Materials
[28]
Iodoform,
[28]
[29]
tetraiodomethane,
trans-2-hydrogen-2-oxo-4-methyl-1,3,2-dioxaphosphinanes
diethyl phosphite,
[
cis- and
were pre-
30]
pared according to the known procedures.
[
27,32]
Diallyl phosphite
the action of phosphorus trichloride on the allyl alcohol in dichloro-
was prepared by standard method, involving
ꢁ
ꢁ
[32] 31
methane, b.p.: 42 C/0.1 mmHg, (b.p.: 58–61 C/1 mmHg),
8.2 (CDCl ), J
ꢀ
P NMR
703 Hz, MS(CI) (isobutane) m/z 163 [Mþ1], yield 78%.
3
P–H
General Procedure for Todd-Atherton
Reaction with Use of Iodoform
(
a) Through a stirred solution of 1 equiv. of 1 and 1.1 equiv. of
dialkyl phosphite in dry toluene 30–35 mL, the dried ammonia
was passed at room temperature until the yellow color of the

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´
reaction solution disappeared. The solvent was distilled off in
vacuo. The remaining material was dissolved in dry chloro-
form, and solidified ammonium iodide was filtered off. The
filtrate was evaporated under reduced pressure (1–2 mmHg at
ꢁ
15–20 C), and product was isolated by crystallization or
distillation.
(
b) Into the vigorously stirred liquid ammonia (15–20 mL),
1.0 equiv. of 1 and 1.1 equiv. of dialkyl phosphite at tempera-
ꢁ
ture ꢀ33 C were simultaneously added. The stirring was
continued for 5–10 min. at temperature of the cooling bath
ꢁ
between ꢀ33 and ꢀ35 C. Then the cooling bath was removed,
and the reaction mixture was stirred until the all amount of
ammonia was distilled off. The remaining crude product was
dissolved in dry chloroform and filtered through Celite. The
solvent was evaporated in vacuo, and the product was isolated
by crystallization or distillation.
Diethyl phosphoramidate (3a). (i) Following the general procedure (a)
diethyl phosphite (1.4 g, 10.1 mmol), iodoform (3.9 g, 10.0 mmol),
gaseous ammonia in chloroform (20 mL) gave a solid (1.1 g, 72%); b.p.
ꢁ
9–91 C/0.01 mmHg; P NMR (CDCl ) ꢀ 10.1. MS(CI) (isobutane) m/z
3
31
8
1
[
32] 31
[31]
ꢁ
54 [M þ 1]; (Lit.
P ꢀ 10.9, Lit.
b.p. 131–138 C/0.2 mmHg). (ii)
Following the general procedure (b) diethyl phosphite (2.8 g, 20.3 mmol),
iodoform (7.8 g, 20.0 mmol), liquid ammonia (25 mL) gave a solid pro-
ꢁ
duct (2.5 g, 83%), crystallization: ethyl ether–cyclohexane m.p.: 54 C
ꢁ
[33]
Lit.
(
according to the (a) procedure.
m.p.: 55.5 C). The product 3a was identical with them obtained
Diallyl phosphoramidate (3b). (i) Following the general procedure (b)
diallyl phosphite (3.3 g, 20.3 mmol), iodoform (7.8 g, 20.0 mmol), liquid
ꢁ
ammonia (35 mL) gave an oily liquid (2.6 g, 73.5%) b.p. 125–126 C/
ꢁ
[34]
ꢁ
31
b.p. 130 C/2 mmHg); P NMR
0
.2 mmHg (165–170 C, bath), (Lit.
(
CDCl ) ꢀ 10.43; MS(CI) (isobutane) m/z 178 [M þ 1]. IR (film)
3
ꢀ
1
ꢁ
/cm
506w, 919m, 974s, 1035s, 1070s, 1106m, 1272s, 1362w,
411w, 1651w, 2434w, 2944w(br), 3472w(br); Anal. calcd. for
C H NO P (177.07): C, 40.69; H, 6.82; N, 7.90; P, 17.49; Found: C,
max
1
6
12
3
4
(
0.12; H, 6.80; N, 7.75; P, 17.13%. (ii) Following the general procedure
a) diallyl phosphite (1.70 g, 10.4 mmol), iodoform (3.9 g, 10.0 mmol), and
gaseous ammonia in 30 mL toluene gave a solid product (1.2 g, 68%); b.p.
ꢁ
0–91 C/0.01 mmHg; P NMR (CDCl ) ꢀ 9.8. The obtained product was
3
31
9
identical with the amidate obtained according to the procedure (b).
Diethyl phenylphosphoramidate (4a). (i) The solution of diethyl
phosphite (0.69 g, 5 mmol), aniline (0.93 g, 10 mmol), and 1 (1.96 g,

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Iodoform in Todd-Atherton Reaction
3857
5
mmol) in 15 mL of diethyl ether was stirred at room temperature. The
stirring was continued for 15 h, solvent was evaporated in vacuo, and the
remaining crude product was dissolved in chloroform (30 mL), washed
with water (2 ꢂ 10 mL), 0.5% solution of acetic acid (2 ꢂ 15 mL) and
again with water (3 ꢂ 10 mL). The organic phase was dried with
MgSO , filtered and evaporated. The crude anilidate was purified by
4
ꢁ
31
crystallization (0.87 g, 76.3%). M.p.: 93 C (benzene-hexane); P NMR
[
29]
ꢁ
(
Lit.
CDCl ) 2.66; MS(CI) (isobutane) m/z 230 [M þ 1]; (Lit. m.p.: 96.5 C,
3
35] 31
[
P NMR ꢀ 3.0). (ii) The solution of 2a (0.69 g, 5 mmol), aniline
(
0.46 g, 5 mmol), triethylamine (0.5 g, 5 mmol), and iodoform (1.96 g,
5
The work up of the reaction mixture in the same manner as described
mmol) in 15 mL of Et O was stirred at room temperature for 1.5 h.
2
ꢁ
above, yielded in phosphoramidate 4a (0.93 g, 82%). M.p.: 94.5 C (ethyl
3
1
acetate–hexane), P NMR (CDCl ) ꢀ 2.87. (iii) Into the stirred solution
3
of 2a (0.69 g, 5 mmol), aniline (0.93 g, 10 mmol) in 20 mL Et O, tetraio-
2
domethane (2.59 g, 5 mmol) was added at room temperature in one por-
tion. The solvent was distilled off and the red–brown syrupy material was
dissolved in 20 mL CHCl , washed with H O (3 ꢂ 15 mL) and dried with
3
2
MgSO . The solvent was removed in vacuo and from the residual mate-
4
ꢁ
rial (0.32 g, 28%) of amide 4a m.p.: 91–94 C (yellow prisms) was isolated
by fractional crystallization from benzene–hexane and ethyl
3
acetate-hexane solution, P NMR (CDCl ) ꢀ 2.1.
1
3
Diethyl iodophosphate (5a). Into the solution of 2a (0.069 g,
.5 mmol) and 1 (0.196 g, 0.5 mmol) in dry toluene (0.5 mL) placed in
mm diameter NMR tube, triethylamine (0.05 g, 0.5 mmol) was added
0
5
ꢁ
31
at temperature 20 C. The P NMR spectrum of the reaction mixture
recorded in 5 min after the coupling of the reagents shows the presence
of the following lines: at ꢀ 7.53 (39%) 2a, the group of the signals of
unidentified products with ꢀ from ꢀ8.07 to ꢀ ꢀ13.3 and signal at ꢀ40.97
3
1
ascribed for iodophosphate 5a (ꢀ P ꢀ41.0). The continuous monitoring
3
1
of the reaction solution by P NMR shows that the intensity of the line at
40.97 is decreased progressively and after 3 h this signal in the registered
spectra is no more observed.
ꢀ
Trans-2-amino-2-oxo-4-methyl-1,3,2-dioxaphosphinane (8). (i) Fol-
lowing the general procedure (a) phosphite cis-6 (0.68 g, 5 mmol), (19 g,
5
(
mmol) of 1 and gaseous ammonia in 30 mL of chloroform gave trans-8
ꢁ
31
0.65 g, 86%). M.p.: 176–178 C (ethanol). P NMR (EtOD) 7.25; (Lit.
[23]
ꢁ
31
m.p.: 178–180 C, ꢀ P 9.2); MS(FAB) m/z 152.0 [M þ 1]. (ii) Following
the general procedure (b) phosphite cis-6 (1.36 g, 10 mmol), (3.93 g,
10 mmol) of 1, 35 mL liquid ammonia gave trans-8 (1.4 g, 92%). M.p.:
ꢁ
177–179 C, product identical with that obtained according to the
procedure (a).

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858
Mielniczak and Bopusinski
´
Cis-2-amino-2-oxo-4-methyl-1,3,2-dioxaphosphinane (8). (i) Following
the procedure (a) trans-phosphite 6 (90% trans-, 10% cis-) (1.36 g,
1
0 mmol), iodoform (3.93 g, 10 mmol) 1, and gaseous ammonia gave
.5 g of the product as a mixture of cis-8 (89%) ꢀ 6.3 and trans-8
1
3
11%) ꢀ 9.2 isomers identified by P NMR integrated spectrum. From
1
(
this a (0.93 g, 70%) of cis-8 P NMR (EtOD) ꢀ 6.4 m.p.: 127–128 C;
3
1
ꢁ
[23]
ꢁ
31
Lit. m.p.: 128–130 C, ꢀ P 6.0) was isolated by fractional crystalliza-
(
tion from ethanol-ethyl acetate. MS(FAB) m/z 152 [M þ 1]. (ii) Following
the procedure (b) trans-phosphite 6 (76% trans-, 24% cis-) (0.13 g,
1
cis-6 ꢀ 6.75 (75%) and trans-6 ꢀ 9.68 (25%) identified by P NMR.
mmol) of 1 and 12 mL of liquid ammonia gave a mixture of amidate
3
1
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Iodoform in Todd-Atherton Reaction
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Received in Poland April 8, 2003

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