Catalyst- and Oxidant-Free Desulfonative C?P Couplings for the Synthesis of Phosphine Oxides and Phosphonates

Article abstract of DOI:10.1002/adsc.201700886

An efficient and practical approach towards phosphine oxides and phosphonates has been successfully developed through the desulfonative coupling of various sulfones with secondary phosphine oxides and phosphites. This protocol features simple experimental

Full text of DOI:10.1002/adsc.201700886

Title: Catalyst- and Oxidant-Free Desulfonative C-P Couplings for the
Synthesis of Phosphine Oxides and Phosphonates
Authors: Wen-Jing Xiao, Hong-Mei Guo, Quan-Quan Zhou, Xuan
Jiang, and De-Qing Shi
This manuscript has been accepted after peer review and appears as an
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To be cited as: Adv. Synth. Catal. 10.1002/adsc.201700886
Link to VoR: http://dx.doi.org/10.1002/adsc.201700886

10.1002/adsc.201700886
Advanced Synthesis & Catalysis
COMMUNICATION
DOI: 10.1002/adsc.201 ((will be filled in by the editorial staff))
Catalyst- and Oxidant-Free Desulfonative C-P Couplings for
the Synthesis of Phosphine Oxides and Phosphonates
Hong-Mei Guo,a,‡ Quan-Quan Zhou,a,‡ Xuan Jiang,a De-Qing Shia,* and Wen-Jing
Xiaoa,*
a
Hubei International Scientific and Technological Cooperation Base of Pesticide and Green Synthesis, Key Laboratory
of Pesticides & Chemical Biology, Ministry of Education, College of Chemistry, Central China Normal University, 152
Luoyu Road, Wuhan, Hubei 430079, China
Fax: (+86)-27-67862041; Tel: (+86)-27-67862041; E-mail: chshidq@mail.ccnu.edu.cn; wxiao@mail.ccnu.edu.cn
These two authors contribute to this work equally.
‡
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######.
(Figure 1),[2e] but also function as important building
Abstract: An efficient and practical approach towards
blocks in organic chemistry for the synthesis of
bifunctional adducts, carbo- and hetero-cyclic
compounds.[5] Therefore, it is not surprising that many
synthetic endeavours have been made to access the P-
containing compounds.[6] Among them, the
transition-metal-catalyzed cross-coupling reaction of
aryl halides or triflates (-OTf) with secondary
phosphines has established as one of the most
efficient and promising procedures for C-P bond
formations.[7] The pioneering work was disclosed by
phosphine oxides and phosphonates has been successfully
developed through the desulfonative coupling of various
sulfones with secondary phosphine oxides and phosphites.
This protocol features simple experimental procedures
under mild conditions (i.e., catalyst- and oxidant-free, room
temperature and open to air). By doing so, a variety of
alkynyl, alkenyl and allyl phosphine oxides or
phosphonates can be produced in generally good reaction
efficiency and selectivity (31 examples, up to 98% yield).
Keywords: phosphorus compounds; sulfones; desulfona-
tive coupling; catalyst-free; oxidant-free
Organophosphorus compounds are of great impor-
tance in many functional materials and bioactive fine
chemicals, such as agrochemicals, pharmaceuticals
and natural products.[1,2] Moreover, they are widely
employed as versatile synthetic reagents or precursors
in organic synthesis,[3] i.e., phosphonates in
Wadsworth- Horner-Emmons reaction, phosphonium
salts in Wittig reaction, phosphine ligands in
transition metal catalysis or nucleophilic catalysts.[4]
In particular, alkynyl, alkenyl and allyl phosphorus
compounds not only display significant pharma-
ceutical properties, for example, the progesterone
receptor antagonist,[2c] the blood-pressure lowering
fosinopril[2d] and the biologically active ethisterone
Scheme 1. Synthetic methods for C-P bond formation.
Hirao and coworkers, who developed a palladium
-catalyzed phosphination of aryl halides with P(O)H
compounds.[8] Since then, a variety of C-P coupling
reactions have been established, especially using
palladium,[9] copper,[10] silver[11] or nickel[12] catalysis.
Despite these remarkable advances, many transfor-
mations often suffered from harsh and hazardous
Figure 1. Some important biologically active P-containing
molecules.
1
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10.1002/adsc.201700886
Advanced Synthesis & Catalysis
conditions, for example, transition metal residual, solvents (PhCF3, CH3CN, DMSO) proved detrimental
moisture or air sensitivity, multi-step-manufactured for the reaction (Table 1, entries 7-11).
ligands, stoichiometric oxidants, and/or elevated
temperature. In this regard, the development of an Table 2. Scope of the alkynylation of phosphine oxides and
efficient and environmentally benign method for the phosphites.[a,b]
direct construction of C(sp, sp2, sp3)-P bonds under
transition metal- and oxidant-free conditions is still
highly desirable.[13] Based on our continued interest in
the C-P bond formation reactions,[14] we herein
present a novel and practical method for the formation
of a variety of C-P bonds through the desulfonative
coupling[15] of alkynyl, alkenyl and allyl sulfones with
secondary phosphine oxides and phosphites in a
single-flask operation under mild conditions. This
strategy provides the highly regioselective synthesis
of
structural
diversely
functionalized
organophosphorus compounds in good to excellent
reaction efficiency.
Table 1. Optimization of the reaction conditions.[a]
[a] Standard condtions as indicated in entry 4 of Table 1. [b] Isolated
yield. [c] At 60 C.
o
3aa
Yield[b] (%)
Under optimized reaction conditions, we probed
the substrates scope of the C-P coupling reaction of
diphenylphosphine oxide (1a) with various alkynyl
sulfones. As highlighted in Table 2, the coupling
reaction underwent well and gave the desired
products in good to excellent yields. Substrates
bearing either electron-donating groups (e.g., CH3,
OCH3, tBu, and nBu) or electron- withdrawing groups
(e.g., F and Br), either para- or meta-substituted on
the benzene ring, were found to be suitable for the
reaction, and corresponding products 3aa-3ai were
obtained in moderate to high yields (Table 2, 62-98%
yields). Notably, the bromo-substituted substrate
tolerated well in this reaction and gave the
bromo-containing product 3ag (Table 2, 62% yield),
Entry Base
Solvent
Time (h)
1
Na2CO3
THF
THF
1
1
1
1
1
1
1
1
1
3
3
8
2
K3PO4
KOH
27
56
98
95
5
29
37
72
80
63
3
THF
THF
4
5[c]
Cs2CO3
Cs2CO3
THF
6
THF
7
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
CHCl3
CH3OH
PhCF3
CH3CN
DMSO
8
9
10
11
[a]
Reaction conditions: 1a (0.2 mmol), 2a (0.3 mmol), base (0.3
mmol), solvent (2.0 mL) at room temperature under air
atmosphere. [b] Isolated yield. [c] In an open flask.
which
is
usually
difficult
for
transition-metal-catalyzed C-P coupling reactions.
Moreover, functional groups typically sensitive to
transition metal catalysis were tolerated, which
included unactivated alkynyl and unprotected amino
groups (Table 2, 3aj-3ak: 63-81% yields).
Furthermore, heteroaryl-substituted alkynyl sulfone
reagent 2l was applicable as well, affording the
desired product 3al in a moderate yield (Table 2, 42%
yield). In addition, the effect of the different leaving
groups of alkynes on the alkynylation were also
explored. When [(methylsulfonyl)ethynyl]benzene
(2m) or [(trifluoromethylsulfonyl)ethynyl]benzene
(2n) was used as the substrate under the standard
condition, to our delight, the P-alkynylation reaction
underwent smoothly and the desired product 3aa was
afforded in 81% and 43% isolated yields, respectively.
When (bromoethynyl)benzene (2o) was employed,
unfortunately, the reaction did not occurred and no
desired product was obtained. These results might
imply that substituted sulfonyl groups played a vital
role on the P-alkynylation (see the supporting
information). With regard to secondary phosphine
We initiated this study using 1-methyl-4-
((phenylethynyl)sulfonyl)benzene (2a) and diphenyl-
phosphine oxide (1a) as model substrates for the
desulfonative coupling reaction. To our delight, this
reaction did indeed work in THF with the use of
Na2CO3 as the base and the desired product
diphenyl(phenylethynyl)phosphine oxide (3aa) was
isolated in 8% yield (Table 1, entry 1). Subsequently,
some inorganic bases, such as K3PO4, KOH and
Cs2CO3, were evaluated (Table 1, entries 2-4), and
product 3aa was delivered in 98% yield when Cs2CO3
was used (Table 1, entry 4). It is worth noting that,
the reaction could be conducted in an open flask
condition at room temperature without affecting the
reaction efficiency (Table 1, entry 5: 95% yield).
Control experiment showed that the base is crucial in
the desulfonative alkynylation (Table 1, entry 6: 5%
yield). Solvent screening indicated that THF is the
optimal reaction media (Table 1, entry 5). Other
solvents, such as protic solvent CH3OH, medium
polar solvent CHCl3, or more high dielectric aprotic
2
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10.1002/adsc.201700886
Advanced Synthesis & Catalysis
oxides, bis-(4-tolyl)- and bis-(3,5-dimethylphenyl)
substituted phosphine oxides could undergo this
coupling reaction and structurally diverse products
3ba-3ca were delivered in good to excellent yields
(Table 2, 73-81% yields). In addition, diethyl
phosphite was amenable to the coupling reaction and
gave the desired phosphonate product 3da in
moderate yield (Table 2, 65% yield).
After our success on the C(sp)-P coupling, we
wonder whether this procedure is suitable for
C(sp2)-P bond formations. After briefly screening the
reaction conditions,[16] we successfully carried out the
desulfonative alkenylation of Ph2P(O)H with a variety
[a] Reaction conditions: 1 (0.2 mmol), 6 (0.3 mmol), KOH (0.3 mmol),
and CHCl3 (2.0 mL) at room temperature under air atmosphere.
Isolated yield.
Table 3. Scope of the alkenylation of phosphine oxides.[a,b]
[b]
to the best of our knowledge, there is no report on the
direct P-allylation of phosphine oxides with allyl
sulfones under transition metal- and oxidant-free
conditions. Encouraged by above results, we tried to
extend our strategy to the direct P-allylation under
mild conditions. To our delight, P-allylation product
7aa was obtained in an excellent yield after a simple
optimization study.[20] As presented in Table 4, a
variety of allyl sulfone substrates exhibited good
reactivity (Table 4, 7aa-7ad: 64-95% yields). Further-
more, a variety of secondary phosphine oxides were
compatible in the P-allylation, affording the
corresponding products 7ba-7ca in excellent yields
(Table 4, 89-96% yields).
The synthetic application of this direct C-P bond
formation was performed. Firstly, the reaction of
diphenylphosphine oxide (1a) and cholesterol-derived
allyl sulfone (6e) was carried out, producing allyl-
phosphine oxide 7ae in 78% yield (Scheme 2, eq. 1).
Then, a gram-scale alkynylation reaction of substrates
1a and 2a was implemented and this reaction
proceeded smoothly to afford the desired coupling
product 3aa in 82% yield (Scheme 2, eq. 2).
Additionally, a “one-pot” alkynylation of diphenyl-
phosphine oxide (1a) with ethynylbenzene (8a) was
also executed, P-alkynylation product 3aa could be
obtained in 96% yield under the optimal condition
(Scheme 2, eq. 3). Furthermore, diphenyl(phenylethy-
nyl)phosphine oxide 3aa can be easily transformed to
benzo[b]phosphole oxide 10a through a photoredox
catalyzed oxidative C−H/P−H functionalization. As a
result, a promising scaffold of organic electronics and
bioimaging probes was constructed in 81% yield
(Scheme 2, eq. 4).[21]
Some control experiments were performed in
order to probe a possible mechanism for this
transformation. As shown in Scheme 3, when radical
scavengers, such as TEMPO or BHT, were introduced
to the model reaction of substrates 1a and 2a, reaction
efficiencies were not affected. These results can rule
out the radical pathway (Scheme 3a). In addition, the
desulfonative coupling reaction of diphenylphosphine
oxide (1a) and (Z)-methyl-3-phenyl-2-((phenylsul-
fonyl)methyl)acrylate (6f) was performed under the
standard condition, the single product 7af was
[a] Reaction conditions: 1a (0.3 mmol), 4 (0.2 mmol), KOH (0.3 mmol)
and THF (5.0 mL) at room temperature in air atmosphere . Isolated
yield.
[b]
of vinyl sulfones under mild conditions. Note that the
reaction displayed high regioselectivity and afforded
the α-aryl vinyl phosphine oxides in moderate yields.
The structure 5aa was confirmed by X-ray
single-crystal diffraction.[17] Based on the importance
of α-aryl vinyl phosphine oxides,[2e,18] we explored the
functional group tolerance of various vinyl sulfones in
the direct P-alkenylation. As summarized in Table 3,
a range of vinyl sulfones could be employed
successfully in this desulfonative alkenylation. The
electronic and steric properties of substituents on the
benzene ring (e.g., F, Cl, Me, OMe and tBu) had no
obvious influence on the reaction efficiency, and the
corresponding coupling products 5aa-5ag were
provided in moderate isolated yields (Table 3,
45-72%
yields).
It
was
found
that
naphthalene-containing substrate could also be
transformed successfully into the corresponding
product 5ah (Table 3, 73% yield).
In addition, allylphosphine oxides are also very
useful building blocks for the synthesis of natural
products and pharmaceutical molecules.[19] However,
Table 4. Scope of the allylation of phosphine oxides.[a,b]
3
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10.1002/adsc.201700886
Advanced Synthesis & Catalysis
obtained in 17% yield (Scheme 3b), which suggested
a SN2' substitution mechanism.
Scheme 4. Proposed mechanisms.
In conclusion, we have developed a novel and
convenient protocol for the desulfonative alkynylation,
alkenylation and allylation of secondary phosphine
oxides or phosphites. These desulfonative C-P
coupling reactions proceeded well in the absence of
any catalyst and oxidant. This process features a
broad substrate scope and functional group tolerance,
thus providing an attractive access to construct
C(sp)-P, C(sp2)-P and C(sp3)-P bonds in moderate to
good yields under very mild conditions.
Scheme 2. Synthetic applications of the methodology.
Experimental Section
Typical Procedure for the Synthesis of Alkynylphos-
phine Oxides: To a 10 mL Schlenk tube equipped with a
magnetic stir bar was charged with 1a (0.30 mmol, 60.66
mg), 2a (0.20 mmol, 51.26 mg) and Cs2CO3 (0.30 mmol,
97.75 mg) in 2 mL of THF. The solution was stirred at
room temperature and monitored to completion by TLC
analysis. After that the reaction solution was concentrated
under vacuum and the crude was purified by flash
chromatography, eluting with petroleum ether and ethyl
acetate to afford the product 3aa as a white solid in 98%
yield.
Scheme 3. Experiments for the mechanistic study.
On the basis of our observations and some related
literatures,[22] a plausible mechanism for direct desul-
fonative coupling reactions was proposed in scheme 4.
Initially, phosphine oxide anion A was formed from
H-phosphine oxides in the presence of base, then A
processed a nucleophilic addition with 2a to
generated intermediate B, which subsequently
underwent desulfonylation to provide alkynyl
phosphine oxide 3aa for P-alkynylation. The good
regioselectivity of the reaction might be due to the
elimination of benzenesulfinate anion and gave a
stable alkynyl phosphine oxide. (Scheme 4a). On
the other hand, A was acted with 4a and 6f
respectively to give the intermediates C and E
through a nucleophilic addition, which underwent the
elimination of benzenesulfinate (a 1,2-proton transfer
for P-alkenylation) to give the alkenyl/allyl phosphine
oxide 5aa and 7af, respectively. (Scheme 4b).
Typical Procedure for the Synthesis of alkenylphos-
phine Oxides: To a 10 mL Schlenk tube equipped with a
magnetic stir bar was charged with 1a (0.30 mmol, 60.66
mg), 4a (0.20 mmol, 48.82 mg) and KOH (0.30 mmol,
16.83 mg) in 5 mL of THF. The solution was stirred at
room temperature and monitored to completion by TLC
analysis. After that the reaction solution was concentrated
under vacuum and the crude was purified by flash
chromatography, eluting with petroleum ether and ethyl
acetate to afford the product 5aa as a white solid in 72%
yield.
Typical Procedure for the Synthesis of allylphosphine
Oxides: To a 10 mL Schlenk tube equipped with a
4
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10.1002/adsc.201700886
Advanced Synthesis & Catalysis
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room temperature and monitored to completion by TLC
analysis. After that the reaction solution was concentrated
under vacuum and the crude was purified by flash
chromatography, eluting with petroleum ether and ethyl
acetate to afford the product 7aa as a white solid in 95%
yield.
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Acknowledgements
We are grateful to the National Natural Science Foundation of
China (NO. 21472057, 21232003) for support of this research.
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6
This article is protected by copyright. All rights reserved.

10.1002/adsc.201700886
Advanced Synthesis & Catalysis
COMMUNICATION
Catalyst- and Oxidant-Free Desulfonative C-P
Couplings for the Synthesis of Phosphine Oxides
and Phosphonates
Adv. Synth. Catal. Year, Volume, Page – Page
Hong-Mei Guo,a,‡ Quan-Quan Zhou,a,‡ Xuan Jiang,a
De-Qing Shia,* and Wen-Jing Xiaoa*
7
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