Synthesis of aryl-thiophosphonates via a [1,2] or [1,3] phospho-fries rearrangement

Article abstract of DOI:10.1080/10426507.2010.520291

The synthesis of O,O-diethyl arylthiophosphonates is achieved following a baseinduced [1,2] or [1,3] phospho-Fries rearrangement that makes use of O,O-diethyl O-aryl thiophosphates as substrates. The coordination properties of O,O-diethyl arylthiophosphon

Full text of DOI:10.1080/10426507.2010.520291

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Phosphorus, Sulfur, and Silicon and the
Related Elements
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Synthesis of Aryl-Thiophosphonates
via A [1,2] or [1,3] Phospho-Fries
Rearrangement
Céline Denis a , Aurore Fraix a , Mathieu Berchel a , Jean-Yves Salaün
a & Paul-Alain Jaffrès a
a CEMCA, UMR CNRS 6521, Université de Brest , Université
Européenne de Bretagne , Brest , France
Published online: 25 Apr 2011.
To cite this article: Céline Denis , Aurore Fraix , Mathieu Berchel , Jean-Yves Salaün & Paul-
Alain Jaffrès (2011) Synthesis of Aryl-Thiophosphonates via A [1,2] or [1,3] Phospho-Fries
Rearrangement, Phosphorus, Sulfur, and Silicon and the Related Elements, 186:4, 790-791, DOI:
10.1080/10426507.2010.520291
To link to this article: http://dx.doi.org/10.1080/10426507.2010.520291
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Phosphorus, Sulfur, and Silicon, 186:790–791, 2011
Copyright ꢀC Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426507.2010.520291
SYNTHESIS OF ARYL-THIOPHOSPHONATES VIA A [1,2]
OR [1,3] PHOSPHO-FRIES REARRANGEMENT
Ce´line Denis, Aurore Fraix, Mathieu Berchel,
Jean-Yves Salau¨n, and Paul-Alain Jaffre`s
CEMCA, UMR CNRS 6521, Universite´ de Brest, Universite´ Europe´enne de
Bretagne, Brest, France
Abstract The synthesis of O,O-diethyl arylthiophosphonates is achieved following a base-
induced [1,2] or [1,3] phospho-Fries rearrangement that makes use of O,O-diethyl O-aryl
thiophosphates as substrates. The coordination properties of O,O-diethyl arylthiophosphonates
are also discussed.
Keywords Coordination; phospho-Fries; rearrangement; thiophosphate; thiophosphonate
Thiophosphonates are usually synthesized by making use of air- and/or water-sensitive
intermediates (e.g., thiooxydation of P(III) species). On the other hand, the application of the
phospho-Fries rearrangement (Scheme 1) requires less reactive and thus more convenient
to handle P(V) intermediates. According to this method of synthesis, the rearrangement can
S
OEt
P
OH
O
S
P
OEt
OEt
OEt
[1,3]
Br
n-BuLi
95% yield
1
S
N
OEt
OEt
H
S
P
H
EtO
EtO
S
[1,2]
n-BuLi
N
S
P
N
1. Cl-P(S)(OEt)2, NaH
P
OEt
OEt
P
OEt
OEt
95% yield
2. n-BuLi
[1,2]
2
3
Scheme 1 Synthesis of O,O-diethyl arylthiophosphonate following either a [1,3] or a [1,2] phospho-Fries rear-
rangement.
be achieved on phenol1 or pyrrole2 derivatives, giving rise to diethyl arylthiophosphonates
in high yields. The study of this rearrangement by NMR at low temperature indicates that
the reaction proceeds first by an ortho-metallation (via a metal halogen exchange or a
Received 23 August 2010; accepted 28 August 2010.
Address correspondence to Paul-Alain Jaffre`s, CEMCA, UMR CNRS 6521, Universite´ de Brest, Universite´
Europe´enne de Bretagne, 6 avenue Le Gorgeu, 29238 Brest, France. E-mail: pjaffres@univ-brest.fr
790

SYNTHESIS OF ARYL-THIOPHOSPHONATES
791
Cl
Pd
S
OEt
S
OEt
EtO
EtO
N
S
P
S
P
N
Pd
P
P
N
OEt
OEt
EtO
EtO
5
4
Figure 1 Palladium coordination complexes 4 and 5 synthesized, respectively, from compounds 2 and 3 and a
palladium salt.
deprotonation step) followed by the migration of diethyl thiophosphonate group. For the
[1,3] rearrangement performed on phenol derivatives, the first step is rapid at −78◦C when
the metallation is achieved by a halogen–metal exchange (typically with n-BuLi). The
lithiated intermediate is not detectable, since the [1,3] rearrangement is immediate even at
low temperature (−78◦C). The chemical behavior is different for the [1,2] rearrangement
on pyrrole. Indeed, the metallation occurs between −35 to −40◦C by deprotonation (n-
BuLi is used) while the rearrangement is very slow at this temperature. Consequently, a
full characterization of the lithiated intermediate by low temperature NMR (COSY 1H-1H,
HMBC 1H-13C, HMBC 1H-31P, HMBC 1H-15N, and HMQC 1H-13C) has been achieved.
Besides the synthetic aspect, coordination properties of thiophosphonates have been
evaluated.3 Palladium and silver were selected as metal, and the compounds 2 and 3
as potential bidentate or tridentate ligands. With palladium as metal, the coordination
complexes 4 and 5 were isolated (Figure 1).2,3 When a silver salt was associated with the
bidentate ligand 2, an unstable coordination complex was obtained, but its stabilization can
be achieved by the addition of triphenylphosphine.
REFERENCES
1. Dieng, T.; Fraix, A.; Salau¨n, J. Y.; Dez, I.; Klein Gebbink, R. J. M.; van Koten, G.; Jaffre`s, P. A.
Synlett 2008, 3121–3124.
2. Marie, S.; Lutz, M.; Spek, A. L.; Klein Gebbink, R. J. M.; van Koten, G.; Kervarec, N.; Michaud,
F.; Salau¨n, J. Y.; Jaffre`s, P. A. J. Organomet. Chem. 2009, 694, 4001–4007.
3. Fraix, A.; Lutz, M.; Spek, A. L.; Klein Gebbink, R. J. M.; van Koten, G.; Salau¨n, J. Y.; Jaffre`s, P.
A. Dalton Trans. 2010, 39, 2942–2946.