Palladium-Catalyzed Olefination of N-Tosylhydrazones as β-Diazo Phosphonate Precursors with Arylhalides

Article abstract of DOI:10.1002/ejoc.202000981

An efficient palladium-catalyzed olefination of N-tosylhydrazones as β-diazo phosphonate precursors with aryl halides has been developed. 2,2-Disubstituted vinylphosphonates bearing versatile functional groups were easily accessed in moderate to excellent

Full text of DOI:10.1002/ejoc.202000981

European Journal of Organic Chemistry
Accepted Article
Accepted Article
Title: Palladium-catalyzed olefination of N-tosylhydrazones as β-diazo
phosphonate precursors with arylhalides
Authors: Jing He, Yijiao Feng, Fang Yang, Bin Dai, and Ping Liu
This manuscript has been accepted after peer review and appears as an
Accepted Article online prior to editing, proofing, and formal publication
of the final Version of Record (VoR). This work is currently citable by
using the Digital Object Identifier (DOI) given below. The VoR will be
published online in Early View as soon as possible and may be different
to this Accepted Article as a result of editing. Readers should obtain
the VoR from the journal website shown below when it is published
to ensure accuracy of information. The authors are responsible for the
content of this Accepted Article.
To be cited as: Eur. J. Org. Chem. 10.1002/ejoc.202000981
Link to VoR: https://doi.org/10.1002/ejoc.202000981
01/2020

10.1002/ejoc.202000981
European Journal of Organic Chemistry
FULL PAPER
Palladium-catalyzed olefination of N-tosylhydrazones as β-diazo
phosphonate precursors with arylhalides
Jing He, Yijiao Feng, Fang Yang, Bin Dai,* and Ping Liu*
Dedication ((optional))
[*]
J. He, Y. Feng, F. Yang, Prof. Dr. B. Dai,* Prof. Dr. P. Liu*
School of Chemistry and Chemical Engineering, the Key Laboratory for Green Processing of Chemical Engineering off Xinjiang Bingtuan
Shihezi University,
Shihezi City, 832004, China.
E-mail: db_tea@shzu.edu.cn; liuping1979112@aliyun.com. http://www.escience.cn/people/liuping1979112/index.html.
Supporting information for this article is given via a link at the end of the document.((Please delete this text if not appropriate))
Abstract: An efficient palladium-catalyzed olefination of N-
tosylhydrazones as β-diazo phosphonate precursors with aryl
halides has been developed. 2,2-Disubstituted vinylphosphonates
bearing versatile functional groups were easily accessed in
moderate to excellent yields. Various aryl halides could be employed
as the coupling partners, such as (hetero)arylbromides, aryliodides,
and even arylchlorides. Moreover, with similar strategy (2,2-
diphenylvinyl)diarylphosphine oxides can also be attained by the
reaction of N-tosylhydrazones and aryl bromides. This protocol
features easily available raw materials, simple reaction conditions,
broad substrate scope as well as scale-up ability. Moreover, the
potential application of this product was exemplified by further
transformations.
Introduction
Scheme 1. Palladium-catalyzed couplingg of α- or β-diazo phosphonates.
Main Text Paragraph.As an important family member of organic
phosphates, substituted vinyl phosphates have been applied in
the fields of pharmaceuticals, agricultural chemistry, and
materials science due to their unique biological activity and
chemical properties.1 Furthermore, alkenylphosphates can also
be very useful synthetic precursors, which can be variously
transformed to provide pharmacologically active compounds and
other functional molecules.2,3 Therefore, the efficient
stereoselective synthesis of alkenylphosphates is a significant
objective for organic chemists. In the past decades, a variety of
methods have been developed to access substituted
vinylphosphates, mainly including transition-metal catalyzed
Suzuki-type reaction,4 Heck reactions of aryl halides with
vinylphosphonates,5 decarboxylative C–P coupling reaction,6
nucleophilic addition of aryl alkynes with H-phosphine oxide,7
dehydrogenative coupling of aryl alkenes or precursors with H-
phosphine oxide,8 and 1,2-aryl migration of diarylmethylated
diazomethylphosphonates.9 Although notable advances have
been made, these methods usually encounter some drawbacks
such as relatively harsh reaction conditions, narrow substrate
scope, low yields of the products, the need to prepare
In recent years, N-tosylhydrazones as a class of readily
accessible and stable diazo precursors have been extensively
used in organic synthesis.10 In particular, a palladium-catalyzed
cross-coupling reaction via diazo compound has been
established as a powerful tool for the formations of carbon-
carbon double bonds.11 It is worth mentioning that Wang et.al
demonstrated an efficient strategy on the synthesis of 1,2-
disubstituted vinylphosphonates through the palladium-catalyzed
coupling reaction of α-diazo phosphonates with benzyl or allyl
halides. Moreover, with similar strategy 1,2,2-trisubstituted
vinylphosphonates can also be attained by using N-
tosylhydrazones as α-diazo phosphonates precursors (Scheme
1a).12 Inspired by this work, we speculated 2,2-disubstituted
phosphates should be achieved by employing easily available β-
diazophosphonates as coupling partners to react with aryl
halides in the presence of Pd-catalyst (Scheme 1b).
As shown in Scheme 2, the plausible pathway of palladium-
catalyzed olefination involves four fundamental steps: 1)
oxidative addition of the aryl halide to a Pd(0) complex to form
aryl-palladium-halide complex A; 2) palladium carbene
formation; 3) migratory insertion; and 4) β-hydride elimination.
Besides, an important reason we tend to adopt such a strategy
to construct 2,2-disubstituted phosphates is that the β-
ketophosphonates used to prepare β-diazophosphonates
precursors are readily available.13 Moreover, condensation of β-
prefunctionalized alkenylphosphonates or
a
stoichiometric
amount of metal reagents, and poor regioselectivity. In addition,
the methods for synthesizing 2,2-substituted vinylphosphonates
are still limited. Therefore, it is still highly desirable to develop
efficient and complementary strategies with mild reaction
conditions and readily available reagents.
1
This article is protected by copyright. All rights reserved.

10.1002/ejoc.202000981
European Journal of Organic Chemistry
FULL PAPER
keto phosphonates with TsNHNH2 gives the corresponding N-
tosylhydrazones in good yields. As a part of our research
interest in N-tosylhydrazones,14 herein we described a Pd-
catalyzed olefination reaction of N-tosylhydrazones as β-
diazophosphonate precursors and aryl halides for the synthesis
of 2,2-disubstituted phosphates and derivatives.
delight, the coupling reaction did occur and afford the desired
coupling product 3a in 25% yield (entry 1). Encouraged by this
result, we screened a series of bases (entries 2-7). The strong
base NaOH did not show an influence on the yield (entry 2).
Lithium tert-butoxide (LiOtBu),10,11 as a base commonly used in
olefination reactions involving N-tosylhydrazones, did not show
good results in this reaction (entry 3). In contrast, potassium and
cesium salts showed good effects (entries 4-6), and K2CO3
turned out the best base to accomplish the transformation (entry
7, 85% yield). Subsequently, the effect of solvent was
investigated (entries 8-11), and it was found that DMF also was
an excellent solvent (entry 11, 85% yield) in terms of efficiency
(entry 7). To our delight, the yield of product 3a was dramatically
raised to ≥90% with prolonged reaction time to 12 hours (entries
12 and 13). In addition, reducing the reaction temperature or
increasing the amount of K2CO3 did not significantly improve the
yield of the olefination (entries 14 and 15).
Table 2. Reaction of N-tosylhydrazoness formed by β-ketophosphonates with
aryl halides.[a]
Scheme 2. A possible mechanism pathway.
Results and Discussion
Table 1. Optimization of reaction conditions.[a]
Entry
1
Catalyst
Base
Solvent
Dioxane
Dioxane
Dioxane
Dioxane
Dioxane
Dioxane
Dioxane
THF
t (h)
5
Yield (%)b
25
Pd(PPh3)4
Pd(PPh3)4
Pd(PPh3)4
Pd(PPh3)4
Pd(PPh3)4
Pd(PPh3)4
Pd(PPh3)4
Pd(PPh3)4
Pd(PPh3)4
Pd(PPh3)4
Pd(PPh3)4
Pd(PPh3)4
Pd(PPh3)4
Pd(PPh3)4
Pd(PPh3)4
Na2CO3
NaOH
LiOtBu
K3PO4
KOH
2
5
26
[a] Reaction condition:1 (0.2 mmol), aryyl bromide (2a, 0.24 mmol), Pd(PPh3)4
(5 mol%), K2CO3 (2 equiv.), 1,4-dioxanne (4 mL), 100 oC, 12 h, under Ar
atmosphere. Isolated yields. [b] PhI (2b, 0.24 mmol), [c] PhCl (2c, 0.24 mmol).
3
5
50
4
5
70
5
5
72
6
Cs2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
5
75
With the optimized conditions in hand (Table 1, entry 12), we
explored the substrate scope of the palladium-catalyzed
olefination. As demonstrated in Table 2, a variety of N-
tosylhydrazones formed by β-ketophosphonates reacted with
aryl bromides smoothly to provide the corresponding olefination
products (3a–3d, 3f-3i, 3k-3n, 3p-3s) in 65-93% yields. In
general, both electron-rich and electron-deficient groups (4-Me,
4-MeO, or 4-Cl) substituted N-tosylhydrazones or aryl bromides
were suitable for this protocol, and the desired products were
obtained in good to excellent yields. Moreover, the structure of
the phosphate groups (POR2, R = OEt, OnBu, OiBu, OiPr) on the
N-tosylhydrazones did not have a significant effect on the
reactivity. In contrast, the reaction of N-tosylhydrazones with
diphenylphosphine oxide group can also react with aryl
bromides, giving the corresponding products (3e, 3j, 3o, and 3t)
in 45-70% yields. It is worth mentioning these (2,2-
diarylvinyl)diphenylphosphine oxides could be easily reduced
7
5
85
8
5
75
9
DCE
5
50
10
11
12
13
14[c]
15[d]
MeCN
5
65
DMF
5
85
Dioxane
DMF
12
12
24
12
93
90
Dioxane
Dioxane
82
87
[a] Reaction conditions
Base (2 equiv.)solvent (4 mL), 100 oC
yields [d] K2CO3 (3 equiv.).
[c] 80 o
:
1a (0.2 mmol), 2a (0.24 mmol), Pd
(
PPh3)4 (5 mol%),
,
under Ar atmosphere. [b] Isolated
.
C.
To assess whether the olefination process could be achieved,
we chose the diethyl (2-phenyl-2-(2-
tosylhydrazono)ethyl)phosphonate (1a, 0.2 mmol) and
into
(2,2-diarylvinyl)diphenylphosphane.
This
type
of
organophosphorus ligand has very promising applications in
transition-metal catalyzed coupling reactions.15 In addition,
aryliodides could also be used for the reaction, and the
corresponding products (3a-3e) could be obtained with good to
bromobenzene (2a, 0.24 mmol) as model substrates (Table 1).
Initially, the reaction was performed in 1,4-dioxane (4.0 mL) at
100 °C for 5 hours under argon in the presence of Pd(PPh3)4 (5
mol%) as catalyst and Na2CO3 as base (2.0 equiv.). To our
2
This article is protected by copyright. All rights reserved.

10.1002/ejoc.202000981
European Journal of Organic Chemistry
FULL PAPER
excellent yields. Notably, even chlorobenzene could take part in
the olefination to provide the desired product 3a, albeit with a
relatively lower yield.
methyl iodobenzene with 1a can furnish an excellent yield, but
the ratio of Z/E remains unchanged.
Interestingly, iodomethane as a substrate also participated the
title reaction smoothly, delivering the product diethyl (2-
phenylallyl)phosphonate 4l in 63% yield with high selectivity,
accompanied by a 12% yield of the product (Z)-diethyl (2-
phenylprop-1-en-1-yl)phosphonate 4l' (Scheme 3a). When
Table 3. Reaction of aryl halides with N-tosylhydrazone (1a) formed by diethyl
(2-oxo-2-phenylethyl)phosphonate [a]
.
diethyl
(E)-(2-(2-tosylhydrazono)propyl)phosphonate
was
selected as the substrate to react with bromobenzene, similar
results could also be obtained (Scheme 3b). These results
indicated that the hydrogen on the methyl group preferentially
underwent the β-H elimination compared to the hydrogen on the
methylene group. Also, when diethyl (1-(2-tosylhydrazono)-2,3-
dihydro-1H-inden-2-yl)phosphonate was used as the substrate,
the olefination with aryl iodides also delivered the desired
products 4m and 4n in 40% and 32% yields, respectively
(Scheme 3c).
[a] Reaction condition: 1a (0.2 mmol), aryl bromide (2, 0.24 mmol), Pd(PPh3)4
(5 mol%), K2CO3 (2 equiv.), 1,4-dioxane (4 mL), 100 oC, 12 h, under Ar
atmosphere. Isolated yields. [b] PhI (0.24 mmol).
We next evaluated the scope of aryl and heteroaryl bromides for
this olefination. Due to the difference of the di-substituted groups
at the 2,2-position, the products have two configurations of Z
and E, and the ratio is determined by 1H NMR. As shown in
Table 3, an array of substituents on the phenyl ring of
arylbromides were well tolerated, and affording the desired
products 4a-4k in moderate to excellent yields. The substrates
bearing an electron-donating group (4-Me and 4-OMe) at the
para position of aryl bromides gave the desired products 4a and
4f in excellent yields (Z/E = 1:1). Moreover, aryl bromides with 4-
fluoro, 4-formyl and 4-acetyl groups were transformed into their
corresponding products 4b, 4d, and 4e in excellent yields (Z/E =
1:1‒1:1.2). 1-Bromo-4-nitrobenzene with a strong electron-
withdrawing group as substrate was also tolerated in this
transformation, albeit with moderate yield (Z/E = 1:1). In addition,
2- or 3-substituted methoxybromobenzene was also compatible
with the current reaction conditions, affording the expected
products 4g and 4h with 65% and 52% yields (Z/E = 1:1.1 and
Scheme 3. The olefinations of N-tosylhyddrazones with other substrates.
To demonstrate the practical application of this method, a gram-
scale synthesis of 3a was performed. Gratifyingly, the reaction
could be conducted on a 6.5 mmol scale to provide 1.64 g of
product 3a in 80% yield (Scheme 4).
Scheme 4. A gram-scale synthesis of 3aa.
1:1.2),
respectively.
Furthermore,
3,4,5-
trimethoxybromobenzene was used as a substrate to participate
in the reaction to give the product 4i in 70% yield (Z/E = 1:1.5).
Encouragingly, this reaction could be further extended into
heteroaryl bromides. When 3-bromothiophene and 3-
bromopyridine were used as partners in this reaction, the
desired products 4j and 4k were obtained in 68% and 48%
yields (Z/E = 1:5.5 and 1:1.4), respectively. Also, the reaction of
Scheme 5. Derivatization reactions of 3aa and 3t.
3
This article is protected by copyright. All rights reserved.

10.1002/ejoc.202000981
European Journal of Organic Chemistry
FULL PAPER
was purified by flash chromatography on silica gel (petroleum
Synthetic transformations of products 3a and 3t were also
conducted (Scheme 5). The product 3a could be easily
ether/EtOAc) to give the final products 3a (1.64 g, 80% yield).
hydrolyzed to
a monoester product ethyl hydrogen (2,2-
Hydrolysis of diethyl (2,2-diphenylvinyl)phosphonate 3a
diphenylvinyl)phosphonate 5a in 95% yield by treatment with 10%
aqueous NaOH (Scheme 5a). Additionally, in the presence of
excess HSiCl3, the product 3t could be directly reduced into
bis(4-chlorophenyl)(2,2-diphenylvinyl)phosphane (5t) with 98%
yield (Scheme 5b). This type of organophosphorus ligand has
very promising applications in transition-metal catalyzed
coupling reactions.[15]
Diethyl (2,2-diphenylvinyl)phosphonate 3a (0.5 mmol) was refluxed in 5
mL of 10% aqueous NaOH for 12 h. The solution was cooled to room
temperature and acidified with 10% aqueous HCl. The water was
evaporated, and the obtained solid was dissolved in chloroform. The
organic phase was dried over anhydrous Na2SO4. Then the filtrate
obtained after filtration was distilled to give the product 5a as a white
solid with a 95% yield.
Reduction of alkenylphosphine oxide 3t
(2,2-Bis(4-chlorophenyl)vinyl)diphenylphosphine oxide 3t (0.2 mmol) and
excess HSiCl3 (20 equiv.) in toluene (2 mL) at room temperature under
an argon atmosphere. Then the mixture was stirred at 120 °C for 12 h.
After cooling to room temperature, the solution was added 10% aqueous
NaOH carefully to quench unreacted HSiCl3. Next, the mixture was
diluted with water (10 mL) and extracted with ethyl acetate(10 mL× 3).
The combined organic phase was dried over anhydrous Na2SO4 and
concentrated under reduced pressure. The residue was purified by
column chromatography on silica gel using petroleum ether/ethyl acetate
= 150/1 as eluent to give the target product 5t as white solid with 98%
yield.
Conclusion
In summary, we have demonstrated an efficient Pd(PPh3)4-
catalyzed olefination of N-tosylhydrazones as β-diazo
phosphonate precursors with aryl halides, which constitutes a
novel strategy to synthesize 2,2-disubstituted vinylphosphonates
in moderate to excellent yields. Various aryl halides could be
employed
(hetero)arylbromides, aryliodides, and even arylchlorides. This
transformation also could efficiently produce (2,2-
as
the
coupling
partners,
such
as
diphenylvinyl)diarylphosphine oxides, which shows its eminent
merits such as inexpensive Pd(PPh3)4 as catalyst, easily
available β-diazo phosphonate precursors, broad substrate
scope and facile scalability.
Acknowledgements
We gratefully acknowledge the financial support of this work by
the National Natural Science Foundation of China (No.
21563025, 2171101076 and 21872060) and the Shihezi
University (No. CXRC201602).
Experimental Section
Unless otherwise noted, all synthetic steps were performed under an Ar
atmosphere using Schlenk tubes. The materials obtained from
commercial sources were used without further purification. 1H NMR and
13C NMR spectra were recorded on a Brucker Advance III HD 400 MHz
spectrometer in CDCl3 or CD3OD solution. All chemical shifts were
reported in ppm (δ) relative to the internal standard TMS (0 ppm). High-
resolution mass spectra (HRMS) were acquired in electrospray ionization
(ESI) mode using a TOF mass analyzer.
Keywords: olefination • N-tosylhydrazone •β-diazo phosphonate
• aryl halide • vinylphosphonate
[1]
[2]
(a) L. Bialy, H. Waldmann, Angeww. Chem. Int. Ed. 2005, 44, 3814. (b) A.
George, A. Veis, Chem. Rev. 20008, 108, 4670. (c) K. C. Nicolaou, P.
Maligres, J. Shin, E. Leon, D. Riddeouts, J. Am. Chem. Soc. 1990, 112,
7826. (d) R. Haynes, K. W. A. Looughlin, T. W. Hambley, J. Org. Chem.
1991, 56, 5785. (e) R. K. Hayness, S. C. Vonwiller, T. W. Hambley, J.
Org. Chem. 1989, 54, 5162.
General procedure for the reaction of N-tosylhydrazones formed by
β-ketophosphonates and bromobenzene.
(a) D.-P. Zhao, R. Wang, Chem. SSoc. Rev. 2012, 41, 2095. (b) Y. Li, M.
Josowicz, L.-M. Tolbert, J. Am. CChhem. Soc. 2010, 132, 10374. (c) A.-X.
Zhou, L.-L. Mao, G.-W. Wang, S..-D. Yang, Chem. Commun. 2014, 50,
8529. (d) F.-R. Alexandre, A. Amaador, S. Bot, C. Caillet, T. Convard, J.
Jakubik, C. Musiu, B. Poddesu, L. Vargiu, M. Liuzzi, A. Roland, M.
Seifer, D. Standring, R. Storer, C..-B. Dousson, J. Med. Chem. 2011, 54,
392.
A
Schlenk tube (25 mL) was charged with (E)-(2-Aryl-2-(2-
toluenesulfonyl)ethyl)phosphinate (1, 0.2 mmol), aryl bromide (2, 0.24
mmol), K2CO3 (0.4 mmol) and Pd(PPh3)4 (5 mol%) in 1,4-dioxane (4 mL)
at room temperature under an argon atmosphere. Then the mixture was
stirred at 100 °C for 12 h. After cooling to room temperature, the reaction
mixture was diluted with EtOAc (5 mL), and washed with saturated NaCl
solution (5 mL), and the organic layer was separated. Then the aqueous
layer was extracted with EtOAc (5 mL × 3). The combined organic phase
was dried over anhydrous Na2SO4 and concentrated under reduced
pressure. The crude material was purified by column chromatography on
silica gel to afford the final product 3 or 4.
[3]
[4]
(a) V. V. Grushin, Chem. Rev. 2004, 104, 1629. (b) H. Fernández-
Pérez, P. Etayo, A. Panossian, AA. VidalFerran, Chem. Rev. 2011, 111,
2119. (c) D. S. Surry, S. L. Buchwwald, Angew. Chem. Int. Ed. 2008, 47,
6338.
(a) I. Pergament, M. Srebnik, Teetrahedron Lett. 2001, 42, 8059. (b) I.
Pergament, M. Srebnik, Org. Leett. 2001, 3, 217. (c) G. Evano, K.
Tadiparthi, F. Couty, Chem. Commmun. 2011, 47, 179. (d) S. Thielges, P.
Bisseret, J. Eustache, Org. Lett. 22005, 7, 681. (e) K. Jouvin, A. Coste,
A. Bayle, F. Legrand, G. Karrthikeyan, K. Tadiparthi, G. Evano,
Organometallics, 2012, 31, 7933. (f) L. Liu, Y.-L. Wang, Z.-P. Zeng, P.-
X. Xu, Y.-X. Gao, Y.-W. Yin, Y.-FF. Zhao, Adv. Synth. Catal., 2013, 355,
659. (g) Y.-Y. Xu, J.-Z. Xia, H.-J. Guo, Synthesis, 1986, 8, 691. (h) Y.
Fang, L. Zhang, X. Jin, J. Li, M. YYuan, R. Li, T. Wang, T. Wang, H. Hu,
J. Gu, Eur. J. Org. Chem. 2016, 88, 1577.
General procedure for gram-scale experiment.
A mixture of N-tosylhydrazone 1a (6.5 mmol), PhBr 2a (7.8 mmol),
Pd(PPh3)4 (5 mol%), K2CO3 (2 equiv.), and 1,4-dioxane (20 mL) were
added into a Schlenk tube. The solution was stirred at 100 ºC for 15 h.
After reaction completion, the reaction mixture was diluted with EtOAc
(50 mL), and washed with saturated NaCl solution (50 mL), and the
organic layer was separated. Then the aqueous layer was extracted with
EtOAc (50 mL × 3). The combined organic phase was dried over
anhydrous Na2SO4 and concentrated under reduced pressure. The crude
[5]
(a) H. Brunner, N. L. C. Courcy, JJ.-P. Genêt, Synlett, 2000, 2, 201. (b)
A. Burini, S. Cacchi, P. Pace, B. RR. Pietroni, Synlett, 1995, 6, 677. (c) G.
4
This article is protected by copyright. All rights reserved.

10.1002/ejoc.202000981
European Journal of Organic Chemistry
FULL PAPER
W. Kabalka, S. K. Guchhait, A. Naravane, Tetrahedron Lett., 2004, 45,
4685. (d) K. Jouvin, A. Coste, A. Bayle, F. Legrand, G. Karthikeyan, K.
Tadiparthi, G. Evano, Organometallics, 2012, 31, 7933. (e) Y. Uozumi,
T. Kimura, Synlett, 2002, 34, 2045. (f) W. A. Maksoud, J. Mesnager, F.
Jaber, C. Pinel, L. J. Djakovitch, Organomet. Chem. 2009, 694, 3222.
Vaccaro, P. Liu, Y. Gu, 2020, 8, 4466. (j) Z. Sun, J. He, W. Li, X. Li, Y.
Feng, Y. Liu, P. Liu, S. Han, ChemmistrySelect 2020, 5, 7396.
[15] K. Suzuki, Y. Hori, T.Nishikawa,TT. Kobayashi, Adv. Synth. Catal. 2007,
349, 2089.
[6]
(a) J. Hu, N. Zhao, B. Yang, Ge. Wang, L.-N. Guo, Y.-M. Liang, S.-D.
Yang, Chem. Eur. J. 2011, 17, 5516. (b) X. Li, F. Yang, Y. Wu, Y. Wu,
Org. Lett. 2014, 16, 992. (c) G.-B. Hu, Y.-X. Gao, Y.-F. Zhao, Org. Lett.
2014, 16, 4464. (d) Y.-L. Wu, L. Liu, K.-L. Yan, P.-X. Xu, Y.-X. Gao, Y.-
F. Zhao, J. Org. Chem. 2014, 79, 8118. (e) L. Tang, L. Wen, T. Sun, D.
Zhang, Z. Yang, C. Feng, Z. Wang, Asian J. Org. Chem. 2017, 6, 1683.
(f) L. Ren, M. Ran, J. He, D. Xiang, F. Chen, P. Liu, C. He, Q. Yao, Eur.
J. Org.Chem. 2019, 33, 5656.
[7]
(a) L.-B. Han, C. Zhang, H. Yazawa, S. Shimada, J. Am. Chem. Soc.
2004, 126, 5080. (b) L.-B. Han, R. Hua, M. Tanaka, Angew. Chem. Int.
Ed. 1998, 37, 94. (c) K. Takaki, M.Takeda, G. Koshoji, T. Shishido, K.
Takehira, Tetrahedron Lett. 2001, 34, 6357. (d) K. Takaki, G. Koshoji, K.
Komeyama, M. Take da, T. Shishido, A. Kitani, K. Takehira, J. Org.
Chem. 2003, 68, 6554. (e) M.-Y. Niu, H. Fu, Y.-Y. Jiang, Y.-F. Zhao,
Chem. Commun. 2007, 39, 272. (f) I. G. Trostyanskaya, I. P.
Beletskaya, Tetrahedron, 2014, 70, 2556. (g) L.-B. Han, C.-Q. Zhao, M.
J. Tanaka, Org. Chem. 2001, 66, 5929. (h) T. Chen, C.-Q. Zhao, L.-
B.Han, J. Am. Chem. Soc. 2018, 140, 3139. (i) L. Chen, Y. X. Zou, X. Y.
Liu, X. J. Gou, Adv. Synth. Catal. 2019, 361, 3490.
[8]
[9]
(a) L. L. Mao, A. X. Zhou, N. Liu, Synlett, 2014, 25, 2727. (b) Z. Tan, Q.
Gui, L. Hu, X. Chen, J. Liu, Chem. Commun. 2015, 51, 13922. (c) J. Gu,
C. Cai, Org. Biomol. Chem. 2017, 15, 4226. (d) L. Wang, Z. Yang, H.
Zhu, H. Liu, S. Lv, Y. Xu, Eur. J. Org. Chem. 2019, 2019, 2138. (e) P.
Xie, J. Fan, Y. Liu, X. Wo, W. Fu, T. P. Loh, Org. Lett. 2018, 20, 3341.
(f) W. Q. Liu, T. Lei, S. Zhou, X. L. Yang, J. Li, B. Chen, J. Sivaguru, C.-
H. Tung, L. Z. Wu, J. Am. Chem. Soc. 2019, 141, 13941.
A. K. Gupta, S. Ahamad, N. K. Vaishanv, R. Kant, K. Mohanan, Org.
Biomol. Chem. 2018, 16, 4623.
[10] (a) J. R. Fulton, V. K. Aggarwal, J. de Vicente, Eur. J. Org. Chem. 2005,
2005, 1479. (b) Y. Xia, Y. Zhang, J. Wang, ACS Catalysis, 2013, 3,
2586. (c) M. Jia, S. Ma, Angew. Chem. Int. Ed. 2016, 55, 9134. (d) Y.
Xia, J. Wang, Chem. Soc. Rev. 2017, 46, 2306. (e) R. Barroso, M. P.
Cabal, C. Valdés, Synthesis, 2017, 49, 4434.
[11] (a) J. Barluenga, C. Valdés, Angew. Chem. Int. Ed. 2011, 50, 7486. (b)
Z. Shao, H. Zhang, Chem. Soc. Rev. 2012, 41, 560. (c) Q. Xiao, Y.
Zhang, J. Wang, Acc. Chem. Res. 2013, 46, 236. (d) Y. Xia, D. Qiu, J.
Wang, Chem. Rev. 2017, 117, 13810.
[12]
Y. Zhou, F. Ye, X. Wang, S. Xu, Y. Zhang, J. Wang, J. Org. Chem.
2015, 80, 6109.
[13] (a) W. Wei, J. X. Ji, Angew. Chem. Int. Ed. 2011, 50, 9097. (b) Q. Fu, D.
Yi, Z. Zhang, W. Liang, S. Chen, L. Yang, Org. Chem. Front. 2017, 4,
1385. (c) D. Yi, Q. Fu, Chen, Y. S. M. Gao, L. Yang, Z. J. Zhang,
Tetrahedron Lett, 2017, 58, 2058. (d) M. S. Li, Q. Zhang, D. Y. Hu, W.
W. Zhong, M. Cheng, J. X. Ji, W. Wei, Tetrahedron Lett, 2016, 57, 2642.
(e) Z. J. Zhang, D. Yi, Q. Fu, W. Liang, S. Y. Chen, L. Yang, W. Wei,
Tetrahedron Lett, 2017, 58, 2417. (f) W. W. Zhong, Q. Zhang, M. S. Li,
D. Y. Hu, M. Cheng, F. T. Du, W. Wei, Synth. Commun. 2016, 46, 1377.
(g) K. Lee, D. F. Wiemer, K. Lee, D. F. Wiemer, J. Org. Chem. 1991, 56,
5556. (h) T. Calogeropoulou, G. B. Hammond, D. F. Wiemer, T.
Calogeropoulou, G. B. Hammond, D. F. Wiemer, J. Org. Chem. 1987,
52, 4185. (i) J. A. Murphy, F. Rasheed, S. J. Roome, N. Lewis, J. A.
Murphy, F. Rasheed, S. J. Roome, N. Lewis, Chem. Commun. 1996, 6,
737. (j) Y. Han, L. Zhu, Y. Gao, C.-S. Lee, Org. Lett. 2011, 13, 588.
[14] (a) Y. Liu, L. Chen, Z. Wang, P. Liu, Y. Liu, B. Dai, J. Org. Chem. 2019,
84, 204. (b) Z. Sun, C. Du, P. Liu, Y. Wei, L. Xu, B. Dai,
ChemistrySelect, 2018, 3, 900. (c) Z. Sun, P. Liu, B. Dai. J. Saudi
Chem. Soc. 2018, 22, 930. (d) X. Shen, P. Liu, Y. Liu, Y. Liu, B. Dai,
Tetrahedron, 2017, 73, 785. (e) X. Shen, P. Liu, Y. Liu, B. Dai,
Tetrahedron, 2017, 73, 6558. (f) Y. Liu, P. Liu, Y. Liu, Y. Wei, Chin. J.
Chem. 2017, 35, 1141. (g) X. Shen, N. Gu, P. Liu, X. Ma, J. Xie, Y. Liu,
B. Dai, Chin. J. Chem. 2016, 34, 1033; Z. Yang, J. He, Y. Wei, W.i Li, P.
Liu, Org. Biomol. Chem., 2020, 18, 3360. (h) J.Zhang, W. Li, Y. Liu, P.
Liu, ChemistrySelect 2020, 5, 5497. (i) W. Li, J. Zhang, J. He, L. Xu, L.
5
This article is protected by copyright. All rights reserved.

10.1002/ejoc.202000981
European Journal of Organic Chemistry
FULL PAPER
Entry for the Table of Contents
An efficient Pd-catalyzed olefination of N-tosylhydrazones as β-diazo phosphonate precursors with aryl halides was described. A
series of 2,2-disubstituted vinylphosphonates and (2,2-diphenylvinyl)diarylphosphine oxides were easily obtained in moderate to
excellent yields.
Institute and/or researcher Twitter usernames: ((optional))
6
This article is protected by copyright. All rights reserved.