Silver-Catalyzed Oxyphosphorylation of Unactivated Alkynes

Article abstract of DOI:10.1002/adsc.202100226

Here, we describe an application of hydroazidation in the instant activation of alkynes for achieving the oxyphosphorylation of unactivated alkynes with diarylphosphinoyl radicals under mild reaction conditions. This reaction provides a method for accessing β-ketophosphine oxides and phosphorus-containing pyrroles. (Figure presented.).

Full text of DOI:10.1002/adsc.202100226

Title: Silver-Catalyzed Oxyphosphorylation of Unactivated Alkynes
Authors: Zikun Wang, Zhaohong Liu, Binbin Liu, and Qingmin Song
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10.1002/adsc.202100226
Advanced Synthesis & Catalysis
COMMUNICATION
DOI: 10.1002/adsc.202((will be filled in by the editorial staff))
Silver-Catalyzed Oxyphosphorylation of Unactivated Alkynes
Binbin Liu,a Qingmin Song,a Zhaohong Liu*a and Zikun Wang*a
a
Jilin Province Key Laboratory of Organic Functional Molecular Design & Synthesis, Department of Chemistry,
Northeast Normal University, Changchun 130024, China . * E-mail: wangzk076@nenu.edu.cn; liuzh944@nenu.edu.cn
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######.
requires high temperature,[4] light[5] or electricity[6]
Abstract: Here, we describe an application of
hydroazidation in the instant activation of alkynes for
achieving the oxyphosphorylation of unactivated alkynes
with diarylphosphinoyl radicals under mild reaction
conditions. This reaction provides a method for accessing
β-ketophosphine oxides and phosphorus-containing
pyrroles.
(Scheme 1A). Therefore, the reaction between
unactivated alkynes and lowly reactive phosphorus-
centered radicals under mild reaction conditions is
highly desirable to synthetic chemists.
Keywords: Alkynes; Silver-catalyzed; Hydroazidation;
β-Ketophosphine oxides; Pyrroles
Organophosphorus compounds are of fundamental
importance in synthetic and biological chemistry.
They are widely found in natural products,
nucleotides and pharmaceuticals, playing a central
role in biology as structural elements and key
mediators of biological processes and serving as vital
materials for organic synthesis.[1] As a result, their
preparation has received much attention, and the
reaction of unsaturated hydrocarbons with
phosphorus-centered radicals is an efficient, step-
economic, and extensively used method for their
preparation.[2] However, in contrast to the wide
applicability of the reaction of alkenes with
phosphorus-centered radicals, the reaction of alkynes
with phosphorus-centered radicals is often limited to
the use of activated alkynes or highly reactive
Scheme 1. (A) The reaction of phosphinoyl radicals with
alkynes; (B) Silver-catalyzed oxyphosphorylation of
unactivated alkynes.
In the past years, our group has engaged in
research on the activation and conversion of alkynes
for the synthesis of nitrogen-containing molecules.[7]
In this context, we have employed a strategy for
activating terminal alkynes by employing silver cata-
lysts, thus developing a general hydroazidation
method for unactivated terminal alkynes to access
vinyl azides.[8] Vinyl azides are highly reactive and
versatile building blocks for many transformations.
The azidyl group of vinyl azides can not only activate
alkenes to facilitate their addition reaction with
radicals[9] but also act as an amino source or a leaving
group to promote the conversion of vinyl azides.[10]
Combined with the above-mentioned properties of
vinyl azides and the high efficiency and good
compatibility of the silver-catalyzed hydroazidation
of alkynes, we speculated that the silver-catalyzed
hydroazidation of alkynes could provide an efficient
strategy for the instant activation of alkynes. Given
the importance of organophosphorus compounds in
people’s daily lives and our continued research
interest in the activation of alkynes, we herein
phosphorus-centered
radical
(such
as
diethoxyphosponyl radical) precursors as raw
materials.[2,3] For example, the reaction of
dialkyl/diaryl H-phosphonate and alkynes can be
easily catalyzed by transition metal, such as Cu,[3b,3d]
Pd,[3i] and Ag,[3a] under mild conditions through
dialkyloxyphosphonyl/diaryloxyphosphonyl radical
intermediates. There have been few reports on the
synthesis of organophosphorus compounds from
unactivated alkynes and lowly reactive dia-
rylphosphinoyl radicals, and all showed poor
functional group tolerance because the reaction
1
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10.1002/adsc.202100226
Advanced Synthesis & Catalysis
establish a silver-catalyzed oxyphosphorylation of
unactivated alkynes via hydroazidation under mild
conditions. This reaction provides a simple and
practical method for the preparation of β-
ketophosphine oxides and phosphorus-containing
pyrroles (Scheme 1B).
concentration of oxygen increases, the rate of
phosphinoyl radical generation increases. Under an
atmosphere of pure oxygen, the rate of phosphinoyl
radical generation is so fast that the generated
radicals are consumed, thereby reducing the yield of
compound 3. Finally, the effect of the amount of
silver salt on the reaction efficiency was also
investigated. The results listed in entries 10 and 11
showed that both increasing and decreasing the
amount of silver salt reduced the yield of compound 3.
With the optimal reaction conditions in hand, the
scope of alkynes was next explored (Scheme 2A).
Alkynes bearing either alkyl chains or cyclic alkyl
groups could participate in this reaction, and the
corresponding β-ketophosphine oxides (1-6) could be
obtained in moderate to high yields. An alkyne with a
three-membered tension ring could retain the three-
membered ring (5) in this reaction. Notably, the
functional groups in the alkyl-bearing alkynes were
not altered in this reaction (7-23), and for alkynes
with internal olefins or internal alkynyl groups, the
reaction could occur selectively at the terminal
alkynes (7-9). For aryl alkynes, the electronic effect
and steric effect of substituents on the benzene ring
had no obvious influence on the reaction, and the
corresponding β-ketophosphine oxides could be
obtained in good yield (24-37). Moreover, fused aryl-
and heteroaryl-substituted alkynes also showed good
tolerance to this reaction (38-42).
Table 1. Optimization of the reaction conditions.a
[Ag] (20
mol%)
Gas
atmosphere
Entry
T (oC)
Yield (%)b
1
2
3
4
5
6
7
Ag2CO3
AgN3
80
80
80
80
65
50
65
Air
Air
Air
Air
Air
Air
47
21
24
61
68
57
56
AgNO3
Ag3PO4
Ag3PO4
Ag3PO4
Ag3PO4
N2
N2/O2 (v/v =
1/1)
8
9
Ag3PO4
Ag3PO4
Ag3PO4
65
65
65
82
73
75
O2
N2/O2 (v/v =
1/1)
10c
N2/O2 (v/v =
1/1)
11d
Ag3PO4
65
63
a Reaction conditions: 1-octyne (0.5 mmol), Ph2P(O)H (1.0
mmol), TMSN3 (1.0 mmol), H2O (1.0 mmol) and [Ag] (0.1
mmol) in DMSO (2 mL) at 65 °C under N2/O2 (v/v = 1/1)
for 10 h; b Isolated yield; c Ag3PO4 (0.15 mmol); d Ag3PO4
(0.05 mmol).
Next, we used 1-octyne as the raw material to
examine the tolerance of diarylphosphine oxides in
the oxyphosphorylation of alkynes (Scheme 2B). The
electronic effect of substituents on the benzene ring
of the diphenylphosphine oxides greatly affected this
reaction. Electron-donating groups, such as methyl
and methoxyl groups, were conducive to reaction
(43-46), while electron-withdrawing groups, such as
chloro and trifluoromethyl groups, were not
conducive to reaction (47 and 48). This difference
may result from the fact that electron-donating groups
can increase the reactivity of diarylphosphine oxide
radicals while electron-withdrawing groups can
stabilize diarylphosphine oxide radicals.[2b,11] Notably,
the reaction also showed good tolerance with
dialkylphosphine oxide, and could give the desired
product 49 with a yield of 44%. The application of
oxyphosphorylation to the functionalization of
alkynes in selected natural products afforded β-
ketophosphine oxides 50-54 in good yields (Scheme
2C), showing functional group tolerance and potential
for functionalizing more-complex molecules of
biological relevance. In addition, when terminal
alkynes with a carbonyl group at the γ position were
used as raw materials, the reaction afforded phospho-
rus-containing pyrroles (55-61) in moderate yields
(52-62%) (Scheme 2D). The structure of product 55
was further confirmed by single-crystal X-ray
diffraction analysis.[12] This method can access 2,5-
disubstituted or 2,3,5-trisubstituted phosphorus-
To verify the feasibility of the strategy for
activating
alkynes
via
hydroazidation,
diphenylphosphine oxide was added to the standard
reaction system for hydroazidation of 1-octyne (Table
1, entry 1).[8] This reaction gave β-ketophosphine
oxide 3 in a yield of 47% after 10 h. To determine the
optimal conditions for this reaction, the catalyst,
temperature, and gaseous atmosphere were varied.
The type of silver catalyst affected the efficiency of
this reaction, and the reaction with silver phosphate
as the catalyst gave the highest yield of compound 3
(entries 2-4). As the reaction temperature was
decreased to 65 °C, the yield of compound 3
increased to 68% (entry 5). However, the yield of
compound 3 decreased to 57% when the reaction
temperature was further lowered to 50 °C (entry 6).
The gas atmosphere had a considerable impact on the
reaction (entries 7-9), and an aerobic environment
was conducive to the reaction (entry 5 vs entry 7). To
a certain extent, as the amount of oxygen increased,
the yield of compound 3 increased (entry 6 vs entry
8). However, the yield of compound 3 under a pure
oxygen atmosphere was not as high as that under a
N2/O2 mixture (entry 8 vs entry 9), potentially be-
cause oxygen may directly/indirectly promote the
generation of phosphinoyl radicals; thus, as the
containing pyrroles
via
a
simple
route.
2
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10.1002/adsc.202100226
Advanced Synthesis & Catalysis
Scheme 2. Scope of the reaction of alkynes with diarylphosphine oxides.
equiv), THF (5 mL), RT, 12 h; h) NaH (1.1 equiv), 3-
bromopropyne (1.1 equiv), THF (5 mL), RT, 8 h.
β-Ketophosphine oxides are important phosphorus-
containing compounds that have a wide range of
applications in organic chemistry, coordination
chemistry, and biochemistry.[13] To test the
practicality of our method for the synthesis of β-
ketophosphine oxides, a multigram-scale experiment
was conducted. Compound 3 was obtained in a yield
of 72% when 20 mmol of 1-octyne was added to the
standard reaction system (Scheme 3), indicating that
this method has the potential for scaled-up production.
Subsequently, several transformations of β-
ketophosphine oxide 3 were carried out. For example,
the carbonyl group in compound 3 could be reduced
to a hydroxyl group (62) almost quantitatively[14] and
could also be converted into a sulfonyl hydrazone
(63) in high yield.[15] The conversion could also occur
at the methylene group of compound 3, introducing a
diazo group (64)[16] or selectively introducing one or
Scheme 3. Gram-scale synthesis and further product
transformations. (a) NaBH4 (0.75 equiv ), MeOH (2 mL),
RT, 1 h; (b) TsNHNH2 (1.2 equiv), CH3COOH (3-5 drop),
o
C2H5OH (2 mL), 70 C, 12 h; (c) TsN3 (1.0 equiv), DBU
o
(1.5 equiv), MeCN (2 mL), 0 C to RT, 12 h; (d) NaH (2.0
equiv), CH3I (2.0 equiv), THF (5 mL), RT, 8 h; (e)
o
selectfluor (3.0 equiv), H2O / CH3CN = 1:1 (2 mL), 40 C,
24 h; (f) Selectfluor (1.1 equiv), H2O / CH3CN = 1:1 (2
mL), RT, 12 h; (g) NaH (2.0 equiv), allyl bromide (1.5
3
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10.1002/adsc.202100226
Advanced Synthesis & Catalysis
of silver salt under an N2/O2 atmosphere did not
produce target product 3 but instead produced
compound 71 (eq. 3), demonstrating that the
diarylphosphine oxide radical was not produced by
the oxidation of oxygen, but by the oxidation of the
silver salt. The reaction of compound 71 under
standard conditions did not afford target product 3
(eq. 4), indicating that compound 71 was not an
intermediate. To verify that redox cycling of silver
occurs in the reaction system, we used powder XRD
to detect the changes in silver species in the reaction
system under different gas atmospheres. As shown in
Scheme 4B, we found that in the reactions under an
N2, O2, or N2/O2 atmosphere, the silver species
detected were elemental silver, silver azide, and a
mixture of elemental silver and silver azide,
respectively, indicating that the conversion of Ag(0)
to Ag(I) in the reaction system depended on the
oxidation of oxygen.
two alkyl or other functional groups, for example (65-
69).[17]
To understand the mechanism of this reaction,
systemic control experiments were carried out. The
oxyphosphorylation of the alkyne was completely
suppressed in the presence of TEMPO, and a small
amount of vinyl azide 70 was detected (Scheme 4A,
eq. 1). Moreover, the reaction of Sp-72 with 90% ee
value and p-toluene acetylene under standard reaction
conditions gave a racemic product 73 (eq. 5). The
above results indicated that the reaction might
involve a radical process and vinyl azide might be a
reaction intermediate. The reaction involves a radical
process was further confirmed by EPR analysis
spectroscopy (Figure S3). The reaction in which vinyl
azide 70 was added instead of an alkyne under
standard reaction conditions afforded compound 3 in
91% yield (eq. 2), confirming that vinyl azide is an
intermediate in this reaction. The reaction of vinyl
azide 70 and diphenylphosphine oxide in the absence
Scheme 4. Mechanistic investigation of the reaction to form β-ketophosphine oxide 3. (A) Control experiments; (B)
Reaction monitoring by powder XRD; (C) Proposed mechanism and DFT rationalization.
On the basis of the above investigations, a
plausible mechanism for the oxyphosphorylation of
alkynes is given in Scheme 4C, and the proposed
mechanism was verified with density functional
theory (DFT) calculations run at the PCM-M06-
2X/6-311++G(d,p) level (for additional details, see
Figure S5). Initially, vinyl azide 70 was generated
from the hydroazidation of an alkyne, and
4
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10.1002/adsc.202100226
Advanced Synthesis & Catalysis
diphenylphosphine oxide radical A was generated
from the reaction of Ag(I) and diphenylphosphine
oxide via TS1 (∆G‡ = 21.5 kcal·mol-1).[18] The
transformation of Ag(0) to Ag(I) in the reaction
system depended on the oxidation by oxygen. The
reaction of vinyl azide 70 with diphenylphosphine
oxide radical A gave imine radical 70-1 via TS2 (∆G‡
= 3.7 kcal·mol-1) and TS3 (∆G‡ = 1.1 kcal·mol-1). [19]
Then, imine radical 70-1 was reduced by
diphenylphosphine oxide to generate imine 70-2 and
diphenylphosphine oxide radical A via TS4 (∆G‡ =
12.4 kcal·mol-1). Finally, imine 70-2 was hydrolyzed
to β-ketophosphine oxide 3 via TS5 (∆G‡ = 22.5
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(The process of the generation of pyrrole see Figure
S4 in Surpporting Information.)
In conclusion, we have described an effective
reaction between unactivated alkynes and
phosphinoyl radicals under mild reaction conditions,
opening up a new application for the hydro-azidation
of alkynes and providing a simple and practical
method for the preparation of β-ketophosphine oxides
and phospho-rus-containing pyrroles. In addition, the
combination of control experiments, powder XRD
analysis of the silver species in the system, and DFT
calculations clearly reveals the specific reaction
mechanism, which not only gives people a deeper
understanding of the chemistry of vinyl azides and
phosphorus radicals, but also provides a new means
for the study of mechanism.
Experimental Section
General procedure for the synthesis of 3
To a 10 mL Schlenk reaction tube were added 1-octyne (55
mg, 0.5 mmol), dry DMSO (2 mL), then TMSN3 (0.132
mL, 1.0 mmol), H2O (0.018 mL, 1.0 mmol), Ag3PO4 (42
mg, 0.1 mmol), diphenylphosphine oxide (1.0 mmol,
dissolved in 1 mL DMSO) were added. The mixture was
then stirred at 65 oC for 8-12 h under two balloons with the
same volume O2 and N2. Upon completion of the reaction,
saturated NH4Cl (aq.) was added to quench the reaction
and the mixture was extracted with CH2Cl2 (3 x 50 mL).
The combined organic layers were washed with H2O, brine,
dried over MgSO4, filtered, and concentrated in vacuo. The
resulting mixture was purified by silica gel column
chromatography using (petroleum ether/ethyl acetate =
1:1) to afford 3 in 80% yield as a white solid.
[6] V. V. Khrizanforova, K. V. Kholin, M. N.
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Acknowledgements
[7] For reviews, see: a) P. Sivaguru, S. Cao, K. R. Babu,
X. Bi, Acc. Chem. Res. 2020, 53, 662-675; See also:
b) J. Liu, Z. Fang, Q. Zhang, Q. Liu, X. Bi, Angew.
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We are grateful for the financial support from National Natural
Science Foundation of China (21604082), the Department of
Science and Technology of Jilin Province (20190103128JH, and
20200801065GH), and the Fundamental Research Funds for the
Central Universities (2412019FZ006, and 2412020ZD003).
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10.1002/adsc.202100226
Advanced Synthesis & Catalysis
COMMUNICATION
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