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recycled to catalyze the C‐O cleaved hydrolysis of
afford quantitative yields of HP(O)Z2 ( ).
2
without affecting the reaction efficiencyDaOt Ia: l1l0..A10ll39th/Ce9sGeCc0l1e2a5r4lKy
revealed the method’s usefulness and potential practical
utilities in industrial manufacturing.
Acknowledgements
Financial supports from AIST were acknowledged. Q. Xu thanks
NNSFC (21672163).
Notes and references
Scheme 2. Proposed mechanism for the Brønsted acids‐
catalyzed C‐O cleavage reactions of P(III) esters.
1
(a) R. Engel, Handbook of Organophosphorus Chemistry,
Marcel Dekker, Inc., New York, 1992; (b) F. R. Hartley, The
Chemistry of Organophosphorus Compounds, Vol. 4, John
Wiley & Sons, Chichester, 1996; (c) L. D. Quin, A Guide to
Organophosphorus Chemistry; Wiley‐Interscience: New York,
2000; (d) V. P. Kukhar, H. R. Hudson, Aminophosphonic and
Aminophosphinic Acids: Chemistry and Biological Activity,
John Wiley & Sons, Chichester, 2000; (e) J. P. Majoral, New
Aspects in Phosphorus Chemistry; Springer: Berlin, Vols. 1‐5;
(f) W. Tang, X. Zhang, Chem. Rev., 2003, 103, 3029; (g) P. J.
Murphy, Organophosphorus Reagents; Oxford University
Press: Oxford, U.K., 2004; (h) T. Baumgartner, R. Réau,
Chem. Rev., 2006, 106, 4681; (i) D. E. C. Corbridge,
Phosphorus: Chemistry, Biochemistry and Technology, Sixth
Edition; CRC Press: London, 2013; (j) C. Queffélec, M. Petit, P.
Janvier, D. A. Knight, B. Bujoli, Chem. Rev., 2012, 112, 3777;
(k) G. P. Horsman, D. L. Zechel, Chem. Rev., 2017, 117, 5704.
(a) A. L. Schwan, Chem. Soc. Rev., 2004, 33, 218; (b) C. S.
Demmer, N. Krogsgaard‐Larsen, L. Bunch, Chem. Rev., 2011,
111, 7981; (c) J.‐L. Montchamp, Acc. Chem. Res., 2014, 47, 77;
(d) F. M. J. Tappe, V. T. Trepohl, M. Oestreich, Synthesis,
2010, 3037; (e) R. Engel, J. I. Cohen, Synthesis of Carbon‐
Phosphorus Bonds, CRC Press, New York, 2004; (f) R. A.
Stockland, Practical Functional Group Synthesis; John Wiley
& Sons, Waukegan, IL, 2016, Chapter 4, pp 219‐470; (g) C. A.
Bange, R. Waterman, Chem. Eur. J., 2016, 22, 12598; (h) R.
Waterman, Chem. Soc. Rev., 2013, 42, 5629; (i) L.‐B. Han, M.
Tanaka, Chem. Commun., 1999, 395; (j) Q. Xu, L.‐B. Han, J.
Organomet. Chem., 2011, 696, 130; (k) Q. Xu, Y.‐B. Zhou, C.‐
In the absence of water, once a catalytic amount of TfOR
(ca. 2 mol% based on the 2 mol% TfOH added)18 is generated
from the reaction of TfOH and (RO)PZ2 (
with
to give a new phosphonium salt R‐P+Z2(OR)∙‐OTf (
According to preceding mechanistic findings, it is more likely
that TfO‐ will attack the RO moiety of
through a
monomolecular SN2‐type reaction to give C‐O cleaved and
rearranged R‐P(O)Z2
) and regenerate TfOR.20 By further
1), it may further react
1
6).
6
(
3
reacting with the remaining (RO)PZ2, TfOR works as the
catalyst to drive the reaction forward to complete. In contrast,
the bimolecular mechanism is less possible according to the
experimental findings and preliminary theoretical calculation
2
of TS2
.
It should also be pointed out that the above
monomolecular SN2‐type mechanism may not be applied to all
substrates.19 Clearly, for phosphites bearing an PhO group
(Table 3, entries 7‐9), the sp2 Ph group cannot undergo SN2‐
type reactions with either TfO‐ or water nucleophiles.
Alternatively, the Ph‐O bond may cleave first to give the
product and a Ph+. For the same reason, (PhO)PZ2 cannot
attack the Ph of TfOPh via SN2‐type process to give the
corresponding phosphonium salt. Hence, P(OPh)3 (1i) could
not afford the target product (Table 3, right column, entry 9)
Q. Zhao, S.‐F. Yin, L.‐B. Han, Mini‐Rev. Med. Chem., 2013, 13
,
824; (l) J. Yang, T. Chen, L.‐B. Han, J. Am. Chem. Soc., 2015,
137, 1782.
and the reactions of 1g
‐
1h selectively occurred at the MeO
3
4
(a) H. G. Cook, H. McCombie, B. C. Saunders, J. Chem. Soc.,
1945, 873; (b) W. F. Barthel, P. A. Giang, S. A. Hall, J. Am.
Chem. Soc., 1954, 76, 4186; (c) C. H. Cambell, D. H. Chadwick,
S. Kaufman, Ind. Eng. Chem., 1957, 49, 1871; (d) H. Fakhraian,
moiety to give 3g‐3h (Table 3, right column, entries 7‐8).
Conclusions
A. Mirzaei, Org. Process Res. Dev., 2004, 8, 401.
The Michalis‐Arbuzov reaction of trialkyl phosphites with
alkyl halides, is one of the most useful methods for the
construction of C‐P(O) bonds.5 However, drawbacks of this
method such as the use of toxic alkyl halides, harsh
conditions, heavy pollution, low efficiency, and release of
toxic gas are also obvious. To solve the problems, modified
methods have been developed.6,7 For example, trimethylsilyl
Lewis acids were used to catalyze the Michaelis–Arbuzov
rearrangement of trivalent phosphorus esters,6 but these
methods either have a limited substrate scope or the used
P(III) esters are not readily available. More recently, modified
Michaelis–Arbuzov reactions using alcohols instead of alkyl
halides have also been reported under ZnI2, ZnBr2, or
PPh3/DDQ‐mediated conditions,7 but these methods
generally require anhydrous conditions, stoichiometric
amounts of activators, restricted to the more reactive allylic
In summary, water can determine the selectivity of the
Brønsted acid‐catalyzed C‐O cleavage reactions of trialkyl
phosphites: with water, the reaction occurs quickly at room
temperature to afford quantitative yields of H‐phosphonates;
without water, the reaction selectively leads to the production
of alkylphosphonates, demonstrating a mild and efficient
halide‐free alternative for the Michaelis‐Arbuzov reaction.
Mechanistic studies and the results of bulky substrates showed
that the reaction perhaps takes place via a monomolecular
mechanism. This method is general in substrate scope as it can
be readily extended to phosphonites and phosphinites for
preparation
of
the
corresponding
H‐phosphinates,
alkylphosphinates, H‐phosphine oxides, and alkylphosphine
oxides. This method can also be easily scaled up to 100 gram
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