Tf2O/DMSO-Promoted P-O and P-S Bond Formation: A Scalable Synthesis of Multifarious Organophosphinates and Thiophosphates

Article abstract of DOI:10.1021/acs.orglett.0c04127

A Tf2O/DMSO-based system for the dehydrogenative coupling of a wide range of alcohols, phenols, thiols, and thiophenols with diverse phosphorus reagents has been developed. This metal- and strong-oxidant-free strategy provides a facile approach to a great variety of organophosphinates and thiophosphates. The simple reaction system, good functional-group tolerance, and broad substrate scope enable the application of this method to the modification of natural products and the direct synthesis of bioactive molecules and flame retardants.

Full text of DOI:10.1021/acs.orglett.0c04127

pubs.acs.org/OrgLett
Letter
Tf2O/DMSO-Promoted P−O and P−S Bond Formation: A Scalable
Synthesis of Multifarious Organophosphinates and Thiophosphates
Jian Shen, Qi-Wei Li, Xin-Yue Zhang, Xue Wang, Gui-Zhi Li, Wen-Zuo Li, Shang-Dong Yang,
and Bin Yang*
Cite This: Org. Lett. 2021, 23, 1541−1547
Read Online
sı
*
Metrics & More
Article Recommendations
Supporting Information
ACCESS
ABSTRACT: A Tf2O/DMSO-based system for the dehydrogen-
ative coupling of a wide range of alcohols, phenols, thiols, and
thiophenols with diverse phosphorus reagents has been developed.
This metal- and strong-oxidant-free strategy provides a facile
approach to a great variety of organophosphinates and
thiophosphates. The simple reaction system, good functional-
group tolerance, and broad substrate scope enable the application
of this method to the modification of natural products and the
direct synthesis of bioactive molecules and flame retardants.
Scheme 1. Strategies for the Phosphinoylation of RO−H and
RS−H
hemical structures possessing a P−O or P−S bond are
Cubiquitous motifs that display remarkable chemical and
biological properties,1 which give them a broad utility in a range
of diverse fields from the pharmaceutical chemistry2 to
agrochemistry,3 organic synthesis,4 and materials chemistry.5
Accordingly, synthetic chemists have devoted considerable
efforts to exploring efficient and convenient methods for the
formation of P−O and P−S bonds, and remarkable progress has
been made during recent years.6−8 Among them, phosphinoy-
lation of alcohols and thioalcohols continues to be a compelling
and straightforward strategy (Scheme 1a), as chemicals
containing an −OH or −SH group are abundant in nature
and readily available.
The traditional routes for the phosphinoylation of R−OH and
R−SH relies on their substitution with R2P(O)X reagents,
including nucleophilic substitution with the toxic and moisture-
sensitive phosphoryl halides9 (Scheme 1a, path I), and the
Atherton−Todd process10 with toxic polyhaloalkanes as both
the reagent and solvent (Scheme 1a, path II). The direct
dehydrogenation phosphinoylation of P(O)−H reagents with
R−OH and R−SH represents one of the most attractive
strategies for P−O and P−S bond formation as it is a comparably
etom-economical and efficient method for the synthesis of these
compounds. In recent years, a variety of dehydrogenative
methods, including CDC11,12 (cross-dehydrogenative coupling)
and P-radical-involved phosphinoylation reactions,13 have been
developed (Scheme 1a, path III). In 2017, Hirano and Miura
pioneered an elegant metal-free strategy for dehydrogenative
phosphinoylation14 in which a P(III) intermediate was first
generated. Following another oxidation step by H2O2, a P(V)
product was produced. In 2018, Lu’s group successfully applied
this new strategy to the phosphinoylation of phenols and
thiophenols (Scheme 1a, path IV);15 however, aliphatic alcohols
and thiols, as well as other phosphorus reagents, were not
compatible in this Tf2O/H2O2 system.
Although tremendous progress has been made in the field of
the phosphinoylation of RO−H and RS−H, the existing
Received: December 14, 2020
Published: February 24, 2021
https://dx.doi.org/10.1021/acs.orglett.0c04127
© 2021 American Chemical Society
Org. Lett. 2021, 23, 1541−1547
1541

Organic Letters
pubs.acs.org/OrgLett
Letter
approaches still suffer from a number of limitations, such as the
use of precious metal salts and strong oxidants, harsh conditions.
Additionally, the reactions of RO−H and RS−H with
arylphosphine oxide, phosphites, or other P(O)−H reagents
are often incompatible in the same reaction. Therefore,
developing new reaction systems that are more practical,
environmentally friendly, and display an enhanced substrate
compatibility would be highly desirable to the synthetic
community. Due to our continued interest in discovering new
organophosphorus transformations,16 herein we describe a facile
metal- and strong-oxidant-free system for the dehydrogenative
coupling of a wide range of R−OH and R−SH compounds with
diverse P(O)−H reagents (Scheme 1b). This one-step protocol
exhibits a good functional-group tolerance and provides an
extremely versatile approach to organophosphinates and
thiophosphates.
were higher than those of the secondary alcohols (1h−1i),
whereas the phosphinoylation did not take place with a tertiary
alcohol (1j). Moreover, alcohols with a variety of functional
groups (S1k−S1dd) were found to be well tolerated. In
addition, substrates containing N-heterocyclic moieties were
also tolerated (1ee−1ff).
We then investigated the scope of phenol derivatives (Table 2,
second row). It was shown that higher yields were obtained with
electron-withdrawing groups (2d−2k) than with electron-
donating groups (2b and 2c). Moreover, multisubstituted
substrates (S2l and S2m) and 2-naphthol (S2n) also reacted
smoothly.
Subsequently, the substrate-scope study with regard to the
RS−H compounds was explored (Table 2, third row). For
thiophenol derivatives, both electron-rich and electron-deficient
substrates gave the corresponding products 3a−3j in excellent
yields. It is interesting to note that the transformation occurred
with complete chemoselectivity when 4-mercaptophenol (S3k)
was used as a substrate, generating product 3k in a good yield.
For thiol derivatives, the phosphinoylation also proceeded well.
Substrates bearing alkyl (S3l−S3n), ester (S3o), cycloalkyl
(S3p), benzyl (S3q), and dithiol (S3r) substituents afforded the
corresponding products 3l−3r in moderate to good yields.
Furthermore, various natural products were directly used as
substrates to evaluate the potential of this method in the
modification of bioactive molecules (Table 2, fourth row).
Natural products, including L-(−)-menthol (S4a), vitamin D3
(S4b), cholesterol (S4c), (−)-β-citronellol (S4d), and L-
(−)-borneol (S4e), performed well in the reaction conditions.
We also examined the scope of the P(O)−H reagents (Table
2, last row). Pleasingly, a broad range of phosphorus reagents are
compatible with this Tf2O/DMSO system (5a−5z). As shown,
various diarylphosphine oxides performed well with thiophenol
(5a−5d). Gratifyingly, phosphites and other P(O)−H reagents
could be successfully reacted with thiophenols to generate the
corresponding products 5e−5m in good yields. In addition, such
P(O)−H reagents were also reactive with different thiols (5n−
5v). When using alcohols and phenols, DOPO (9,10-dihydro-9-
oxa-10-phosphaphenanthrene 10-oxide) still exhibited a high
reactivity (5w and 5x, respectively), while butyl phenyl-
phosphine oxide or ethyl phenylphosphinate performed
relatively poorly (5y or 5z, respectively). No reaction was
observed when using diethyl phosphites with alcohols or
phenols (5aa or 5bb, respectively).
In practice, we chose ethanol (S1a), phenol (S2a), and p-
methylthiophenol (S3a) as substrates to screen the reaction
parameters (see the Supporting Information for full optimiza-
tion details). The optimized reaction conditions for each model
substrate are shown in Table 1 (entries 1, 5, and 8). We also
a
Table 1. Reaction Optimization
a
b
Stirred under N2 overnight, isolated yield. S1a (0.2 mmol, 9.2 mg)/
c
P(O)−H/Tf2O/DMSO 1:2.5:2:2, DMF (2.0 mL), RT. P(O)−H
(0.2 mmol, 40.4 mg)/Tf2O/DMSO 1:3:2, S1a (1.0 mL), 75 °C,
d
To demonstrate the practicality of this method, large-scale
(4.0 mmol) reactions were carried out with a representative
range of coupling partners (Scheme 2). Under the relevant
standard conditions for each, compounds 1e, 2d, 3a, and 5x
were synthesized in excellent yields.
yields were calculated based on HP(O)Ph2. S2a/P(O)−H (0.2
mmol, 40.4 mg)/Tf2O/DMSO 5:1:3:2, MeCN (2.0 mL), 90 °C,
e
yields were calculated based on HP(O)Ph2. S3a (0.2 mmol, 24.8
mg)/P(O)−H/Tf2O/DMSO 1:2:2:2, MeCN (2.0 mL), RT.
Moreover, we also applied our method to the efficient
synthesis of various bioactive molecules, flame retardants, and
phosphorus-containing ligands (Scheme 3). A variety of
bioactive molecules, including pesticide 6, anticholinesterase
7, antistatic agent 8, curing accelerator 9, and inezin 10 were
synthesized with Tf2O/DMSO conditions (Scheme 3A).8c,o
The DOPO-type flame retardants 11−14,5e which have
excellent performance as flame retardants, were also smoothly
synthesized (Scheme 3B). In addition, commonly used chiral
auxiliaries diacetone-D-glucose 15 and (S)-BINOL 17 were
successfully modified via our phosphinoylation process to
produce the P−O ligand scaffolds 16 and 18, respectively
(Scheme 3C).4d
found that a higher yield was obtained when ethanol (S1a) was
employed as both a reactant and a solvent (Table 1, entry 4).
Control experiments revealed the requirement for Tf2O, as
when it was excluded from the system no product formation was
detected (Table1, entries 2, 6, and 9). Additionally, the yield of
the reaction dropped significantly in the absence of DMSO
(Table 1, entries 3, 7, and 10).
With the optimized conditions in hand, we explored the scope
of the reaction (Table 2). We were excited to find that a very
broad range of RO−H and RS−H compounds efficiently
underwent phosphinoylation to yield the corresponding
products 1−5. First, a variety of alcohols were tested (Table 2,
first row). As shown, the yields of the primary alcohols (1a−1g)
1542
https://dx.doi.org/10.1021/acs.orglett.0c04127
Org. Lett. 2021, 23, 1541−1547

Organic Letters
pubs.acs.org/OrgLett
Letter
Table 2. Substrate Scope
a
b
Conditions A: alcohols S1(0.2 mmol)/P(O)−H/Tf2O/DMSO 1:2.5:2:2, DMF (2.0 mL), RT. Conditions B: P(O)−H (0.2 mmol, 40.4 mg)/
c
Tf2O/DMSO 1:3:2, alcohols S1 (1.0 mL), 75 °C, yields were calculated based on HP(O)Ph2. Conditions C: phenols S2/P(O)−H (0.2 mmol,
40.4 mg)/Tf2O/DMSO 5:1:3:2, MeCN (2.0 mL), 90 °C, yields were calculated based on HP(O)Ph2. Conditions D: thiols or thiophenols S3 (0.2
mmol)/P(O)−H/Tf2O/DMSO 1:2:2:2, MeCN (2.0 mL), RT. Performed under conditions A with P(O)−H (0.6 mmol) instead. Performed
under conditions D with P(O)−H (0.6 mmol) instead.
d
e
f
To deduce key information about the reaction mechanism
and examine the actual role of Tf2O and DMSO in this reaction,
a series of control experiments were conducted (see the
Supporting Information for more details). Some key results
are listed in Scheme 4. First, when DMSO was replaced by
DMSO18, both 3a and the O18 isotope-labeled product 3a′ were
isolated as a mixture with a ratio of 3.8:1 (Scheme 4a). This
indicates that some oxygen atom incorporation into the product
come from DMSO. Moreover, the replacement of DMSO with
butylsulfoxide led to the generation of dibutyl sulfide 19
(Scheme 4b). The alkanethiols, which were incompatible with
the Tf2O/H2O2 system,15 could successfully react with HP(O)-
1543
https://dx.doi.org/10.1021/acs.orglett.0c04127
Org. Lett. 2021, 23, 1541−1547

Organic Letters
pubs.acs.org/OrgLett
Letter
Scheme 2. Large-Scale Preparation
Scheme 4. Control Experiments
a
b
c
d
Conditions A. Conditions C. Conditions D. Conditions B.
Scheme 3. Applications
reagent (RP-21) was used in the phosphinoylation with
thiophenol S3b, a mixture of the R-configuration product 22
and the S-configuration product 23 was obtained with a total
yield of 51% and a ratio of 1:3.3 (Scheme 4e). It should be noted
that in an SN2-type Atherton−Todd reaction only the complete
stereo-inversion product RP-22 was obtained.10d,f When
compared with our experimental results, this suggests that the
products were partially racemized during the reaction.
On the basis of the above mechanistic studies and previous
literature,14,15,17 a tentative mechanism was proposed (Scheme
5). First, the P(O)−H reagent undergoes tautomerization to the
less-stable P(III) form, which then reacts with Tf2O to generate
an electrophilic phosphorus species I. Subsequently, the R−YH
compound adds to species I via a nucleophilic pathway,
generating the P(III) intermediates A. As shown by the control
experiments, there are two sources of the oxygen atoms in the
product. Accordingly, we propose two possible pathways to
deliver the final P(V) products from A (Scheme 5, paths a and
b). In path a, following the steps of a nucleophilic attack of the
P(III) intermediate on Tf2O, an intramolecular rearrangement
of B,17d and further electron transfer, the P(III) intermediate
captures an oxygen atom from Tf2O to afford the desired P(V)
product. In path b, an Albright−Goldman type process17i is
involved. Tf2O first reacts with DMSO to produce complex D
and the triflate exchange complex D′, followed by the
nucleophilic attack of A and the intermolecular attack by
TfO− at the phosphonium to generate E and E′, which undergo
the intramolecular rearrangement to release dimethyl sulfi-
de.17e−g The subsequent electron transfer of F and F′ produces
the desired P(V) products.
a
Performed under conditions D with P(O)−H (0.6 mmol) instead.
b
Performed under conditions A with P(O)−H (0.6 mmol), Tf2O (0.6
c
d
mmol), and DMSO (0.6 mmol) instead. Conditions B. Conditions
C.
Ph2 to generate the corresponding products 3l−3r. It is possible
that DMSO may also act as a base to enhance the nucleophilicity
of the R−SH substrates.12d Next, to verify our hypothesis that
the P(V) product is formed by the oxidation of a P(III)
intermediate, compound 20 was employed as a substrate
(Scheme 4c). Indeed, the P(III) compound 20 could be
smoothly converted to the desired P(V) product 2a under the
standard conditions (Scheme 4c, eq 1). Notably, the P(V)
product was not detected in the absence of Tf2O (Scheme 4c, eq
2). In contrast, product 2a could be obtained in a 50% yield with
only Tf2O in the system (Scheme 4c, eq 3). By combining this
with the above result in Scheme 4a, we believed that some
oxygen atom incorporation into the product may come from
Tf2O. In the competition experiment between primary alcohol
S1d and the secondary alcohol S1i with HP(O)Ph2, the
products 1d and 1i, respectively, were obtained with a ratio of
1.4:1, suggesting that an SN2-type process might be involved in
this reaction (Scheme 4d). Moreover, when a chiral phosphorus
In summary, we have developed a mild and efficient Tf2O/
DMSO-based system for the dehydrogenative phosphinoylation
of a wide range of R−OH or R−SH compounds with diverse
phosphorus reagents to provide a simple and practical approach
1544
https://dx.doi.org/10.1021/acs.orglett.0c04127
Org. Lett. 2021, 23, 1541−1547

Organic Letters
pubs.acs.org/OrgLett
Letter
Scheme 5. Plausible Mechanistic Pathway
to various organophosphinates and thiophosphates. The broad
substrate scope and the good functional-group tolerance enable
the application of this method in the direct synthesis of bioactive
molecules and phosphorus flame retardants. This one-step
approach does not require strong oxidants, and a broad range of
phosphorus reagents and R−YH (Y = O, S) compounds are
compatible. Further investigations into the mechanism and
more applications of this strategy are ongoing in our laboratory.
Xin-Yue Zhang − College of Chemistry and Chemical
Engineering, Yantai University, Yantai 264005, P. R. China
Xue Wang − College of Chemistry and Chemical Engineering,
Yantai University, Yantai 264005, P. R. China
Gui-Zhi Li − College of Chemistry and Chemical Engineering,
Yantai University, Yantai 264005, P. R. China
Wen-Zuo Li − College of Chemistry and Chemical Engineering,
Yantai University, Yantai 264005, P. R. China
Shang-Dong Yang − State Key Laboratory of Applied Organic
Chemistry, Lanzhou University, Lanzhou 730000, P. R.
China; orcid.org/0000-0002-4486-800X
ASSOCIATED CONTENT
■
sı
* Supporting Information
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.orglett.0c04127
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acs.orglett.0c04127.
1
Experimental procedures; characterization data; and H,
Notes
31P, 19F and 13C NMR spectra (PDF)
The authors declare no competing financial interest.
FAIR data, including the primary NMR FID files, for
compounds 1a−1ff, 2a−2n, 3a−3r′, 4a−4e, 5a−5z, 6−
14, 16, and 18 (ZIP)
ACKNOWLEDGMENTS
■
We gratefully acknowledge the National Natural Science
Foundation of China (no. 22001225), the Natural Science
Foundation of Shandong Province (no. ZR2017LB007 and
ZR2016BM23), Chemical Engineering and Process of Shan-
dong Province Key Laboratory Open Funds (Grant KF1811),
and Graduate Innovation Foundation of Yantai University
(GIFYTU, no. YDZD2008) for financial support.
Accession Codes
CCDC 2015154 contains the supplementary crystallographic
data for this paper. These data can be obtained free of charge via
www.ccdc.cam.ac.uk/data_request/cif, or by emailing data_
request@ccdc.cam.ac.uk, or by contacting The Cambridge
Crystallographic Data Centre, 12 Union Road, Cambridge
CB2 1EZ, UK; fax: +44 1223 336033.
REFERENCES
■
AUTHOR INFORMATION
■
(1) (a) Huang, P. J. J.; Wang, F.; Liu, J. Anal. Chem. 2015, 87, 6890−
6895. (b) Montchamp, J.-L. Acc. Chem. Res. 2014, 47, 77−87. (c) Li, N.
S.; Frederiksen, J. K.; Piccirilli, J. A. Acc. Chem. Res. 2011, 44, 1257−
1269. (d) Olsen, J. V.; Blagoev, B.; Gnad, F.; Macek, B.; Kumar, C.;
Mortensen, P.; Mann, M. Cell 2006, 127, 635−648. (e) Organo-
phosphorus Reagents: a Practical Approach in Chemistry; Murphy, P. J.,
Ed.; Oxford University Press: New York, NY, 2004.
(2) (a) Horsman, G. P.; Zechel, D. L. Chem. Rev. 2017, 117, 5704−
5783. (b) McGrath, J. W.; Chin, J. P.; Quinn, J. P. Nat. Rev. Microbiol.
2013, 11, 412−419. (c) Kumar, T. S.; Yang, T.; Mishra, S.; Cronin, C.;
Chakraborty, S.; Shen, J.-B.; Liang, B. T.; Jacobson, K. A. J. Med. Chem.
2013, 56, 902−914. (d) Roux, L.; Priet, S.; Payrot, N.; Weck, C.;
Corresponding Author
Bin Yang − College of Chemistry and Chemical Engineering,
Yantai University, Yantai 264005, P. R. China; orcid.org/
0000-0001-5794-4991; Email: yangbin_hy@ytu.edu.cn
Authors
Jian Shen − College of Chemistry and Chemical Engineering,
Yantai University, Yantai 264005, P. R. China
Qi-Wei Li − College of Chemistry and Chemical Engineering,
Yantai University, Yantai 264005, P. R. China
1545
https://dx.doi.org/10.1021/acs.orglett.0c04127
Org. Lett. 2021, 23, 1541−1547

Organic Letters
pubs.acs.org/OrgLett
Letter
́
Fournier, M.; Zoulim, F.; Balzarini, J.; Canard, B.; Alvarez, K. Eur. J.
Med. Chem. 2013, 63, 869−881.
Tetrahedron Lett. 2019, 60, 150965. (h) Kovacs, S.; Bayarmagnai, B.;
Aillerie, A.; Gooßen, L. J. Adv. Synth. Catal. 2018, 360, 1913−1918.
(i) Zhang, X.; Wang, D.; An, D.; Han, B.; Song, X.; Li, L.; Zhang, G.;
Wang, L. J. Org. Chem. 2018, 83, 1532−1537. (j) Chang, C.-Z.; Liu, X.;
Zhu, H.; Wu, L.; Dong, Z.-B. J. Org. Chem. 2018, 83, 13530−13535.
(k) Min, C.; Zhang, R.; Liu, Q.; Lin, S.; Yan, Z. Synlett 2018, 29, 2027−
2030. (l) Wen, C.; Chen, Q.; Huang, Y.; Wang, X.; Yan, X.; Zeng, J.;
Huo, Y.; Zhang, K. RSC Adv. 2017, 7, 45416−45419. (m) Moon, Y.;
Moon, Y.; Choi, H.; Hong, S. Green Chem. 2017, 19, 1005−1013.
(n) Wang, L.; Yang, S.; Chen, L.; Yuan, S.; Chen, Q.; He, M.-Y.; Zhang,
Z.-H. Catal. Sci. Technol. 2017, 7, 2356−2361. (o) Xu, J.; Zhang, L.; Li,
X.; Gao, Y.; Tang, G.; Zhao, Y. Org. Lett. 2016, 18, 1266−1269.
(9) Selected example for the substitution of P(O)−Cl: (a) Kenny, N.
P.; Rajendran, K. V.; Gilheany, D. G. Chem. Commun. 2015, 51, 16561−
16564. (b) Murray, J. I.; Woscholski, R.; Spivey, A. C. Chem. Commun.
2014, 50, 13608−13611. (c) Hong, H.-J.; Bae, A. R.; Um, I.-H. Bull.
Korean Chem. Soc. 2013, 34, 2251−2255. (d) Begec, S.; Alatas, S.; Kilic,
A. Phosphorus, Sulfur Silicon Relat. Elem. 2011, 186, 1531−1537.
(10) Selected examples for the Atherton−Todd reaction: (a) Trofi-
mov, B. A.; Gusarova, N. K.; Volkov, P. A.; Ivanova, N. I.; Khrapova, K.
O. Heteroat. Chem. 2016, 27, 44−47. (b) Li, W. S.; Chen, T.; Saga, Y.;
Han, L.-B. RSC Adv. 2015, 5, 71544−71546. (c) Le Corre, S. S.;
(3) (a) Quin, L. D. A Guide to Organophosphorus Chemistry; Wiley
Interscience: New York, NY, 2000. (b) Gallo, M. A.; Lawryk, N. J.
Organic Phosphorus Pesticides. In The Handbook of Pesticide
Toxicology; Hayes, W. J., Laws, E. R., Eds.; Academic Press: San
Diego, CA, 1991. (c) Melnikov, N. N. Chemistry of Pesticides; Gunther,
F. A., Gunther, J. D., Eds.; Springer-Verlag: New York, NY, 1971.
(d) Khasawneh, F. E.; Sample, E. C.; Kamprath, E. J. The Role of
Phosphorus in Agriculture; American Society of Agronomy: WI,
Madison, 1980.
(4) (a) Ozturk, T.; Ertas, E.; Mert, O. Chem. Rev. 2010, 110, 3419−
3478. (b) Martin, R.; Buchwald, S. L. Acc. Chem. Res. 2008, 41, 1461−
1473. (c) McReynolds, M. D.; Dougherty, J. M.; Hanson, P. R. Chem.
Rev. 2004, 104, 2239−2258. (d) Tang, W.; Zhang, X. Chem. Rev. 2003,
103, 3029−3070.
(5) (a) Howell, B. A.; Alrubayyi, A. Polym. Degrad. Stab. 2019, 162,
196−200. (b) Steinbach, T.; Wurm, F. R. Angew. Chem., Int. Ed. 2015,
54, 6098−6108. (c) Qiu, Y.; Worch, J. C.; Chirdon, D. N.; Kaur, A.;
Maurer, A. B.; Amsterdam, S.; Collins, C. R.; Pintauer, T.; Yaron, D.;
Bernhard, S.; Noonan, K. J. T. Chem. - Eur. J. 2014, 20, 7746−7751.
(d) Noro, M.; Fujita, S.; Wada, T. Org. Lett. 2013, 15, 5948−5951.
(e) Hirata, K.; Ishikawa, A.; Kobayashi, J.; Matsuda, N.; Miwa, K. WO
2011099461 A1, 2011
̀
̀
Berchel, M.; Couthon-Gourves, H.; Haelters, J.-P.; Jaffres, P.-A.
Beilstein J. Org. Chem. 2014, 10, 1166−1196. (d) Xiong, B.; Zhou, Y.;
Zhao, C.; Goto, M.; Yin, S.-F.; Han, L.-B. Tetrahedron 2013, 69, 9373−
9380. (e) Wagner, S.; Rakotomalala, M.; Bykov, Y.; Walter, O.; Doring,
M. Heteroat. Chem. 2012, 23, 216−222. (f) Wang, G.; Shen, R.; Xu, Q.;
Goto, M.; Zhao, Y.; Han, L.-B. J. Org. Chem. 2010, 75, 3890−3892.
(g) Atherton, F.; Todd, A. J. Chem. Soc. 1947, 674−678.
(11) Recent examples for P−O bond formation: (a) Yu, X.; Zhang, S.;
Jiang, Z.; Zhang, H.-S.; Wang, T. Eur. J. Org. Chem. 2020, 2020, 3110−
3113. (b) Saito, Y.; Cho, S. M.; Danieli, L. A.; Kobayashi, S. Org. Lett.
2020, 22 (8), 3171−3175. (c) Anitha, T.; Ashalu, K. C.; Sandeep, M.;
Mohd, A.; Wencel-Delord, J.; Colobert, F.; Reddy, K. R. Eur. J. Org.
Chem. 2019, 2019, 7463−7474. (d) Eljo, J.; Murphy, G. K. Tetrahedron
Lett. 2018, 59, 2965−2969. (e) Chen, Q.; Zeng, J.; Yan, X.; Huang, Y.;
Wen, C.; Liu, X.; Zhang, K. J. Org. Chem. 2016, 81, 10043−10048.
(f) Li, C.; Chen, T.; Han, L.-B. Dalton Trans. 2016, 45, 14893−14897.
(g) Xiong, B.; Feng, X.; Zhu, L.; Chen, T.; Zhou, Y.; Au, C.-T.; Yin, S.-F.
ACS Catal. 2015, 5, 537−543. (h) Liu, N.; Mao, L.-L.; Yang, B.; Yang,
S.-D. Chem. Commun. 2014, 50, 10879−10882. (i) Dhineshkumar, J.;
Prabhu, K. R. Org. Lett. 2013, 15, 6062−6065.
(12) Recent examples for P−S bond formation: (a) Xue, J.-W.; Zeng,
M.; Zhang, S.; Chen, Z.; Yin, G. J. Org. Chem. 2019, 84, 4179−4190.
(b) Huang, H.; Ash, J.; Kang, J. Y. Org. Biomol. Chem. 2018, 16, 4236−
4242. (c) Song, S.; Zhang, Y.; Yeerlan, A.; Zhu, B.; Liu, J.; Jiao, N.
Angew. Chem., Int. Ed. 2017, 56, 2487−2491. (d) Sun, J.-G.; Weng, W.-
Z.; Li, P.; Zhang, B. Green Chem. 2017, 19, 1128−1133. (e) He, W.;
Hou, X.; Li, X.; Song, L.; Yu, Q.; Wang, Z. Tetrahedron 2017, 73, 3133−
3138. (f) Zhu, Y.; Chen, T.; Li, S.; Shimada, S.; Han, L. B. J. Am. Chem.
Soc. 2016, 138, 5825−5828. (g) Bi, X.; Li, J.; Meng, F.; Wang, H.; Xiao,
J. Tetrahedron 2016, 72, 706−711.
(6) For recent reviews, see: (a) Jones, D. J.; O’Leary, E. M.; O’Sullivan,
T. P. Adv. Synth. Catal. 2020, 362, 2801−2846. (b) Peng, K.; Dong, Z.-
B. Eur. J. Org. Chem. 2020, 2020 (34), 5488−5495. (c) Hosseinian, A.;
Farshbaf, S.; Fekri, L. Z.; Nikpassand, M.; Vessally, E. Top Curr. Chem.
2018, 376 (3), 23. (d) Jones, D. J.; O’Leary, E. M.; O’Sullivan, T. P.
Tetrahedron Lett. 2018, 59, 4279−4292. (e) Yang, J.; Xiao, J.; Zhou, Y.
B.; Chen, T. Q.; Yin, S. F.; Han, L. B. Youji Huaxue 2017, 37, 1055−
1068. (f) Sobkowski, M.; Kraszewski, A.; Stawinski, J. Recent Advances
in H-Phosphonate Chemistry. Part 1. H-Phosphonate Esters: Synthesis
and Basic Reactions. In Phosphorus Chemistry II: Synthetic Methods;
Montchamp, J.-L., Ed.; Topics in Current Chemistry, Vol. 361);
Springer: Heidelberg, Germany, 2015; pp 137−177.
(7) For recent papers on P−O bond formation, see: (a) Inial, A.;
Morlet-Savary, F.; Lalevée, J.; Gaumont, A.−C.; Lakhdar, S. Org. Lett.
2020, 22, 4404−4407. (b) Ying, J.; Gao, Q.; Wu, X.-F. Chem. - Asian J.
2020, 15, 1540−1543. (c) Qian, Y.; Dai, Q.; Li, Z.; Liu, Y.; Zhang, J.
Org. Lett. 2020, 22, 4742−4748. (d) Wang, M.; Yang, J.; Wang, S.;
Zhong, H. Tetrahedron Lett. 2020, 61, 151971. (e) Wang, G.; Xiong, B.;
Zhou, C.; Liu, Y.; Xu, W.; Yang, C.-A.; Tang, K.-W.; Wong, W.-Y. Chem.
- Asian J. 2019, 14, 4365−4374. (f) Duan, L.; Zhao, K.; Wang, Z.;
Zhang, F.-L.; Gu, Z. ACS Catal. 2019, 9, 9852−9858. (g) Zhang, D.;
Lian, M.; Liu, J.; Tang, S.; Liu, G.; Ma, C.; Meng, Q.; Peng, H.; Zhu, D.
Org. Lett. 2019, 21, 2597−2601. (h) Li, H.; Lei, J.; Liu, Y.; Chen, Y.; Au,
C.-T.; Yin, S.-F. Org. Biomol. Chem. 2019, 17, 302−308. (i) Xiong, B.;
Wang, G.; Zhou, C.; Liu, Y.; Yang, C.-A.; Zhang, P.; Tang, K.; Zhou, Q.
J. Organomet. Chem. 2019, 885, 21−31. (j) Huang, H.; Denne, J.; Yang,
C.-H.; Wang, H.; Kang, J. Y. Angew. Chem., Int. Ed. 2018, 57, 6624−
6628. (k) Adler, P.; Pons, A.; Li, J.; Heider, J.; Brutiu, B. R.; Maulide, N.
Angew. Chem., Int. Ed. 2018, 57, 13330−13334. (l) Xiong, B.; Wang, G.;
Zhou, C.; Liu, Y.; Zhang, P.; Tang, K. J. Org. Chem. 2018, 83, 993−999.
(m) Huang, H.; Ash, J.; Kang, J. Y. Org. Lett. 2018, 20, 4938−4941.
(n) Xiong, B.; Hu, C.; Gu, J.; Yang, C.; Zhang, P.; Liu, Y.; Tang, K.
ChemistrySelect. 2017, 2, 3376−3380. (o) Xiong, B.; Hu, C.; Li, H.;
Zhou, C.; Zhang, P.; Liu, Y.; Tang, K. Tetrahedron Lett. 2017, 58,
2482−2486.
(13) (a) Zeng, F.-L.; Chen, X.-L.; Sun, K.; Zhu, H.-L.; Yuan, X.-Y.; Liu,
Y.; Qu, L.-B.; Zhao, Y.-F.; Yu, B. Org. Chem. Front. 2021,
DOI: 10.1039/D0QO01410A. (b) Ou, Y.; Huang, Y.; He, Z.; Yu, G.;
Huo, Y.; Li, X.; Gao, Y.; Chen, Q. Chem. Commun. 2020, 56, 1357−
1360. (c) Deng, L.; Wang, Y.; Mei, H.; Pan, Y.; Han, J. J. Org. Chem.
2019, 84, 949−956. (d) Li, Q.-Y.; Swaroop, T. R.; Hou, C.; Wang, Z.-
Q.; Pan, Y.-M.; Tang, H.-T. Adv. Synth. Catal. 2019, 361, 1761−1765.
(e) Li, Y.; Yang, Q.; Yang, L.; Lei, N.; Zheng, K. Chem. Commun. 2019,
55, 4981−4984. (f) Li, C.-Y.; Liu, Y.-C.; Li, Y.-X.; Reddy, D. M.; Lee,
C.-F. Org. Lett. 2019, 21, 7833−7836. (g) Zhang, H.; Zhan, Z.; Lin, Y.;
Shi, Y.; Li, G.; Wang, Q.; Deng, Y.; Hai, L.; Wu, Y. Org. Chem. Front.
2018, 5, 1416−1422. (h) Fu, H.; Yang, T.; Shang, J.-Q.; Zhou, J.-L.;
Sun, M.; Li, Y.-M. Org. Chem. Front. 2017, 4, 1777−1780. (i) Wang, D.;
Zhao, J.; Xu, W.; Shao, C.; Shi, Z.; Li, L.; Zhang, X. Org. Biomol. Chem.
2017, 15, 545−549. (j) Liao, L. L.; Gui, Y. Y.; Zhang, X. B.; Shen, G.;
Liu, H. D.; Zhou, W. J.; Li, J.; Yu, D. G. Org. Lett. 2017, 19, 3735−3738.
(8) For recent papers on P−S bond formation, see: (a) Shi, S.; Zhang,
P.; Luo, C.; Zhuo, S.; Zhang, Y.; Tang, G.; Zhao, Y. Org. Lett. 2020, 22,
1760−1764. (b) Jones, D. J.; O’Leary, E. M.; O’Sullivan, T. P. Adv.
Synth. Catal. 2020, 362, 1825−1830. (c) Liu, T.; Zhang, Y.; Yu, R.; Liu,
J.; Cheng, F. Synthesis 2020, 52, 253−262. (d) Shi, S.; Chen, J.; Zhuo,
S.; Wu, Z. A.; Fang, M.; Tang, G.; Zhao, Y. Adv. Synth. Catal. 2019, 361,
3210−3216. (e) Chen, X.-Y.; Pu, M.; Cheng, H.-G.; Sperger, T.;
Schoenebeck, F. Angew. Chem., Int. Ed. 2019, 58, 11395−11399.
(f) Choudhary, R.; Singh, P.; Bai, R.; Sharma, M. C.; Badsara, S. S. Org.
Biomol. Chem. 2019, 17, 9757−9765. (g) Mondal, M.; Saha, A.
̈
(k) Noel-Duchesneau, L.; Lagadic, E.; Morlet-Savary, F.; Lohier, J. F.;
1546
https://dx.doi.org/10.1021/acs.orglett.0c04127
Org. Lett. 2021, 23, 1541−1547

Organic Letters
pubs.acs.org/OrgLett
Letter
Chataigner, I.; Breugst, M.; Lalevée, J.; Gaumont, A. C.; Lakhdar, S.
Org. Lett. 2016, 18, 5900−5903. (l) Sun, J.-G.; Yang, H.; Li, P.; Zhang,
B. Org. Lett. 2016, 18, 5114−5117. (m) Wang, J.; Huang, X.; Ni, Z.;
Wang, S.; Wu, J.; Pan, Y. Green Chem. 2015, 17, 314−319.
(14) Unoh, Y.; Hirano, K.; Miura, M. J. Am. Chem. Soc. 2017, 139,
6106−6109.
(15) Yuan, T.; Huang, S.; Cai, C.; Lu, G.-P. Org. Biomol. Chem. 2018,
16, 30−33.
(16) (a) Shen, J.; Xiao, B.; Hou, Y.; Wang, X.; Li, G.-Z.; Chen, J.-C.;
Wang, W.-L.; Cheng, J.-B.; Yang, B.; Yang, S.-D. Adv. Synth. Catal.
2019, 361, 5198−5209. (b) Shen, J.; Yu, R.-X.; Luo, Y.; Zhu, L.-X.;
Zhang, Y.; Wang, X.; Xiao, B.; Cheng, J.-B.; Yang, B.; Li, G.-Z. Eur. J.
Org. Chem. 2019, 2019, 2065−2070. (c) Yang, B.; Hou, S.-M.; Ding, S.-
Y.; Zhao, X.-N.; Gao, Y.; Wang, X.; Yang, S.-D. Adv. Synth. Catal. 2018,
360, 4470−4474.
(17) Tian, J.; Yuan, H.; Zhang, J. J. Comput. Chem. 2020, 41, 1709−
1717. (b) Tashrifi, Z.; Khanaposhtani, M. M.; Larijani, B.; Mahdavi, M.
Adv. Synth. Catal. 2020, 362, 65−86. (c) Ghosh, A.; Lecomte, M.; Kim-
Lee, S.-H.; Radosevich, A. T. Angew. Chem., Int. Ed. 2019, 58, 2864−
2869. (d) Ouyang, Y.; Xu, X.-H.; Qing, F.-L. Angew. Chem. 2019, 131
(51), 18679−18683. (e) Jiang, L.; Ding, T.; Yi, W.; Zeng, X.; Zhang, W.
Org. Lett. 2018, 20, 2236−2240. (f) Riemer, D.; Mandaviya, B.;
̈
̈
Schilling, W.; Gotz, A. C.; Kuhl, T.; Finger, M.; Das, S. ACS Catal. 2018,
8, 3030−3034. (g) Chachignon, H.; Maeno, M.; Kondo, H.; Shibata,
N.; Cahard, D. Org. Lett. 2016, 18, 2467−2470. (h) Janesko, B. G.;
Fisher, H. C.; Bridle, M. J.; Montchamp, J.-L. J. Org. Chem. 2015, 80,
10025−10032. (i) Albright, J.-D.; Goldman, L. J. Am. Chem. Soc. 1965,
87, 4214−4216.
1547
https://dx.doi.org/10.1021/acs.orglett.0c04127
Org. Lett. 2021, 23, 1541−1547