Mukaiyama reagent-promoted metal-free preparation of alkynyl sulfones and phosphonates under mild conditions

Article abstract of DOI:10.1016/j.tet.2019.06.035

An efficient and mild route for the formation sulfur or phosphor-substituted alkynes was herein demonstrated. The Mukaiyama reagent-mediated transformation started from easily-accessible substrates without carbon-carbon triple bonds, and the reaction proceeded under mild conditions (room temperature) in a one-pot manner, requiring for no transition metal-catalysts. The practical protocol featured for good functional groups tolerance (up to 41 examples) and high efficiency (up to 91% yields) towards alkynyl sulfones and alkynyl phosphonates at low cost.

Full text of DOI:10.1016/j.tet.2019.06.035

Accepted Manuscript
Mukaiyama reagent-promoted metal-free preparation of alkynyl sulfones and
phosphonates under mild conditions
Danyang Qi, Wanrong Dong, Zhihong Peng, Yingjun Zhang, Delie An
PII:
S0040-4020(19)30707-0
https://doi.org/10.1016/j.tet.2019.06.035
TET 30427
DOI:
Reference:
To appear in: Tetrahedron
Received Date: 9 March 2019
Revised Date: 14 June 2019
Accepted Date: 22 June 2019
Please cite this article as: Qi D, Dong W, Peng Z, Zhang Y, An D, Mukaiyama reagent-promoted metal-
free preparation of alkynyl sulfones and phosphonates under mild conditions, Tetrahedron (2019), doi:
https://doi.org/10.1016/j.tet.2019.06.035.
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Mukaiyama Reagent-Promoted Metal-free
Preparation of Alkynyl Sulfones and
Phosphonates under Mild Conditions
Danyang Qi, Wanrong Donga,*, Zhihong Penga, Yingjun Zhangb and Delie Ana,*
aState Key Laboratory of Chemo/Biosensing and Chemometrics, College of Chemistry and Chemical
Engineering, Hunan University, Lushan South Rd. 2, Changsha, 410082, P.R. China
wanrongdong@hnu.edu.cn; deliean@hnu.edu.cn;
bState Key Laboratory of Anti-Infective Drug Development (NO. 2015DQ780357), Sunshine Lake Pharma
Co.,Ltd, Dongguan 523871, P. R. China
A Mukaiyama reagent-mediated protocol towards alkynyl sulfones and alkynyl phosphonates was herein described without
participation of any transition metal catalysts. The transformation proceeded under the mild conditions in a one-pot manner
from the easily-accessible substrates without carbon-carbon triple bonds, featuring for good functional groups tolerance (up
to 41 examples) and high efficiency (up to 91% yields) towards alkynyl sulfones and alkynyl phosphonates at low cost.

1
ACCEPTED MANUSCRIPT
Tetrahedron
journal homepage: www.elsevier.com
Mukaiyama Reagent-Promoted Metal-free Preparation of Alkynyl Sulfones and
Phosphonates under Mild Conditions
Danyang Qi, Wanrong Donga,*, Zhihong Penga, Yingjun Zhangb and Delie Ana,*
aState Key Laboratory of Chemo/Biosensing and Chemometrics, College of Chemistry and Chemical Engineering, Hunan University, Lushan South Rd. 2,
Changsha, 410082, P.R. China
bState Key Laboratory of Anti-Infective Drug Development (NO. 2015DQ780357), Sunshine Lake Pharma Co.,Ltd, Dongguan 523871, P. R. China.
ARTICLE INFO
ABSTRACT
Article history:
Received
Received in revised form
Accepted
An efficient and mild route for the formation sulfur or phosphor-substituted alkynes was herein
demonstrated. The Mukaiyama reagent-mediated transformation started from easily-accessible
substrates without carbon-carbon triple bonds, and the reaction proceeded under mild conditions
(room temperature) in a one-pot manner, requiring for no transition metal-catalysts. The
practical protocol featured for good functional groups tolerance (up to 41 examples) and high
efficiency (up to 91% yields) towards alkynyl sulfones and alkynyl phosphonates at low cost.
Available online
Keywords:
Mukaiyama-reagent
Metal-free
2009 Elsevier Ltd. All rights reserved
.
Mild conditions
Alkynyl sulfones
Alkynyl phosphonates
1. Introduction
construction of terminal alkynes with the assistance of LDA and
ClP(O)(OEt)2.[10] But the efficient transformation suffered from
limited scope of substrates and extremely low reaction
temperature (-78 oC). Then, methylthiomethyl phenyl sulfone
(MP-S) was employed towards acetylenic sulfides with
aldehydes.[11] Still, special reagent MP-S restricted the
methodology for general applications. As the long-standing
interests for the formations of sulfur or selenium-substituted
alkynes from our group,[12] we wish to demonstrate a facile
transformation of nitrogen or phosphine-substituted acetylenes
herein from easily-prepared starting materials.
Heteroatom decorated carbon-carbon triple bonds, such as
alkynyl sulfones and alkynyl phosphonates, have aroused broad
research interests for the outstanding biological and photo-
conductive properties (shown in Scheme 1),[1] as well as versatile
intermediates for the preparation of various heterocyclic
molecules of great pharmaceutical significance in the field of
synthetic and methodology chemistry[2]. Thus, great attempts
have been endeavoured for the preparation of the useful
compounds. Typically, expensive substrates containing carbon-
carbon triple bonds were frequently employed for the
construction of alkynyl sulfones and alkynyl phosphonates,
transition metal-catalyzed sp-hybridized C-S or C-P cross-
coupling protocols were generally applied from acetylenes,[3]
acetylenic bromide,[4] arylpropiolic acids,[5] 1,1-dihalo-1-
alkenes[6] etc.[7] and the corresponding S or P containing coupling
partners. However, homo-coupling of the high-cost but instable
acetylenic compounds or dibromoalkenes was unavoidable in the
presence of palladium and copper catalysts. Therefore, attempts
have been devoted to seek the possibilities to form the C-S or C-
P bonds in the absence of any transition metal-catalysts for
higher efficiency. For example, approaches such as halogenated
alkynes coupled with SH reagents or alkynyl lithium reacted with
phosphonyl chloride were successfully developed.[8] Zhao also
reported a transition metal-free protocol from 1,1-dibromo-1-
alkenes and trialkyl phosphites (scheme 1).[9] Yet, research work
has been widely embarked for the construction of triple bonds
from easier-accessible substrates. One of the pioneering
documents was reported by Negishi, using methyl ketones for
Scheme 1.Biologically active alkynyl sulfone and phosphonate
2. Results and discussions
Initially, 1-phenyl-2-tosylethanone (1a) was used as the model
substrate for optimization of the dehydration reactions, as shown
in Table 1. To our satisfactory, in the presence of Mukaiyama’s
reagent, 2-chloro-1-methylpyridinium iodide (CMPI), sodium
hydroxide made the reaction take place smoothly in
dichloromethane (DCM) at room temperature for 3 hours,
providing the desired S-1-phenylethynyl-S-phenyl sulfone (2a) in
medium yield (52% for entry 1). Sodium carbonate (Na2CO3)

2
Tetrahedron
ACCEPTED MANUSCRIPT
allowed the formation of 2a in only 28% yield (entry 2).
affording the desired sulfonyl alkyne 2b in 90% yield (entry 2).
However, K2CO3 offered the desired alkynyl sulfone 2a in good
86% yield (entry 3), superior to other potassium salts like KOAc,
tBuOK did in the system (entries 4 and 5). In the same manner,
no improvement was observed when the reaction was conducted
in the presence of Cs2CO3, and 32% of 2a was successfully
isolated (entry 6). Successively, organic bases such as Et2HN,
Et3N and pyridine, were turned to for higher efficiency. However,
Et3N distinguished from other organic bases tested, giving the
desired alkynyl sulfone 2a in excellent 92% yield (entries 7 – 9).
Furthermore, base was proved of great importance to the useful
transformation, for no product was detected in the absence of any
bases (entry 10). Subsequently, the effects of different solvents
were also tested. Acetonitrile, 1,2-dichloroethane (DCE), N,N-
dimethyl formamide (DMF) ensured the occurrence of the
reaction, but in lower yields, up to 85% (entries 11 – 13). Other
organic solvents, including 1,4-dioxane, toluene, ethyl acetate
were ineffective to the transformation and no reaction was
detected after 3 hours (entries 14 – 16). Finally, no decrease was
observed at room temperature under the argon atmosphere (entry
17).
In the same manner, 2c was successfully isolated in 89% yield
after the treatment with CMPI (entry 3). Moreover, electron-
sufficient aryl groups were also tested in the system, which was
exemplified by the formation of the alkynyl sulfones 2d and 2e in
88% and 85% yields, respectively (entries 4 and 5). Generally,
however, halo substituted substrates gave inferior performance to
alkoxyl-decorated substrates, which probably was attributed to
the inductive effect. For example, 2f, 2g, 2h, 2i and 2j were
smoothly separated after column in yields from 70% to 79%
(entries 5 – 9). And 4-cyanophenylethynyl phenyl sulfone (2k)
was offered in 76% yield (entry 10). Polyaryl substituted
substrates like 4,4’-biphenyl and 1-(7-methoxy-2-naphthyl
substrates (1l and 1m) offerred the desired triple carbon-carbon
bond decorated sulfones 2l and 2m in 80% and 79% yields
(entries 11 and 12). Subsequently, functional groups on sulfonic
part were also examined in the transformation, and general lower
efficiency was acknowledged in the protocol. 1n was smoothly
transformed into the corresponding alkynyl sulfone 2n in
acceptable 60% yield (entry 13). Other electron-rich aryl group,
showed positive effect to the transformation and 1-phenylethynyl
4-methoxyphenyl sulfone (2o) was formed in 68% yield (entry
14). 1-Phenylethynyl 3-chlorophenyl sulfone (2p) and 1-
phenylethynyl 4-iodophenyl sulfone (2q) were furnished
favorably in 52% and 60% yields (entries 15 and 16). Electron-
deficient aryl substituents, such as 1-phenylethynyl 4-
trifloromethylphenyl sulfone (2r) and 1-phenylethynyl 4-
nitrophenyl sulfone (2s) were provided in 48% and 45% yields,
separately (entries 17 and 18). Polyaryl, such as 2-naphthyl
sulfonyl alkynyl (2t) was generated in 72% yield (entry 19).
Worthy of note, phenylethynyl cyclopropyl sulfone (2u) was
observed in 68% yield after the treatment of CMPI at room
temperature (entry 20). Moreover, chained alkyl like 4-phenyl-
butynyl phenyl sulfone 2v was obtained in 70% yield (entry 21).
Table 1. Optimization of the reaction conditions[a]
Entry
1
Base
NaOH
Na2CO3
K2CO3
KOAc
tBuOK
Cs2CO3
Et2NH
Et3N
Sol.
CH2Cl2
Yield (%)b
52
2
CH2Cl2
28
Table 2. Substrate scope towards quinolinyl phosphonates[a]
3
CH2Cl2
86
4
CH2Cl2
20
5
CH2Cl2
20
6
CH2Cl2
32
Entry
1
2
2b
2c
2d
2e
2f
R'
p-Tolyl
o-Tolyl
4-CH3OC6H4
3,4-CH2O2C6H3
4-FC6H4
4-ClC6H4
3,4-Cl2C6H4
4-BrC6H4
4-IC6H4
4-CNC6H4
4-PhC6H4
2-(7-CH3ONaphthyl)
Ph
R
Yield (%)[b]
7
CH2Cl2
n.d.
92
Ph
90
89
88
85
72
79
70
76
70
76
80
79
60
68
52
60
48
45
72
68
70
2
Ph
8
CH2Cl2
3
Ph
Ph
9
Pyridine
--
CH2Cl2
n.d.
n.d.
85
4
5
Ph
10
11
12
13
14
15
16
17
CH2Cl2
6
2g
2h
2i
Ph
Et3N
CH3CN
7
Ph
8
Ph
Et3N
1,2-dichloroethane
DMF
80
9
2j
Ph
10
11
12
13
14
15
16
17
18
19
20
21
2k
2l
Ph
Et3N
60
Ph
Et3N
1,4-dioxane
toluene
n.d.
n.d.
n.d.
90c
2m
2n
2o
2p
2q
2r
2s
2t
Ph
4-tBuC6H4
4-CH3OC6H4
3-ClC6H4
4-IC6H4
4-CF3C6H4
4-NO2C6H4
2-Naphthyl
Cyclo-C3H5
Ph
Et3N
Ph
Et3N
Ethyl acetate
CH2Cl2
Ph
Ph
Et3N
Ph
Ph
a) Conditions: 1a (0.3 mmol), CMPI (0.36 mmol), Base (0.6 mmol) in
Sol. (3.0 mL) at room temperature for 3 hours. b) Isolated yields. c) the
yield was obtained under the argon atmosphere.
Ph
2u
2v
Ph
PhC2H4
Subsequently, the functional groups compatibilities were
also examined in the mild transformation as shown in Table 2. To
our delight, 1b underwent the dehydration protocol smoothly,
a) Conditions: 1 (0.5 mmol), CMPI (0.6 mmol), Et3N (1.0 mmol) in DCE
(5.0 mL) at room temperature for 3 hours. b) Isolated yields.

3
Based on the successful formation of the carbon-carbon triple
bond decorated sulfones, the evaluation of the substrate scope
was then extended on the construction of alkynyl phosphonates,
as shown in Table 3. To our delight, P-phenylethynyl-P,P-diethyl
phosphonate (4a) was successfully furnished under the standard
conditions in 91% yield (entry 1). In an analogous pattern,
To have a better understanding of the dehydration protocol, the
ACCEPTED MANUSCRIPT
reactivities of other pyridinium halides were further examined by
the reaction between 1a and 2a at room temperature, as
summarized in the table 4. 2-chloro-1-ethylpyridinium iodide
offered a decreased yield of 2a under the mild conditions (40%
yield for entry 1). By comparison, 2-bromo-1-methylpyridinium
iodide allowed the formation of the desired product 2a in the
same 40% yield (entry 2). Other different salts, such as 2-chloro-
formations
of
P-(4-methylphenylethynyl)-P,P-diethyl
P-(2-methylphenylethynyl)-P,P-diethyl
phosphonate
(4b),
phosphonate (4c) and P-(3,4-dimethylphenylethynyl)-P,P-diethyl
phosphonate (4d) were achieved by the facile protocol, and a
range of 80% - 89% yields were obtained (entries 2 – 4).
Similarly, electron-rich aryl groups were also found compatible
in the system, and various alkynyl phosphonates 4e – 4g were
also smoothly provided in yields from 70% - 79% (entries 5 – 7).
Tolerance of haloaryl groups was also examined and gratifyingly,
corresponding products 4h – 4k were successfully isolated in
yields from 72% to 80% (entries 8 – 11). Polyaryl substrates
were also readily separated, allowing the formation of the
polyarylalkynyl diethyl phosphonates 4l – 4n in yields from 76%
to 85% (entries 12 – 14). It was noteworthy that heteroaryl
1-methylpyridinium
tetrafluoroborate
and
2-bromo-1-
methylpyridinium triflate furnished the alkynyl sulfone 2a in
higher yields, up to 85% (entries 3 and 4). However, no
pyridinium salts gave better performance than CMPI did under
the mild conditions.
Table 4. Effects of analogous pyridinium saltsa)
substituted starting materials 3o and 3p
underwent the
Entry
R
X
Cl
Br
Cl
Br
Y
I
Yield (%)[b]
dehydration procedure, and 2-furanyl and 2-thiophenyl
substituted alkynyl phosphonates 4o and 4p in acceptable 64%
and 71% yields (entries 15 and 16). Successively, different
functional groups tolerance was also tested in the transformation
and P-(1-phenylethynyl)-P-dimethyl phosphonate (4q), P-(1-
1
2
3
4
Et
40
40
70
85
Me
Me
Me
I
BF4
OTf
phenylethynyl)-P-diisopropyl
phosphonate
(4r),
P-(1-
a) Conditions: 1a (0.5 mmol), pyridinium salt (0.6 mmol), Et3N (1.0 mmol)
phenylethynyl)-P-dibutyl phosphonate (4s) were readily
furnished in yields from 80% to 89% yields (entries 17 – 19).
Surprisingly, P-(2,2-dimethylbutynyl)-P-diethyl phosphonate (4t)
was successfully furnished in acceptable yield, up to 56% (entry
20).
in DCE (5.0 mL) at room temperature for 3 hours. b) Isolated yields.
Based on the previous demonstrations,[13] a plausible mechanism
was proposed for the mild dehydration transformation, which
was described by the reaction between 1a and 2a as shown in
Scheme 2. Firstly, nucleophilic addition reaction took place
between the substrate 1a and CMPI, forming a key intermediate
with a loss of a hydrogen cation. Then, removal of chloride anion
gave an access to another pyridinium intermediate, which could
be transformed easily into the desired alkynyl sulfone 2a.
Table 3. Substrates scope towards triazolyl phosphonatesa)
Ph
SNAr
-H
Ph
O
O
-Cl
Entry
1
4
4a
4b
4c
4d
4e
4f
R’
Ph
R
Et
Et
Et
Et
Et
Et
Et
Et
Et
Et
Et
Et
Et
Et
Et
Et
Me
iPr
nBu
Et
Yield (%)[b]
N
O
O
Cl
N
H
Cl
O
91
89
85
80
79
75
70
78
80
76
72
78
85
76
64
71
88
89
80
56
CH3
H
CH3
O
S
S
2
4-CH3C6H4
2-CH3C6H4
3,4-(CH3)2C6H3
4-CH3OC6H4
2,5-(CH3O)2C6H3
3,4-CH2O2C6H3
4-FC6H4
Ph
Ph
1a
3
CMPI
4
5
Ph
6
-H
2a
+
O
O
N
7
4g
4h
4i
N
H
CH3
8
CH3
O
S
O
9
4-ClC6H4
4-BrC6H4
4-IC6H4
Ph
10
11
12
13
14
15
16
17
18
19
20
4j
Scheme 2. Proposed mechanism
4k
4l
4-PhC6H4
2-Naphthyl
6-CH3O-2-Naphthyl
2-Furanyl
2-Thiophenyl
Ph
3. Conclusion
4m
4n
4o
4p
4q
4r
4s
4t
In conclusion, an effective and practical transformation of
alkynyl sulfones and alkynyl phosphonates was successfully
achieved under the mild conditions without the participation of
any transition metal-catalysts. The methodology offered an facile
access to S or P-substituted alkynes from easily-prepared
substrates of different structure with high efficiency and in low
cost, which made a significant contribution to the development of
the topic.
Ph
Ph
tBu
a) Conditions: 3 (0.5 mmol), CMPI (0.6 mmol), Et3N (1.0 mmol) in DCE
(5.0 mL) at room temperature for 3 hours. b) Isolated yields.
4. Experimental section
4.1 General remarks

4
Tetrahedron
ACCEPTED MANUSCRIPT
All reagents were purchased from commercial companies
114.9, 94.37, 85.0, 21.9 ppm. MS (EI): m/z (%) = 77.04 (48),
and used without further purification.1H and 13C NMR spectra
were recorded on a Varian INOVA-400 spectrometer in
deuterated chloroform at 25 °C with residue solvent peaks as
internal standards (δ = 7.26 ppm for 1H-NMR and δ = 77.16 ppm
for 13C-NMR). Chemical shifts (δ) are reported in ppm, and spin-
spin coupling constants (J) are given in Hz, while multiplicities
are abbreviated by s (singlet), d (doublet), t (triplet), q (quartet)
103.05 (48), 125.00 (29), 165.06 (20), 192.07 (97), 256.00 (100).
IR (KBr): ν = 2962, 2177, 1604, 1508, 1443, 1334, 1155, 1083,
1023, 857, 813, 779, 720, 685, 619, 569, 512 cm-1. HRMS (EI):
Calcd. for [C15H12O2S]+: 256.0558, Found 256.0556.
4.2.5 S-(1-2-Methylphenylethynyl)-S-phenyl sulfone (2c)
Yellow solid (114.1 mg, 89% yield). Melting point: 47-48 oC.
1H NMR (400 MHz, CDCl3) δ = 8.08 (d, J = 7.9 Hz, 2H), 7.68 (t,
J = 7.2 Hz, 1H), 7.59 (t, J = 7.5 Hz, 2H), 7.43 (d, J = 7.7 Hz,
1H), 7.34 (t, J = 7.5 Hz, 1H), 7.23 – 7.12 (m, 2H), 2.35 (s, 3H)
ppm. 13C NMR (100 MHz, CDCl3) δ = 142.6, 142.3, 134.2,
133.2, 131.7, 130.1, 129.5, 127.4, 126.1, 117.8, 93.3, 89.1, 20.5
ppm. MS (EI): m/z (%) = 77.04 (93), 103.05 (57), 115.05
(100),125.00 (37), 165.06 (31), 191.07 (91), 256.00 (66). IR
(KBr): ν = 3059, 2179, 1651, 1325, 1157, 1082, 850, 755, 727,
688, 653, 572, 541 cm-1. HRMS (EI): Calcd. for [C15H12O2S]+:
256.0558, Found 256.0561.
and
m (multiplet). Mass spectra were recorded on a
ThermoFinnigan MAT95XP microspectrometer and High
resolution mass spectra (HRMS) were recorded on an Agilent
Technologies Accurate Mass Q-TOF 6530 microspectrometer.
Infrared (IR) spectra were reported in reciprocal centimeter (cm-
1). Melting points were recorded on a national standard melting
point apparatus (Model: Taike XT-4) and were uncorrected.
4.2 General Procedure
4.2.1 Preparations of starting materials 1 and 3
A sealed tube (35 mL) equipped with a stirring bar was loaded
4.2.6 S-(1-4-Methoxyphenylethynyl)-S-phenyl sulfone (2d)
with
2-bromoethanones
(1.0
mmol),
then
sodium
Yellow solid (119.8 mg, 88% yield). Melting point: 84-85 oC.
1H NMR (400 MHz, CDCl3) δ = 8.07 (d, J = 7.5 Hz, 2H), 7.67 (t,
J = 7.4 Hz, 1H), 7.58 (t, J = 7.6 Hz, 2H), 7.46 (d, J = 8.7 Hz,
2H), 6.86 (d, J = 8.6 Hz, 2H), 3.82 (s, 3H) ppm. 13C NMR (100
MHz, CDCl3) δ = 162.3, 142.2, 134.8, 134.1, 129.4, 127.4, 114.6,
109.6, 94.8, 84.7, 55.6 ppm. MS (EI): m/z (%) = 77.04 (100),
131.05 (88), 207.23 (98), 272.32 (21). IR (KBr): ν = 2939, 2168,
1670, 1598, 1510, 1441, 1321, 1263, 1172, 1153, 1089, 1023,
798, 739, 686, 554, 521 cm-1. HRMS (EI): Calcd. for
[C15H12O3S]+: 272.3190, Found 272.3195.
benzenesulfinate (1.2 mmol) in DMF (20 ml) or phosphite (1.0
mmol) in toluene (20 ml) was added to the tube and the mixtures
were stirred at room temperature till the 2-bromoethanones was
totally consumed as indicated by TLC analysis (ca. 12 hours for 1
and 24 hours for 3). Then, the mixture was diluted with water (20
mL) and extracted with CH2Cl2 (30mL × 3). Next, the organic
phase was combined and dried over anhydrous Na2SO4 . The
solvent was removed by rotary evaporation and the oily mixture
was purified with flash chromatograph column (elute: mixture of
ethyl acetate and n-hexane), giving the desired products. And the
1H-NMR spectra of the purified substrates were in accordance
with the known literatures.[14]
4.2.7 S-(1-3,4-Methylenedioxyphenylethynyl)-S-phenyl sulfone
(2e)
4.2.2 Preparations of alkynyl sulfones 2 or phosphonates 4
Yellow solid (121.7 mg, 85% yield). Melting point: 102-103
1
oC. H NMR (400 MHz, CDCl3) δ = 8.06 (d, J = 7.8 Hz, 2H),
A sealed tube (35 mL) equipped with a stirring bar was loaded
with the substrates 1 or 3 (0.5 mmol) in DCM (5.0 mL), then
CMPI (0.6 mmol, 1.2 equiv.) and Et3N was added to the solution
in one portion. After addition, the tube was sealed and the
mixture was stirred at room temperature for another 3 h. After the
completion of the reaction (monitored by TLC), the mixture was
then washed with dichloromethane (15 mL × 3). The organic
phase was combined and then concentrated. The oily crude
product was purified by column chromatography using silica gel
(200-300 mesh) as stationary phase and a mixture of petroleum
and ethyl acetate as eluent to give the desired product in noted
yields.
7.68 (t, J = 7.3 Hz, 1H), 7.59 (t, J = 7.5 Hz, 2H), 7.09 (d, J = 8.1
Hz, 1H), 6.92 (s, 1H), 6.78 (d, J = 8.1 Hz, 1H), 6.01 (s, 2H) ppm.
13C NMR (100 MHz, CDCl3) δ = 150.9, 147.9, 142.1, 134.2,
129.5, 129.0, 127.5, 112.2, 110.8, 109.0, 102.1, 94.3, 84.3 ppm.
MS (EI): m/z (%) = 77.04 (23), 133.02 (54), 163.04 (31), 222.04
(35), 285.97 (100). IR (KBr): ν = 2964, 2169, 1789, 1651, 1504,
1255, 1161, 1085, 1035, 810, 667 cm-1. HRMS (EI): Calcd. for
[C15H10O4S]+: 286.0300, Found 286.0294.
4.2.8 S-(1-4-Fluorophenylethynyl)-S-phenyl sulfone (2f)
o
Yellow solid (93.7 mg, 72% yield). Melting point: 54-55 C.
1H NMR (400 MHz, CDCl3) δ = 8.07 (d, J = 7.6 Hz, 2H), 7.70 (t,
J = 7.4 Hz, 1H), 7.60 (t, J = 7.5 Hz, 2H), 7.56 – 7.50 (m, 2H),
7.07 (t, J = 8.1 Hz, 2H) ppm. 13C NMR (100 MHz, CDCl3) δ =
164.5 ( JC-F = 255.4 Hz), 141.8, 135.3 (JC-F = 9.1 Hz), 134.4,
129.6, 127.6, 116.5 (JC-F = 22.5 Hz), 114.1 (JC-F = 3.6 Hz), 92.5,
85.4 ppm. 19F NMR (375 MHz, CDCl3) δ = -104.33 ppm. MS
(EI): m/z (%) = 77.04 (20), 107.02 (20), 125.00 (30), 196.04
(100), 259.98 (36). IR (KBr): ν = 2181, 1602, 1504, 1336, 1155,
1085, 839, 794, 723, 684, 617, 568 cm-1. HRMS (EI): Calcd. for
[C14H9FO2S]+: 260.0307, Found 260.0301.
4.2.3 S-(1-Phenylethynyl)-S-phenyl sulfone (2a)
o
1
Yellow solid (65.4 mg, 90% yield). Melting point: 74-75 C. H
NMR (400 MHz, CDCl3) δ = 8.08 (d, J = 7.6 Hz, 2H), 7.69 (t, J
= 7.3 Hz, 1H), 7.60 (t, J = 7.5 Hz, 2H), 7.52 (d, J = 7.6 Hz, 2H),
7.47 (t, J = 7.4 Hz, 1H), 7.37 (t, J = 7.5 Hz, 2H) ppm. 13C NMR
(100 MHz, CDCl3) δ = 141.9, 134.3, 132.9, 131.7, 129.5, 128.82,
127.5, 118.0, 93.6, 85.4 ppm. MS (EI): m/z (%) = 77.04 (51),
89.03 (38), 125.00 (49), 178.06 (100), 241.99 (30). IR (KBr): ν =
2169, 1651, 1455, 1323, 1155, 1081, 866, 756, 720, 688, 653,
569 cm-1. HRMS (EI): Calcd. for [C14H10O2S]+: 242.0402, Found
242.0398.
4.2.8 S-(1-4-Chlorophenylethynyl)-S-phenyl sulfone (2g)
Yellow solid (109.3 mg, 79% yield). Melting point: 91-92 oC.
1H NMR (400 MHz, CDCl3) δ = 8.08 (d, J = 7.6 Hz, 2H), 7.70 (t,
J = 7.3 Hz, 1H), 7.61 (t, J = 7.5 Hz, 2H), 7.46 (d, J = 8.0 Hz,
2H), 7.36 (d, J = 7.9 Hz, 2H) ppm.13C NMR (100 MHz, CDCl3) δ
= 141.7, 138.3, 134.5, 134.1, 129.6, 129.4, 127.6, 116.5 ppm. MS
(EI): m/z (%) = 77.04 (55), 124.99 (97), 176.04 (38), 212.01
(100), 275.94 (48). IR (KBr): ν = 2351, 2179, 1789, 1651, 1556,
4.2.4 S-(1-4-Methylphenylethynyl)-S-phenyl sulfone (2b)
Yellow solid (115.3 mg, 90% yield). Melting point: 82-83 oC.
1H NMR (400 MHz, CDCl3) δ = 8.08 (d, J = 7.8 Hz, 2H), 7.68 (t,
J = 7.3 Hz, 1H), 7.60 (t, J = 7.3 Hz, 2H), 7.42 (d, J = 7.4 Hz,
2H), 7.17 (d, J = 7.6 Hz, 2H), 2.37 (s, 3H) ppm. 13C NMR (100
MHz, CDCl3) δ = 142.6, 142.1, 134.2, 132.9, 129.6, 129.5, 127.5,

5
1340, 1158, 1085, 1013, 852, 802, 732, 697, 587, 417 cm-1.
HRMS (EI): Calcd. for [C14H9ClO2S]+: 276.0012, Found
276.0009.
1H), 7.72 – 7.67 (m, 3H), 7.61 (t, J = 7.5 Hz, 2H), 7.46 (d, J =
ACCEPTED MANUSCRIPT
8.5 Hz, 1H), 7.19 (d, J = 9.0 Hz, 1H), 7.10 (s, 1H), 3.93 (s, 3H)
ppm. 13C NMR (100 MHz, CDCl3) δ = 159.8, 142.2, 136.0,
134.3, 134.2, 130.0, 129.5, 128.4, 128.0, 127.5, 127.5, 120.4,
112.4, 106.0, 95.0, 85.1, 55.6 ppm. MS (EI): m/z (%) = 77.04
(35), 126.04 (37), 139.05 (31), 169.05 (55), 215.06 (44), 322.01
(100). IR (KBr): ν = 2964, 2167, 1867, 1651, 1622, 1327, 1241,
1157, 1085, 1027, 940, 853, 773, 731, 645, 584 cm-1. HRMS
(EI): Calcd. for [C19H14O3S]+: 322.0664, Found 322.0669.
4.2.9 S-(1-4-Chlorophenylethynyl)-S-phenyl sulfone (2h)
Yellow solid (108.9 mg, 70% yield). Melting point: 88-89 oC. 1H
NMR (400 MHz, CDCl3) δ = 8.07 (d, J = 8.0 Hz, 2H), 7.71 (t, J
= 7.3 Hz, 1H), 7.64 – 7.58 (m, 3H), 7.46 (d, J = 8.3 Hz, 1H), 7.35
(d, J = 8.3 Hz, 1H) ppm. 13C NMR (100 MHz, CDCl3) δ = 141.4,
136.7, 134.6, 134.3, 133.5, 131.8, 131.1, 129.6, 127.7, 117.9,
90.3, 86.9 ppm. MS (EI): m/z (%) = 77.04 (36), 125.00 (67),
176.05 (42), 245.95 (100), 309.92 (58). IR (KBr): ν = 2351,
1652, 1539, 1456, 1339, 1163, 1085, 910, 744, 689, 594 cm-1.
HRMS (EI): Calcd. for [C14H8Cl2O2S]+: 309.9622, Found
309.9625.
4.2.15 S-(1-Phenylethynyl)-S-(4-tert-butylphenyl) sulfone (2n)
o
1
Yellow solid (89.5 mg, 60% yield). Melting point: 76-77 C. H
NMR (400 MHz, CDCl3) δ = 7.99 (d, J = 7.7 Hz, 2H), 7.60 (d, J
= 7.7 Hz, 2H), 7.53 (d, J = 7.7 Hz, 2H), 7.47 (t, J = 7.4 Hz, 1H),
7.37 (t, J = 7.5 Hz, 2H), 1.36 (s, 9H) ppm. 13C NMR (100 MHz,
CDCl3) δ = 158.4, 138.9, 132.9, 131.6, 128.8, 127.5, 126.6,
118.2, 93.1, 85.7, 35.5, 31.2 ppm. MS (EI): m/z (%) = 77.04 (31),
91.05 (32), 149.00 (52), 283.01 (100), 298.05 (25). IR (KBr): ν =
2964, 2181, 1593, 1489, 1332, 1161, 1111, 1082, 850, 755, 669,
617, 562, 547, 517 cm-1. HRMS (EI): Calcd. for [C18H18O2S]+:
298.1028, Found 298.1033.
4.2.10 S-(1-4-Bromophenylethynyl)-S-phenyl sulfone (2i)
Yellow solid (122.0 mg, 76% yield). Melting point: 116-117
1
oC. H NMR (400 MHz, CDCl3) δ = 8.07 (d, J = 8.0 Hz, 2H),
7.70 (t, J = 7.4 Hz, 1H), 7.61 (t, J = 7.6 Hz, 2H), 7.52 (d, J = 8.2
Hz, 2H), 7.38 (d, J = 8.1 Hz, 2H) ppm. 13C NMR (100 MHz,
CDCl3) δ = 141.7, 134.5, 134.1, 132.3, 129.6, 127.6, 126.7,
116.9, 92.2, 86.4 ppm. MS (EI): m/z (%) = 77.04 (77), 125 (100),
176.04 (55), 255.94 (64), 321.90 (35). IR (KBr): ν = 2351, 1645,
1506, 1336, 1260, 1162, 1085, 1016, 800, 686, 434 cm-1. HRMS
(EI): Calcd. for [C14H9ClO2S]+: 321.9486, Found 321.9480.
4.2.16 S-(1-Phenylethynyl)-S-(p-methoxyphenyl) sulfone (2o)
o
Yellow solid (92.6 mg, 68% yield). Melting point: 70-71 C.
1H NMR (400 MHz, CDCl3) δ = 8.00 (d, J = 8.0 Hz, 2H), 7.51
(d, J = 7.6 Hz, 2H), 7.46 (t, J = 7.4 Hz, 1H), 7.36 (t, J = 7.5 Hz,
2H), 7.05 (d, J = 8.0 Hz, 2H), 3.90 (s, 3H) ppm. 13C NMR (100
MHz, CDCl3) δ = 164.3, 133.6, 132.8, 131.5, 130.0, 128.8, 118.3,
114.7, 92.6, 86.0, 55.9 ppm. MS (EI): m/z (%) = 77.04 (20),
165.06 (36), 193.04 (46), 208.06 (100), 272.01 (48). IR (KBr): ν
= 2945, 2179, 1593, 1496, 1442, 1330, 1263, 1151, 1082, 1020,
848, 755, 682, 642, 558 cm-1. HRMS (EI): Calcd. for
[C15H12O3S]+: 272.0507, Found 272.0504.
4.2.11 S-(1-4-Iodophenylethynyl)-S-phenyl sulfone (2j)
Yellow solid (128.9 mg, 70% yield). Melting point: 134-135
1
oC. H NMR (400 MHz, CDCl3) δ = 8.08 (d, J = 7.6 Hz, 2H),
7.70 (t, J = 7.3 Hz, 1H), 7.61 (t, J = 7.5 Hz, 2H), 7.46 (d, J = 8.0
Hz, 2H), 7.36 (d, J = 7.9 Hz, 2H) ppm.13C NMR (100 MHz,
CDCl3) δ = 141.7, 138.3, 134.5, 134.1, 129.6, 129.4, 127.6, 116.5
ppm. MS (EI): m/z (%) = 77.04 (55), 124.99 (97), 176.04 (38),
212.01 (100), 275.94 (48). IR (KBr): ν = 2351, 2179, 1789, 1651,
1556, 1340, 1158, 1085, 1013, 852, 802, 732, 697, 587, 417 cm-1.
HRMS (EI): Calcd. for [C14H9ClO2S]+: 276.0012, Found
276.0009.
4.2.17 S-(1-Phenylethynyl)-S-(3-chlorophenyl) sulfone (2p)
1
Yellow oil (71.9 mg, 52% yield). H NMR (400 MHz, CDCl3)
δ = 8.06 (s, 1H), 7.97 (d, J = 7.8 Hz, 1H), 7.65 (d, J = 8.0 Hz,
1H), 7.52 (m, 5H), 7.39 (t, J = 7.5 Hz, 2H) ppm. 13C NMR (100
MHz, CDCl3) δ = 143.5, 135.7, 134.5, 133.0, 132.0, 130.9, 128.9,
127.7, 125.7, 117.7, 94.5, 85.0 ppm. MS (EI): m/z (%) = 77.04
(20), 151.05 (26), 176.05 (100), 212.03 (72), 276.03 (57). IR
(KBr): ν = 2179, 1681, 1575, 1338, 1165, 1118, 1078, 854, 794,
754, 680, 576 cm-1. HRMS (EI): Calcd. for [C14H9ClO2S]+:
276.0012, Found 276.0018.
4.2.12 S-(1-4-Cyanophenylethynyl)-S-phenyl sulfone (2k)
Yellow solid (101.6 mg, 76% yield). Melting point: 107-108
1
oC. H NMR (400 MHz, CDCl3) δ = 8.08 (d, J = 7.9 Hz, 2H),
7.73 (t, J = 7.4 Hz, 1H), 7.69 – 7.61 (m, 6H) ppm. 13C NMR (100
MHz, CDCl3) δ = 141.2, 134.8, 133.3, 132.4, 129.7, 127.8, 122.8,
117.7, 115.1, 90.1, 88.6 ppm. MS (EI): m/z (%) = 77.04 (36), 125
(100), 203.05 (100), 266.98 (34). IR (KBr): ν = 2230, 2185,
1681, 1499, 1449, 1338, 1159, 1081, 854, 745, 682, 603, 554,
431 cm-1. HRMS (EI): Calcd. for [C15H9NO2S]+: 267.0354,
Found 267.0349.
4.2.18 S-(1-Phenylethynyl)-S-(4-iodophenyl) sulfone (2q)
Yellow solid (110.5 mg, 60% yield). Melting point: 106-107
oC. H NMR (400 MHz, CDCl3) δ = 7.96 (d, J = 7.7 Hz, 2H),
1
7.78 (d, J = 7.5 Hz, 2H), 7.50 (m, 3H), 7.38 (t, J = 7.5 Hz, 2H)
ppm. 13C NMR (100 MHz, CDCl3) δ = 141.7, 138.9, 133.0,
131.9, 128.9, 128.9, 117.8, 102.4, 94.2, 85.2 ppm. MS (EI): m/z
(%) = 77.04 (20), 176.04 (25), 250.85 (62), 303.92 (74), 367.86
(100). IR (KBr): ν = 2179, 1867, 1681, 1506, 1338, 1157, 1085,
1005, 850, 734, 659, 590, 536 cm-1. HRMS (EI): Calcd. for
[C14H9IO2S]+: 837.9368, Found 367.9375.
4.2.13 S-(1-4,4’-Biphenylethynyl)-S-phenyl sulfone (2l)
Yellow solid (127.4 mg, 80% yield). Melting point: 92-93 oC.
1H NMR (400 MHz, CDCl3) δ = 8.11 (d, J = 7.7 Hz, 2H), 7.70 (t,
J = 7.2 Hz, 1H), 7.64 – 7.56 (m, 8H), 7.46 (t, J = 7.3 Hz, 2H),
7.39 (t, J = 7.2 Hz, 1H) ppm. 13C NMR (100 MHz, CDCl3) δ =
144.5, 142.0, 139.6, 134.3, 133.4, 129.5, 129.2, 128.5, 127.6,
127.4, 127.3, 116.6, 93.8, 86.0 ppm. MS (EI): m/z (%) = 77.04
(20), 165.06 (36), 254.06 (61), 318.02 (100). IR (KBr): ν = 3062,
2177, 1600, 1481, 1445, 1328, 1163, 1085, 1005, 856, 765, 743,
718, 686, 640, 576, 551 cm-1. HRMS (EI): Calcd. for
[C20H14O2S]+: 318.0715, Found 318.0716.
4.2.19 S-(1-Phenylethynyl)-S-(4-trifloromethylphenyl) sulfone
(2r)
o
Yellow solid (74.5 mg, 48% yield). Melting point: 56-57 C.
1H NMR (400 MHz, CDCl3) δ = 8.22 (d, J = 8.1 Hz, 2H), 7.87
(d, J = 8.1 Hz, 2H), 7.52 (m, 3H), 7.39 (t, J = 7.6 Hz, 2H) ppm.
13C NMR (100 MHz, CDCl3) δ = 145.4, 135.9 (JC-F = 33.3 Hz),
4.2.14 S-(1-7-Methoxy-2-naphthylethynyl)-S-phenyl sulfone (2m)
133.0, 132.1, 128.9, 128.2, 126.7 (JC-F = 3.6 Hz), 123.2 (J C-F
=
271.5 Hz), 117.6, 95.1, 84.8 ppm. 19F NMR (375 MHz, CDCl3) δ
= -63.24 ppm. MS (EI): m/z (%) = 77.04 (46), 89.03 (41), 105.03
Yellow solid (127.3 mg, 79% yield). Melting point: 59-60 oC.
1H NMR (400 MHz, CDCl3) δ = 8.11 (d, J = 7.7 Hz, 2H), 8.02 (s,

6
Tetrahedron
1
(99), 145.02 (100), 246.02 (83), 309.98 (40). IR (KBr): ν =
Colorless oil (112.3 mg, 89% yield). H NMR (400 MHz,
CDCl3) δ = 7.44 (d, J = 8.1 Hz, 2H), 7.16 (d, J = 8.0 Hz, 2H),
4.25 – 4.16 (m, 4H), 2.37 (s, 3H), 1.39 (t, J = 7.1 Hz, 6H) ppm.
13C NMR (100 MHz, CDCl3) δ = 141.5, 132.7, 132.7, 129.4,
116.5, 116.5, 100.1, 99.5, 79.3, 76.3, 63.3, 63.3, 21.8, 16.3, 16.2
ppm. 31P NMR (160 MHz, CDCl3) δ = -4.59 ppm. MS (EI): m/z =
103.1 (5), 116.1 (100), 179.1 (31), 196.1 (11), 209.1 (48), 224.1
(38), 237.1 (8), 252.1 (M+, 46). IR (KBr): ν = 2985, 2934, 2905,
2184, 1508, 1266, 1158, 1023, 973, 863, 815, 788, 739, 608 cm-1.
HRMS (EI): calcd. for [C13H17O3P]+: 252.0915, found 252.0910.
ACCEPTED MANUSCRIPT
2181, 1732, 1681, 1405, 1321, 1163, 1064, 852, 758, 715, 663,
591, 533, 431 cm-1. HRMS (EI): Calcd. for [C15H9F3O2S]+:
310.0275, Found 310.0277.
4.2.20 S-(1-Phenylethynyl)-S-(4-nitrophenyl) sulfone (2s)
Yellow solid (64.7 mg, 45% yield). Melting point: 120-121
oC. H NMR (400 MHz, CDCl3) δ = 8.44 (d, J = 8.3 Hz, 2H),
1
8.28 (d, J = 8.3 Hz, 2H), 7.53 (m, 3H), 7.40 (t, J = 7.5 Hz, 2H)
ppm. 13C NMR (100 MHz, CDCl3) δ = 151.1, 147.3, 133.1,
132.3, 129.0, 129.0, 124.8, 117.3, 96.0, 84.5 ppm. MS (EI): m/z
(%) = 77.04 (33), 89.03 (100), 165.06 (20), 176.05 (38), 193.05
(21), 223.04 (29), 286.97 (70). IR (KBr): ν = 2179, 1685, 1533,
1348, 1159, 1085, 848, 740, 685, 598, 532, 463 cm-1. HRMS
(EI): Calcd. for [C14H9NO4S]+: 287.0252, Found 287.0245.
4.2.25 P-(1-o-Tolylethynyl)-P,P-diethyl phosphonate (4c)
1
Colorless oil (107.2 mg, 85% yield). H NMR (400 MHz,
CDCl3) δ = 7.50 (d, J = 7.6 Hz, 1H), 7.32 (t, J = 7.5 Hz, 1H),
7.22 (d, J = 7.6 Hz, 1H), 7.17 (t, J = 7.6 Hz, 1H), 4.26 – 4.17 (m,
4H), 2.46 (s, 3H), 1.39 (t, J = 7.1 Hz, 6H) ppm. 13C NMR (100
MHz, CDCl3) δ = 141.9, 141.9, 133.19, 133.16, 130.8, 129.9,
125.9, 119.5, 119.4, 104.2, 98.7, 98.2, 83.5, 80.5, 63.4, 63.3,
20.6, 16.3, 16.2 ppm. 31P NMR (160 MHz, CDCl3) δ = -5.87
ppm. MS (EI): m/z = 103.1 (10), 115.1 (100), 178.1(18), 196.1
(39), 224.1 (5), 252.1 (M+, 45). IR (KBr): ν = 2985, 2938, 2911,
2182, 1480, 1453, 1388, 1265, 1161, 1024, 974, 868, 785, 762,
647 cm-1. HRMS (EI): calcd. for [C13H17O3P] +: 252.0907, found
252.0910.
4.2.21 S-(1-Phenylethynyl)-S-(2-naphthyl) sulfone (2t)
Yellow solid (105.2 mg, 72% yield). Melting point: 90-91 oC.
1H NMR (400 MHz, CDCl3) δ = 8.65 (s, 1H), 8.04 (d, J = 7.4 Hz,
3H), 7.95 (d, J = 8.0 Hz, 1H), 7.68 (m, 2H), 7.52 (d, J = 7.6 Hz,
2H), 7.46 (t, J = 7.4 Hz, 1H), 7.36 (t, J = 7.5 Hz, 2H) ppm. 13C
NMR (100 MHz, CDCl3) δ = 138.8, 135.7, 132.9, 132.3, 131.7,
130.0, 129.8, 129.8, 129.4, 128.8, 128.2, 128.0, 122.3, 118.1,
93.9, 85.7 ppm. MS (EI): m/z (%) = 77.04 (20), 127.05 (30),
228.07 (100), 292.00 (27). IR (KBr): ν = 2360, 2177, 1843, 1716,
1648, 1543, 1508, 1338, 1155, 1070, 860, 812, 751, 680, 551,
434 cm-1. HRMS (EI): Calcd. for [C18H12O2S]+: 292.0558, Found
292.0560.
4.2.26
phosphonate (4d)
P-(1-(3,4-Dimethylphenyl)ethynyl)-P,P-diethyl
1
Colorless oil (106.5 mg, 80% yield). H NMR (400 MHz,
CDCl3) δ = 7.32 (s, 1H), 7.29 (d, J = 7.8 Hz, 1H), 7.11 (d, J = 7.8
Hz, 1H), 4.24 – 4.16 (m, 4H), 2.26 (s, 3H), 2.23 (s, 3H), 1.38 (t, J
= 7.1 Hz, 6H) ppm. 13C NMR (100 MHz, CDCl3) δ = 140.3,
137.2, 133.63, 133.60, 130.27, 130.25, 129.9, 116.7, 116.7,
100.4, 99.8, 78.9, 75.9, 63.31, 63.25, 20.1, 19.6, 16.24, 16.17
ppm. 31P NMR (160 MHz, CDCl3) δ = -4.48 ppm. MS (EI): m/z =
115.1 (39), 130.1 (100), 193.1 (10), 223.1 (29), 238.1 (17), 251.1
(4), 266.1 (M+, 21). IR (KBr): ν = 2985, 2938, 2905, 2177, 1450,
1451, 1393, 1268, 1164, 1024, 972, 803, 624 cm-1. HRMS (EI):
calcd. for [C14H19O3P] +: 266.1072, found 266.1066.
4.2.22 S-(1-Phenylethynyl)-S-cyclopropyl sulfone (2u)
1
Brown oil (70.1 mg, 68% yield). H NMR (400 MHz, CDCl3)
δ = 7.59 (d, J = 7.6 Hz, 2H), 7.50 (t, J = 7.4 Hz, 1H), 7.41 (t, J =
7.5 Hz, 2H), 2.89 – 2.74 (m, 1H), 1.52 – 1.41 (m, 2H), 1.18 (q, J
= 6.4 Hz, 2H) ppm. 13C NMR (100 MHz, CDCl3) δ = 132.9,
131.7, 128.9, 118.0, 91.3, 84.2, 35.3, 6.5 ppm. MS (EI): m/z (%)
= 89.05 (28), 115.06 (26), 141.07 (100), 206.03 (70). IR (KBr): ν
= 3057, 2183, 1681, 1488, 1445, 1330, 1143, 888, 850, 757, 713,
652, 547, 532 cm-1. HRMS (EI): Calcd. for [C11H10O2S]+:
206.0402, Found 206.0399.
4.2.27 P-(1-(4-Methoxyphenyl)ethynyl)-P,P-diethyl phosphonate
(4e)
4.2.22 S-(1-Phenylbutynyl)-S-phenyl sulfone (2v)
o
1
Yellow solid (94.6 mg, 70% yield). Melting point: 54-55 C.
Colorless oil (105.9 mg, 79% yield). H NMR (400 MHz,
1H NMR (400 MHz, CDCl3) δ = 7.92 (d, J = 8.0 Hz, 1H),
7.64 (t, J = 7.5 Hz, 1H), 7.49 (t, J = 7.7 Hz, 1H), 7.27 (m,
2H), 7.19 (t, J = 8.0 Hz, 1H), 4.00 (s, 1H), 3.55 (s, 1H). 13C
NMR (101 MHz, CDCl3) δ = 137.8, 135.7, 134.1, 129.1, 128.9,
128.6, 128.0, 126.9, 86.4, 69.9, 49.1, 25.2 ppm. MS (EI) m/z (%)
= 77.04 (51), 117.17 (38), 125.00 (49), 129.30 (100), 165.06
(35), 205.25 (24), 270.35 (M+, 45). HRMS (EI) Calcd. for
[C14H10O2S]+: 270.3462, Found 270.3460.
CDCl3) δ = 7.47 (d, J = 8.7 Hz, 2H), 6.85 (d, J = 8.9 Hz, 2H),
4.23 – 4.13 (m, 4H), 3.80 (s, 3H), 1.37 (t, J = 7.1 Hz, 6H) ppm.
13C NMR (100 MHz, CDCl3) δ = 161.5, 134.50, 134.48, 114.3,
111.4, 111.3, 100.2, 99.6, 78.7, 75.7, 63.23, 63.17, 55.5, 16.23,
16.16 ppm. 31P NMR (160 MHz, CDCl3) δ = -5.43 ppm. MS
(EI): m/z = 107 (1), 119 (4), 132 (100), 195 (8), 225 (15), 240
(16), 268 (M+, 19). IR (KBr): ν = 2982, 2938, 2905, 2182, 1603,
1509, 1295, 1257, 1172, 1024, 973, 866, 837, 787 cm-1. HRMS
(EI): calcd. for [C13H17O4P]+: 268.0864, found 268.0859.
4.2.23 P-(1-Phenylethynyl)-P,P-diethyl phosphonate (4a)
Colorless oil (108.4 mg, 91% yield). 1H NMR (400 MHz,
CDCl3) δ = 7.55 (d, J = 7.1 Hz, 2H), 7.45 (t, J = 7.5 Hz, 1H),
7.36 (t, J = 7.4 Hz, 2H), 4.26 – 4.18 (m, 4H), 1.40 (t, J = 7.0 Hz,
6H) ppm. 13C NMR (100 MHz, CDCl3) δ = 132.8, 132.7, 130.8,
128.7, 119.7, 119.6, 99.4, 98.9, 80.0, 77.0, 63.4, 63.3, 16.3, 16.2
ppm. 31P NMR (160 MHz, CDCl3) δ = -5.92 ppm. MS (EI): m/z =
89.1 (12), 102.1 (100), 165.0 (27), 182.0 (11), 195.0 (18), 210.0
(24), 238.1 (M+, 16). IR (KBr): ν = 3058, 2986, 2934, 2908,
2187, 1489, 1444, 1390, 1265, 1163, 1024, 974, 857, 760, 690,
650 cm-1. HRMS (EI): calcd. for [C12H15O3P]+: 238.0759, found
238.0753.
4.2.28
phosphonate (4f)
P-(1-(2,5-Dimethoxyphenyl)ethynyl)-P,P-diethyl
1
Bright yellow oil (111.9 mg, 75% yield). H NMR (400 MHz,
CDCl3) δ = 7.00 (d, J = 3.1 Hz, 1H), 6.95 (dd, J = 9.1, 3.1 Hz,
1H), 6.81 (d, J = 9.1 Hz, 1H), 4.27 – 4.18 (m, 4H), 3.81 (s, 3H),
3.75 (s, 3H), 1.39 (t, J = 7.1 Hz, 6H) ppm. 13C NMR (100 MHz,
CDCl3) δ = 156.23, 156.21, 153.1, 118.9, 118.48, 118.45, 112.3,
109.3, 109.2, 96.6, 96.1, 83.5, 80.6, 63.4, 63.3, 56.4, 56.0, 16.24,
16.17 ppm. 31P NMR (160 MHz, CDCl3) δ = -5.78 ppm. MS
(EI): m/z = 147 (59), 161 (100), 224 (24), 242 (68), 270 (23), 283
(9), 298 (M+, 77). IR (KBr): ν = 2985, 2938, 2905, 2837, 2181,
1501, 1463, 1267, 1234, 1166, 1024, 962, 804, 724, 662, 611 cm-
1. HRMS (EI): calcd. for [C14H19O5P]+: 298.0970, found
298.0965.
4.2.24 P-(1-p-Tolylethynyl)-P,P-diethyl phosphonate (4b)

7
4.2.29
phosphonate (4g)
P-(1-(3,4-Methylenedioxyphenyl)ethynyl)-P,P-diethyl
760, 668 cm-1. HRMS (EI): calcd. for [C12H14IO3P]+: 363.9725,
found 363.9720.
ACCEPTED MANUSCRIPT
Colorless oil (98.8 mg, 70% yield). 1H NMR (400 MHz,
CDCl3) δ = 7.10 (d, J = 8.0 Hz, 1H), 6.95 (s, 1H), 6.77 (d, J = 8.1
Hz, 1H), 5.99 (s, 2H), 4.23 – 4.15 (m, 4H), 1.37 (t, J = 7.1 Hz,
6H) ppm. 13C NMR (100 MHz, CDCl3) δ = 150.1, 147.7, 128.43,
128.41, 112.61, 112.55, 112.18, 112.16, 108.8, 101.9, 99.8, 99.3,
78.4, 75.4, 63.32, 63.27, 16.24, 16.17 ppm. 31P NMR (160 MHz,
CDCl3) δ = -5.70 ppm. MS (EI): m/z = 133.1 (4), 146.1 (100),
209.0 (9), 239.0 (9), 254.1 (15), 282.1 (M+, 39). IR (KBr): ν =
2986, 2907, 2179, 1604, 1505, 1489, 1443, 1339, 1253, 1207,
1131, 1101, 1029, 974, 822, 754, 664, 593 cm-1. HRMS (EI):
calcd. for [C13H15O5P]+: 282.0657, found 282.0652.
4.2.34 P-(1-Biphenylethynyl)-P,P-diethyl phosphonate (4l)
1
Colorless oil (122.6 mg, 78% yield). H NMR (400 MHz,
CDCl3) δ = 7.64 – 7.55 (m, 6H), 7.44 (t, J = 7.5 Hz, 2H), 7.37 (t,
J = 7.3 Hz, 1H), 4.28 – 4.19 (m, 4H), 1.41 (t, J = 7.1 Hz, 6H)
ppm. 13C NMR (100 MHz, CDCl3) δ = 143.5, 139.7, 133.2,
133.1, 129.0, 128.3, 127.3, 127.2, 118.3, 118.2, 99.4, 99.0, 80.5,
77.4, 63.4, 63.3, 16.3, 16.2 ppm. 31P NMR (160 MHz, CDCl3) δ
= -5.93 ppm. MS (EI): m/z = 165.1(15), 178.1 (100), 241.1 (7),
271.1 (14), 286.1 (19), 314.2 (M+, 38). IR (KBr): ν = 3036, 2982,
2938, 2908, 2184, 1485, 1265, 1023, 974, 861, 765, 695, 635 cm-
1. HRMS (EI): calcd. for [C18H19O3P]+: 314.1072, found
314.1066.
4.2.30 P-(1-(4-Fluorophenyl)ethynyl)-P,P-diethyl phosphonate
(4h)
4.2.35 P-(1-(2-Naphthyl)ethynyl)-P,P-diethyl phosphonate (4m)
Colorless oil (99.8 mg, 78% yield). 1H NMR (400 MHz,
CDCl3) δ = 7.54 (dd, J = 8.6, 5.4 Hz, 2H), 7.05 (t, J = 8.6 Hz,
2H), 4.25 – 4.15 (m, 4H), 1.38 (t, J = 7.1 Hz, 6H) ppm. 13C NMR
(100 MHz, CDCl3) δ = 165.2, 162.7, 135.04, 135.01, 134.95,
134.9, 116.3, 116.1, 115.84, 115.80, 115.78, 115.7, 98.3, 97.7,
79.9, 77.0, 63.4, 63.3, 16.24, 16.18 ppm. 19F NMR (370 MHz,
CDCl3): δ = -122.2 (ppm) 31P NMR (160 MHz, CDCl3) δ = -6.18
ppm. MS (EI): m/z = 107.1 (15), 120.1 (100), 183.1 (20), 200.1
(7), 213.1 (16), 228.1 (16), 256.1 (M+, 10). IR (KBr): ν = 2985,
2935, 2905, 2189, 1599, 1508, 1267, 1236, 1160, 1024, 975, 867,
843, 800, 742 cm-1. HRMS (EI): calcd. for [C12H14FO3P]+:
256.0665, found 256.0659.
1
Colorless oil (122.5 mg, 85% yield). H NMR (400 MHz,
CDCl3) δ = 8.10 (s, 1H), 7.84 – 7.78 (m, 3H), 7.56 – 7.49 (m,
3H), 4.29 – 4.21 (m, 4H), 1.41 (t, J = 7.1 Hz, 6H) ppm. 13C NMR
(100 MHz, CDCl3) δ = 133.89, 133.86, 133.85, 132.5, 128.5,
128.1, 128.0, 127.94, 127.92, 127.89, 127.1, 116.73, 116.67,
99.8, 99.3, 80.0, 77.1, 63.4, 63.3, 16.3, 16.2 ppm. 31P NMR (160
MHz, CDCl3) δ = -5.94 ppm. MS (EI): m/z = 139.1(14), 152.1
(100), 215.1 (7), 245.1 (10), 260.1 (16), 288.1 (M+, 34). IR
(KBr): ν = 3057, 2985, 2932, 2908, 2185, 1266, 1159, 1024, 964,
905, 861, 792, 750, 632, 592 cm-1. HRMS (EI): calcd. for
[C16H17O3P]+: 288.0915, found 288.0910.
4.2.36
phosphonate (4n)
P-(1-(6-Methoxy-2-naphthalenyl)ethynyl)-P,P-diethyl
4.2.31 P-(1-(4-Chlorophenyl)ethynyl)-P,P-diethyl phosphonate
(4i)
1
Bright yellow oil (120.9 mg, 76% yield). H NMR (400 MHz,
CDCl3) δ = 8.02 (s, 1H), 7.68 (dd, J = 8.5, 5.1 Hz, 2H), 7.49 (d, J
= 8.5 Hz, 1H), 7.16 (d, J = 9.0 Hz, 1H), 7.09 (s, 1H), 4.29 – 4.19
(m, 4H), 3.90 (s, 3H), 1.41 (t, J = 7.0 Hz, 6H) ppm. 13C NMR
(100 MHz, CDCl3) δ = 159.4, 135.5, 133.7, 133.6, 129.7, 128.7,
128.6, 128.0, 127.2, 120.1, 114.2, 114.1, 105.9, 100.5, 99.9, 79.4,
76.4, 63.34, 63.29, 55.5, 16.3, 16.2 ppm. 31P NMR (160 MHz,
CDCl3) δ = -5.65 ppm. MS (EI): m/z = 139.1 (21), 182.1 (100),
244.1 (9), 275.1 (7), 290.1 (19), 318.1 (M+, 61). IR (KBr): ν =
2985, 2935, 2905, 2179, 1625, 1480, 1391, 1263, 1262, 1162,
1024, 970, 941, 784, 703, 638 cm-1. HRMS calcd. for
[C17H19O4P]+: 318.1021, found 318.1015.
1
Colorless oil (109.1 mg, 80% yield). H NMR (400 MHz,
CDCl3) δ = 7.47 (d, J = 8.3 Hz, 2H), 7.33 (d, J = 8.3 Hz, 2H),
4.25 – 4.15 (m, 4H), 1.38 (t, J = 7.0 Hz, 6H) ppm. 13C NMR (100
MHz, CDCl3) δ = 137.2, 133.92, 133.89, 130.9, 129.1, 118.1,
118.0, 98.0, 97.4, 81.0, 78.0, 63.44, 63.38, 16.24, 16.17 ppm. 31
P
NMR (160 MHz, CDCl3) δ = -5.31 ppm. MS (EI): m/z = 123.1
(10), 136.1 (100), 199.9 (19), 229.0 (20), 244.0 (18), 272.1 (M+,
17). IR (KBr): ν = 2986, 2935, 2908, 2189, 1587, 1488, 1393,
1267, 1092, 1022, 975, 858, 832, 762, 701 cm-1. HRMS (EI):
calcd. for [C12H14ClO3P]+: 272.0369, found 272.0364.
4.2.32 P-(1-(4-Bromophenyl)ethynyl)-P,P-diethyl phosphonate
(4j)
4.2.37 P-(1-(2-Furanyl)ethynyl)-P,P-diethyl phosphonate (4o)
1
Bright yellow oil (120.5 mg, 76% yield). H NMR (400 MHz,
Bright yellow oil (73.1 mg, 64% yield). 1H NMR (400 MHz,
CDCl3) δ = 7.45 (d, J = 0.8 Hz, 1H), 6.85 (d, J = 3.5 Hz, 1H),
6.42 (dd, J = 3.4, 1.7 Hz, 1H), 4.23 – 4.14 (m, 4H), 1.36 (t, J =
7.1 Hz, 6H) ppm. 13C NMR (100 MHz, CDCl3) δ = 145.9, 134.6,
134.5, 120.24, 120.22, 111.4, 88.9, 88.3, 85.1, 82.2, 63.6, 63.5,
16.2, 16.1 ppm. 31P NMR (160 MHz, CDCl3) δ = -6.79 ppm. MS
(EI): m/z = 92.1 (100), 155.1 (15), 172.1 (7), 185.1 (17), 200.1
(8), 228.1 (M+, 19). IR (KBr): ν = 3122, 2987, 2938, 2908, 2183,
1471, 1391, 1267, 1215, 1162, 1024, 977, 944, 811, 757 cm-1.
HRMS (EI): calcd. for [C10H13O4P]+: 228.0546, found 228.0546.
CDCl3) δ = 7.50 (d, J = 8.5 Hz, 2H), 7.40 (d, J = 8.4 Hz, 2H),
4.25 – 4.16 (m, 4H), 1.39 (t, J = 7.1 Hz, 6H) ppm. 13C NMR (100
MHz, CDCl3) δ = 134.1, 134.0, 132.1, 125.6, 118.61, 118.56,
98.0, 97.5, 81.2, 78.2, 63.5, 63.4, 16.3, 16.2 ppm. 31P NMR (160
MHz, CDCl3) δ = -6.39 ppm. MS (EI): m/z = 101.1 (29), 169.0
(10), 180.0 (100), 260 (9), 273.0 (22), 290.1 (17), 316.1 (M+, 16).
IR (KBr): ν = 2985, 2938, 2905, 2187, 1483, 1391, 1265, 1164,
1025, 976, 857, 823, 761, 680 cm-1. HRMS (EI): calcd. for
[C12H14BrO3P]+: 315.9864, found 315.9858.
4.2.33 P-(1-(4-Iodophenyl)ethynyl)-diethyl phosphonate (4k)
4.2.38 P-(1-(2-Thiophenyl)ethynyl)-P,P-diethyl phosphonate (4p)
Yellow solid (131.1 mg, 72% yield). 1H NMR (400 MHz,
CDCl3) δ = 7.70 (dd, J = 10.1, 8.4 Hz, 2H), 7.24 (dd, J = 11.3,
5.9 Hz, 2H), 4.23 – 4.13 (m, 4H), 1.37 (m, 6H) ppm. 13C NMR
(100 MHz, CDCl3) δ = 138.1, 138.0, 133.92, 133.90, 130.8,
119.1, 119.0, 98.2, 97.7, 81.4, 78.4, 63.5, 63.4, 16.3, 16.2 ppm.
31P NMR (160 MHz, CDCl3) δ = -5.30 ppm. MS (EI): m/z = 89.1
(11), 101.1 (32), 164.1 (6), 193.1 (4), 209.1 (15), 228.0 (100),
290.9 (16), 321.0 (20), 336.0 (25), 364.0 (M+, 27). IR (KBr): ν =
2984, 2938, 2902, 2187, 1479, 1392, 1263, 1024, 975, 856, 820,
1
Bright yellow oil (86.7 mg, 71% yield). H NMR (400 MHz,
CDCl3) δ = 7.42 (d, J = 5.2 Hz, 2H), 7.01 (t, J = 4.3 Hz, 1H),
4.19 (m, 4H), 1.37 (t, J = 7.0 Hz, 6H) ppm. 13C NMR (100 MHz,
CDCl3) δ = 136.1, 136.0, 130.7, 127.5, 119.33, 119.27, 92.8,
92.3, 84.0, 81.0, 63.44, 63.38, 16.23, 16.16 ppm. 31P NMR (160
MHz, CDCl3) δ = -6.27 ppm. MS (EI): m/z = 95.1 (6), 108.1
(100), 171.0 (12), 201.0 (15), 216.1 (12), 244.1 (M+, 13). IR
(KBr): ν = 3077, 2986, 2938, 2908, 2174, 1263, 1174, 1023, 976,

8
Tetrahedron
ACCEPTED MANUSCRIPT
852, 801, 715, 638 cm-1. HRMS (EI): calcd. for [C10H1 O3PS]+:
References
3
244.0319, found 244.0318.
1. (a) Viehe, H. G. Chemistry of Acetylenes; Marcel Dekker: New York,
4.2.39 P-(1-Phenylethynyl)-P,P-dimethyl phosphonate (4q)
1969; Chapter 12, pp 861-912;
(b) Ficini, J. Tetrahedron 1976, 32, 448;
1
Bright yellow oil (92.5 mg, 88% yield). H NMR (400 MHz,
(c) Pitacco, G.; Valentin, E. Chemistry of Functional Groups; 1979;
chapter 15, pp 623-714;
(d) Collard-Motte, J.; Janousek, Z. Top. Curr. Chem. 1986, 130, 89;
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Wiley-VCH, 2005.
CDCl3) δ = 7.54 (d, J = 7.5 Hz, 2H), 7.44 (t, J = 7.4 Hz, 1H),
7.35 (t, J = 7.6 Hz, 2H), 3.83 (d, J = 12.3 Hz, 6H) ppm. 13C NMR
(100 MHz, CDCl3) δ = 132.8, 132.7, 130.9, 128.7, 119.30,
119.28, 100.3, 99.8, 78.4, 75.4, 53.53, 53.47 ppm. 31P NMR (160
MHz, CDCl3) δ = -2.77 ppm. MS (EI): m/z = 89 (9), 102 (100),
115 (48), 179 (6), 195 (6), 210 (M+, 22). IR (KBr): ν = 3063,
3000, 2956, 2852, 2187, 1492, 1450, 1271, 1179, 1033, 861, 840,
765, 689, 647 cm-1. HRMS (EI) calcd. for [C10H11O3P]+:
210.0448, found 210.0440.
4.2.40 P-(1-Phenylethynyl)-P,P-diisopropyl phosphonate (4r)
(h) Iorga, B.; Eymery, F.; Carmichael, D.; Savignac, P. Eur. J. Org.
Chem. 2000, 3103;
1
Bright yellow oil (118.5 mg, 89% yield). H NMR (400 MHz,
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CDCl3) δ = 7.51 (d, J = 7.5 Hz, 2H), 7.40 (t, J = 7.4 Hz, 1H),
7.33 (t, J = 7.5 Hz, 2H), 4.84 – 4.71 (m, 2H), 1.37 (d, J = 6.1 Hz,
12H) ppm. 13C NMR (100 MHz, CDCl3) δ = 132.53, 132.50,
130.6, 128.6, 119.9, 119.8, 98.4, 97.9, 81.4, 78.4, 72.40, 72.35,
24.0, 23.9, 23.7, 23.6 ppm. 31P NMR (160 MHz, CDCl3) δ = -
8.60 ppm. MS (EI): m/z = 89 (17), 102 (100), 165 (55), 183 (78),
209 (80), 225 (69), 266 (M+, 3). IR (KBr): ν = 3063, 3000, 2956,
2852, 2187, 1492, 1450, 1271, 1179, 1033, 861, 840, 765, 689,
647 cm-1. HRMS (EI) calcd. for [C14H19O3P]+: 266.1061, found
266.1066.
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W.-M.
Chin.
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2. a) Couty, S.; Meyer, C.; Cossy, J. Angew. Chem. Int. Ed. 2006, 45, 6726;
(b) Tanaka, K.; Takeishi, K.; Noguchi, K. J. Am. Chem. Soc. 2006, 128,
4586;
4.2.41 P-(1-Phenylethynyl)-P,P-dibutyl phosphonate (4s)
Bright yellow oil (1127.7 mg, 80% yield). 1H NMR (400
MHz, CDCl3) δ = 7.53 (d, J = 7.1 Hz, 2H), 7.42 (t, J = 7.5 Hz,
1H), 7.34 (t, J = 7.4 Hz, 2H), 4.13 (dd, J = 14.2, 6.7 Hz, 4H),
1.74 – 1.65 (m, 4H), 1.48 – 1.38 (m, 4H), 0.92 (t, J = 7.4 Hz, 6H)
ppm. 13C NMR (100 MHz, CDCl3) δ = 132.7, 132.6, 130.7,
128.6, 119.7, 119.6, 99.4, 98.8, 79.9, 76.9, 70.0, 66.9, 32.3, 32.2,
18.8, 13.6 ppm. 31P NMR (160 MHz, CDCl3) δ = -5.60 ppm. MS
(EI): m/z = 89 (6), 102 (36), 165 (30), 183 (100), 209 (7), 223 (6),
239 (27), 294 (M+, 1.5). IR (KBr): ν = 2961, 2935, 2869, 2187,
1465, 1271, 1066, 1025, 992, 900, 858, 761, 695, 653 cm-1.
HRMS (EI) calcd. for [C16H23O3P]+: 294.1374, found 294.1379.
(c) Ashburn, B. O.; Carter, R. G.; Zakharov, L. N. J. Am. Chem. Soc.
2007, 129, 9109;
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26;
4.2.42 P-(2,2-Dimethylbutynyl)-P,P-diethyl phosphonate (4t)
Colorless oil (61.1 mg, 56% yield). 1H NMR (400 MHz,
CDCl3) δ = 4.15 – 4.06 (m, 4H), 1.33 (t, J = 7.1 Hz, 6H), 1.25 (s,
9H) ppm. 13C NMR (100 MHz, CDCl3) δ = 110.6, 110.1, 70.3,
67.3, 63.0, 62.9, 29.98, 29.96, 28.1, 28.0, 16.2, 16.1 ppm. 31P
NMR (160 MHz, CDCl3) δ = -5.65 ppm. MS (ESI) m/z (%): 218
(M+, 100). IR (KBr) ν = 2976, 2935, 2908, 2873, 2215, 2181,
1455, 1392, 1368, 1261, 1164, 1099, 1027, 972, 792, 605 cm-1.
HRMS (ESI) calcd. for [C10H19O3P](M+H+): 219.1072, found
219.1078.
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Acknowledgments
The authors are grateful for the financial support from the
National Natural Science Foundation of China (NSFC) (grant
number 21806033), the Natural Science Foundation of Hunan
Province (No. 2017JJ3027), the Fundamental Research Funds for
Hunan University (No. 531107040840).
(q) Wu, C.; Wang, Z.; Hu, Z.; Zeng, F.; Zhang, X.-Y.; Cao, Z.; Tang, Z.;
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Supplementary Material
Supplementary data related to this article can be found at
http://dx.doi.org/10.1016/j.tet.xx.
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9
(4) (a) Zhang, Y.; Hsung, R. P.; Tracey, M. R.; Kurtz, K. C.; Vera, E. L. Org.
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