Rh(I)-Catalyzed Arylation of α-Diazo Phosphonates with Aryl Boronic Acids: Synthesis of Diarylmethylphosphonates

Article abstract of DOI:10.1002/cjoc.201600487

An efficient synthetic method for diarylmethylphosphonates is presented. A series of phosphonate derivatives with diverse functional groups can be accessed via a rhodium catalyzed cross-coupling reaction between α-diazo phosphonates and aryl boronic acids. Migratory insertion of rhodium carbene intermediates is postulated to be the critical step in this transformation.

Full text of DOI:10.1002/cjoc.201600487

FULL PAPER
DOI: 10.1002/cjoc.201600487
Rh(I)-Catalyzed Arylation of α-Diazo Phosphonates with Aryl
Boronic Acids: Synthesis of Diarylmethylphosphonates
Yujing Zhou,a Yan Zhang,a and Jianbo Wang*,a,b
a Beijing National Laboratory of Molecular Sciences (BNLMS) and Key Laboratory of Bioorganic Chemistry and
Molecular Engineering of Ministry of Education, College of Chemistry, Peking University, Beijing 100871, China
b The State Key Laboratory of Organometallic Chemistry, Chinese Academy of Sciences, Shanghai 200032, China
An efficient synthetic method for diarylmethylphosphonates is presented. A series of phosphonate derivatives
with diverse functional groups can be accessed via a rhodium catalyzed cross-coupling reaction between α-diazo
phosphonates and aryl boronic acids. Migratory insertion of rhodium carbene intermediates is postulated to be the
critical step in this transformation.
Keywords Rh(I)-catalysis, metal carbene, migratory insertion, -diazo phosphonates, aryl boronic acids
Introduction
Scheme 1 Synthetic methods for diarylmethylphosphonates
(a) Michaelis-Abuzov reaction
Organophosphorus compounds are of great im-
portance because of their widespread applications in
chemistry, biology and life sciences.[1] Especially, dia-
rylmethylphosphonates are routinely found as structural
elements in many natural products and bioactive mole-
cules.[2] They can also be used as crucial building blocks
in Horner-Wadsworth-Emmons olefination reactions.[3]
Therefore, many efforts have been devoted to pursuing
the efficient methods for the synthesis of this scaffold
(Scheme 1).
Ar'
Ar'
OR
OR
+
P(OR)3
Ar
Ar
Ar
X
P
X = Br, Cl
O
(b) Friedel-Crafts alkylation
OH
Ar'
FeCl3
OEt
OEt
Ar'H
OEt
+
P
Ar
r.t. to 70 oC
P
OEt
O
O
One of the most commonly utilized methods is
Michaelis-Arbuzov reaction by employing the alkyl
halides and phosphites as the starting materials (Scheme
1a).[4] However, the inconvenient access of diarylmethyl
halides and harsh reaction conditions prevent this trans-
formation from becoming a practical synthetic method.
In 2013, a Friedel-Crafts type reaction was demon-
strated to afford diarylmethylphosphonate compounds in
relatively good yields (Scheme 1b).[5] However, the re-
action suffered from several drawbacks such as limited
arene scope and the formation of regioisomers. Subse-
quently, Walsh and co-workers disclosed a palladium-
catalyzed α-arylation procedure to obtain the phospho-
nate derivatives (Scheme 1c).[6] In this case, a series of
aryl bromides and benzylic phosphonates could be con-
verted to the desired products in high yields with good
functional group compatibility.
(c) Palladium-catalyzed cross-coupling
Pd(OAc)2
Ar'
OiPr
OiPr
OiPr
OiPr
CataCXium A
Ar'Br
+
Ar
P
Ar
P
NaOtBu, CPME
80 oC
O
O
(d) Copper-catalyzed P-H insertion
Ar'
R'
Ar'
O
CuI, Cs2CO3
DME, 80 oC
Ar
P
+
R'
P
R
Ar
H
O
NNHTs
R
(e) Carbene-involved cross-coupling (this work)
N2
Ar'
cat. [Rh]
OMe
OMe
Ar'B(OH)2
+
Ar
P
Ar
P
OMe
OMe
O
O
Additionally, several examples concerning the P-H
insertion reaction of metal carbene intermediates have
been described as complementary strategies for the
synthesis of phosphonate molecules (Scheme 1d).[7]
However, to the best of our knowledge, diaryl substi-
*
E-mail: wangjb@pku.edu.cn
Received July 31, 2016; accepted September 13, 2016; published online XXXX, 2016
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/cjoc.201600487 or from the author.
Dedicated to the Memory of Professor Enze Min.
Chin. J. Chem. 2016, XX, 1—7
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1

Zhou et al.
FULL PAPER
tuted hydrazones were not effective starting substrates
in this transformation due to the steric hindrance. As a
result, diarylmethylphosphonates cannot be generally
accessed through this protocol. Considering the high
importance of phosphorus functionality and limited
synthetic methods currently available, further develop-
ment of efficient and general approaches for the con-
struction of diarylmethylphosphonate motifs is still
highly desirable.
For the past decade, transition-metal-catalyzed car-
bene involved cross-coupling reactions have become an
effective method for the C—C bond formations.[8] In
particular, the Suzuki-type coupling of diazo com-
pounds is frequently employed because organoboron
reagents are usually non-toxic and stable, and many of
them are commercially available.[9] On the other hand,
we have recently disclosed several transformations of
α-diazo phosphonates,[10] which have proved to be good
substrates for the introduction of phosphonate moiety to
the target molecules. As a continuation of our interest in
carbene coupling reactions, we report herein a rhodium-
catalyzed cross-coupling reaction between α-diazo
phosphonates and aryl boronic acids. This reaction rep-
resents an efficient access toward diarylmethylphospho-
nates with diverse substituents.
tile materials. The crude residue was purified by column
chromatography (silica gel, petroleum ether∶EtOAc＝
1∶1) to afford the final products.
Dimethyl
(diazo(phenyl)methyl)phosphonate
(1a)[13] 1H NMR (400 MHz, CDCl3) δ: 7.34－7.38 (m,
2H), 7.13－7.17 (m, 3H), 3.81 (d, J＝11.9 Hz, 6H).
Dimethyl
(diazo(p-tolyl)methyl)phosphonate
(1b)[13] 1H NMR (400 MHz, CDCl3) δ: 7.17 (d, J＝8.4
Hz, 2H), 7.06 (d, J＝8.4 Hz, 2H), 3.80 (d, J＝11.6 Hz,
6H), 2.33 (s, 3H).
Dimethyl ((4-chlorophenyl)(diazo)methyl)phos-
phonate (1c)[13] 1H NMR (400 MHz, CDCl3) δ: 7.31
－7.34 (m, 2H), 7.08－7.11 (m, 2H), 3.82 (d, J＝12.0
Hz, 6H).
Dimethyl ((4-bromophenyl)(diazo)methyl)phos-
phonate (1d)[13] 1H NMR (400 MHz, CDCl3) δ: 7.47
(d, J＝8.6 Hz, 2H), 7.04 (d, J＝8.6 Hz, 2H), 3.81 (d,
J＝11.9 Hz, 6H).
Dimethyl (diazo(4-methoxyphenyl)methyl)phos-
phonate (1e)[13] 1H NMR (400 MHz, CDCl3) δ: 7.09
－7.12 (m, 2H), 6.92－6.94 (m, 2H), 3.81 (d, J＝12.0
Hz, 6H), 3.80 (s, 3H).
Methyl 4-(diazo(dimethoxyphosphoryl)methyl)-
benzoate (1f)[11] 1H NMR (400 MHz, CDCl3) δ: 8.01
(d, J＝8.5 Hz, 2H), 7.21 (d, J＝8.5 Hz, 2H), 3.91 (s,
3H), 3.84 (d, J＝12.0 Hz, 6H).
Dimethyl ((3-chlorophenyl)(diazo)methyl) phos-
phonate (1g) 1H NMR (400 MHz, CDCl3) δ: 7.28 (t,
J＝8.0 Hz, 1H), 7.11－7.14 (m, 2H), 7.04 (d, J＝8.0 Hz,
1H), 3.83 (d, J＝12.0 Hz, 6H).
Experimental
General procedure for the preparation of aryldiazo-
phosphonates 1a－1g[11]
The diazo compounds 1a－1g were prepared ac-
cording to our previously reported method of palladi-
um-catalyzed cross-coupling of dimethyl (1-diazo-2-
oxopropyl)phosphonate with aryl iodide. The dimethyl
(1-diazo-2-oxopropyl)phosphonate was prepared fol-
lowing a literature procedure.[12] A solution of dimethyl
2-oxopropylphosphonate (3.32 g, 20.0 mmol) in toluene
(85 mL) and THF (18 mL) was stirred and cooled to
0 ℃ by ice-water bath for 30 min, and sodium hydride
(60% in oil, 0.88 g, 22.0 mmol) was slowly added into
the flask. The mixture was stirred at 0 ℃ under N2 for
1 h, and p-ABSA (5.28 g, 22.0 mmol) was then added.
The reaction was warmed to room temperature and stir-
ring was continued overnight under N2. The mixture
was filtered through a Celite pad, and the filtrate was
evaporated in vacuo to remove the volatile materials.
The crude residue was purified by chromatography (sil-
ica gel, petroleum ether∶EtOAc＝1∶1) to give the
product as a yellow oil (2.38 g, 62%).
Pd(PPh3)4 (116 mg, 5 mol%), K2CO3 (552 mg, 4.0
mmol) and aryl iodide (2.0 mmol) were suspended in
methanol (5 mL) and toluene (5 mL) in a 25 mL flask
under ambient atmosphere. Dimethyl (1-diazo-2-oxo-
propyl)phosphonate (499 mg, 1.3 equiv.) was then add-
ed, and the resulting solution was stirred at room tem-
perature for 5 h. The mixture was filtered through a
short path of silica gel, eluting with ethyl acetate, and
the filtrate was evaporated in vacuo to remove the vola-
Experimental procedure for the Rh(I)-catalyzed ary-
lation reaction
A 10 mL Schlenk tube was charged with
[Rh(COD)Cl]2 (1 mg, 1 mol%), KOtBu (25 mg, 0.22
mmol, 1.1 equiv.) and aryl boronic acid (0.22 mmol, 1.1
equiv.). The tube was sealed and then evacuated and
backfilled with N2 three times. Then a solution of
α-diazo phosphonate in methyl tert-butyl ether (MTBE)
(0.20 mmol, 1.0 mL) was added, and the mixture was
allowed to stir at 40 ℃ for 12 h. The mixture was fil-
tered through a short path of silica gel, eluting with
ethyl acetate, and the filtrate was evaporated in vacuo to
remove the volatile materials. The crude residue was
purified via column chromatography (silica gel, petro-
leum ether∶EtOAc＝1∶1) to give the final products.
Dimethyl benzhydrylphosphonate (3a)[14] White
solid, yield 92% (51 mg). 1H NMR (400 MHz, CDCl3) δ:
7.52－7.54 (m, 4H), 7.32 (d, J＝7.6 Hz, 4H), 7.23－
7.278 (m, 2H), 4.46 (d, J＝25.2 Hz, 1H), 3.56 (d, J＝
10.8 Hz, 6H).
Dimethyl ((4-chlorophenyl)(phenyl)methyl)phos-
phonate (3b) Colorless oil, yield 95% (60 mg), Rf＝
1
0.40 (petroleum ether∶EtOAc＝1∶1); H NMR (400
MHz, CDCl3) δ: 7.44－7.49 (m, 4H), 7.24－7.35 (m,
5H), 4.43 (d, J＝25.2 Hz, 1H), 3.59 (d, J＝10.8 Hz, 3H),
3.55 (d, J＝10.8 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ:
135.9 (d, J＝5.1 Hz), 135.0 (d, J＝5.2 Hz), 133.2 (d, J＝
2
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Synthesis of Diarylmethylphosphonates
2.6 Hz), 130.6 (d, J＝8.0 Hz), 129.2 (d, J＝7.9 Hz),
128.8 (d, J＝1.0 Hz), 128.8 (d, J＝1.1 Hz), 127.5 (d, J＝
2.0 Hz), 53.5 (d, J＝7.1 Hz), 53.4 (d, J＝7.2 Hz), 50.0 (d,
J＝138.4 Hz); 31P NMR (162 MHz, CDCl3) δ: 26.86; IR
(film) v: 1490, 1251, 1055, 1030, 1016, 826, 755, 730,
699 cm1; EI-MS (m/z, relative intensity): 310 (28), 201
(100), 165 (64); HRMS (ESI) calcd for C15H17ClO3P
(M＋H)＋ 311.0598, found 311.0592.
Dimethyl
((3-methoxyphenyl)(phenyl)methyl)-
phosphonate (3f) Colorless oil, yield 79% (48 mg),
Rf＝0.30 (petroleum ether∶EtOAc＝1∶1); H NMR
1
(400 MHz, CDCl3) δ: 7.51－7.53 (m, 2H), 7.32 (t, J＝8.0
Hz, 2H), 7.21－7.26 (m, 2H), 7.08－7.13 (m, 2H),
7.78－7.81 (m, 1H), 4.43 (d, J＝24.8 Hz, 1H), 3.78 (s,
3H), 3.58 (d, J＝10.8 Hz, 3H), 3.56 (d, J＝10.4 Hz, 3H);
13C NMR (100 MHz, CDCl3) δ: 159.6, 137.8 (d, J＝5.1
Hz), 136.3 (d, J＝5.6 Hz), 129.6, 129.3 (d, J＝7.9 Hz),
128.6, 127.2 (d, J＝2.1 Hz), 121.7 (d, J＝7.9 Hz), 115.2
(d, J＝8.3 Hz), 112.6 (d, J＝2.1 Hz), 55.1, 53.4 (d, J＝
7.1 Hz), 53.4 (d, J＝7.1 Hz), 50.7 (d, J＝137.6 Hz); 31P
NMR (162 MHz, CDCl3) δ: 27.30; IR (film) v: 1597,
1490, 1252, 1030, 829, 732, 703 cm1; EI-MS (m/z, rel-
ative intensity): 306 (35), 197 (100), 182 (18), 165 (19),
153 (6); HRMS (ESI) calcd for C16H20O4P [(M＋H)＋]
307.1094, found 307.1092.
Dimethyl (phenyl(3-(trifluoromethoxy)phenyl)-
methyl)phosphonate (3g) Colorless oil, yield 88%
(63 mg), Rf＝0.60 (petroleum ether∶EtOAc＝1∶1);
1H NMR (400 MHz, CDCl3) δ: 7.45－7.51 (m, 3H), 7.40
(s, 1H), 7.34 (t, J＝7.6 Hz, 3H), 7.26－7.30 (m, 1H),
7.11－7.13 (m, 1H), 4.47 (d, J＝25.2 Hz, 1H), 3.59 (d,
J＝10.8 Hz, 3H), 3.55 (d, J＝10.8 Hz, 3H); 13C NMR
(100 MHz, CDCl3) δ: 149.2, 138.8 (d, J＝5.2 Hz), 135.6
(d, J＝5.4 Hz), 129.9, 129.3 (d, J＝7.8 Hz), 128.8 (d,
J＝1.1 Hz), 127.7 (d, J＝7.8 Hz), 127.6 (d, J＝2.0 Hz),
122.0 (d, J＝7.9 Hz), 120.4 (q, J＝255.6 Hz), 119.6, 53.5
(d, J＝7.0 Hz), 53.3 (d, J＝6.9 Hz), 50.4 (d, J＝138.0
Hz); 31P NMR (162 MHz, CDCl3) δ: 26.41; IR (film) v:
1258, 1215, 1166, 1031, 832, 736, 703 cm1; EI-MS (m/z,
relative intensity): 360 (32), 251 (100), 165 (40); HRMS
(ESI) calcd for C16H17F3O4P [(M＋H)＋] 361.0811, found
361.0806.
Dimethyl
((4-methoxyphenyl)(phenyl)methyl)-
phosphonate (3c) Colorless solid, yield 96% (59 mg),
Rf＝0.30 (petroleum ether∶EtOAc＝1∶1), m.p. 91－
1
93 ℃; H NMR (400 MHz, CDCl3) δ: 7.49－7.51 (m,
2H), 7.43－7.45 (m, 2H), 7.31 (t, J＝7.6 Hz, 2H),
7.22－7.26 (m, 1H), 6.85－6.87 (m, 2H), 4.41 (d, J＝
25.2 Hz, 1H), 3.77 (s, 3H), 3.55 (d, J＝10.8 Hz, 3H),
3.54 (d, J＝10.4 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ:
158.7 (d, J＝2.0 Hz), 136.8 (d, J＝4.9 Hz), 130.4 (d, J＝
8.0 Hz), 129.2 (d, J＝8.0 Hz), 128.6 (d, J＝0.9 Hz),
128.4 (d, J＝5.3 Hz), 127.1 (d, J＝1.9 Hz), 114.0 (d, J＝
0.9 Hz), 55.1, 53.3 (d, J＝7.1 Hz), 53.3 (d, J＝6.9 Hz),
49.8 (d, J＝137.8 Hz); 31P NMR (162 MHz, CDCl3) δ:
27.68; IR (film) v: 1511, 1252, 1181, 1055, 1028, 822,
770, 734, 700 cm1; EI-MS (m/z, relative intensity): 306
(12), 197 (100), 153(12); HRMS (ESI) calcd for
C16H20O4P (M＋H)＋ 307.1094, found 307.1090.
Dimethyl
([1,1'-biphenyl]-4-yl(phenyl)methyl)-
phosphonate (3d) White solid, yield 68% (48 mg),
1
Rf＝0.35 (petroleum ether∶EtOAc＝1∶1). H NMR
(400 MHz, CDCl3) δ: 7.54－7.61 (m, 8H), 7.39－7.43
(m, 2H), 7.30－7.36 (m, 3H), 7.24－7.28 (m, 1H), 4.50
(d, J＝25.2 Hz, 1H), 3.59 (t, J＝10.8 Hz, 6H); 13C NMR
(100 MHz, CDCl3) δ: 140.5, 140.1 (d, J＝2.3 Hz), 136.4
(d, J＝5.3 Hz), 135.5 (d, J＝5.6 Hz), 129.7 (d, J＝7.9
Hz), 129.4 (d, J＝8.0 Hz), 128.7, 127.3 (d, J＝1.1 Hz),
127.3, 127.3, 127.0, 53.4 (t, J＝7.6 Hz), 50.5 (d, J＝
137.5 Hz) (One peak is missing because of overlap); 31P
NMR (162 MHz, CDCl3) δ: 27.33; IR (film) v: 1488,
1250, 1055, 1030, 823, 762, 731, 698 cm1; EI-MS (m/z,
relative intensity): 352 (23), 243 (100), 228 (8), 165 (14);
HRMS (ESI) calcd for C21H22O3P [(M＋H)＋] 353.1301,
found 353.1296.
Dimethyl ((3,5-dimethylphenyl)(phenyl)methyl)-
phosphonate (3h) Colorless oil, yield 90% (55 mg),
Rf＝0.40 (petroleum ether∶EtOAc＝1∶1); H NMR
1
(400 MHz, CDCl3) δ: 7.51－7.52 (m, 2H), 7.31 (t, J＝7.6
Hz, 2H), 7.23－7.25 (m, 1H), 7.13 (s, 2H), 6.88 (s, 1H),
4.38 (d, J＝25.2 Hz, 1H), 3.57 (d, J＝10.8 Hz, 3H), 3.54
(d, J＝10.8 Hz, 3H), 2.29 (s, 6H); 13C NMR (100 MHz,
CDCl3) δ: 138.1, 136.7 (d, J＝5.4 Hz), 136.2 (d, J＝5.1
Hz), 129.3 (d, J＝8.0 Hz), 129.0 (d, J＝1.9 Hz), 128.6 (d,
J＝1.1 Hz), 127.1 (d, J＝2.2 Hz), 127.0 (d, J＝8.5 Hz),
53.3 (d, J＝7.2 Hz), 53.3 (d, J＝7.1 Hz), 50.7 (d, J＝
137.2 Hz), 21.3; 31P NMR (162 MHz, CDCl3) δ: 27.64;
IR (film) v: 1251, 1056, 1030, 827, 711, 696 cm1;
EI-MS (m/z, relative intensity): 304 (34), 195 (100), 180
(31), 165 (35); HRMS (ESI) calcd for C17H22O3P [(M＋
H)＋] 305.1301, found 305.1299.
Dimethyl (phenyl(o-tolyl)methyl)phosphonate (3i)
Colorless oil, yield 95% (55 mg), Rf＝0.40 (petroleum
ether∶EtOAc＝1∶1); H NMR (400 MHz, CDCl3) δ:
7.94 (d, J＝7.6 Hz, 1H), 7.46 (d, J＝7.6 Hz, 2H), 7.20－
7.29 (m, 4H), 7.14－7.18 (m, 2H), 4.70 (d, J＝26.0 Hz,
1H), 3.55 (d, J＝10.8 Hz, 3H), 3.55 (d, J＝10.8 Hz, 3H),
2.32 (s, 3H); 13C NMR (100 MHz, CDCl3) δ: 136.3 (d,
J＝11.9 Hz), 135.9 (d, J＝5.8 Hz), 134.9 (d, J＝3.8 Hz),
Dimethyl ((3-bromophenyl)(phenyl)methyl)phos-
phonate (3e) Colorless oil, yield 97% (69 mg), Rf＝
1
0.40 (petroleum ether∶EtOAc＝1∶1); H NMR (400
MHz, CDCl3) δ: 7.62－7.63 (m, 1H), 7.50－7.53 (m,
3H), 7.32－7.39 (m, 3H), 7.25－7.29 (m, 1H), 7.20 (t,
J＝8.0 Hz, 1H), 4.41 (d, J＝25.2 Hz, 1H), 3.60 (d, J＝
10.8 Hz, 3H), 3.55 (d, J＝10.8 Hz, 3H); 13C NMR (100
MHz, CDCl3) δ: 138.8 (d, J＝5.0 Hz), 135.7 (d, J＝5.2
Hz), 132.3 (d, J＝8.6 Hz), 130.4 (d, J＝1.8 Hz), 130.1 (d,
J＝1.2 Hz), 129.3 (d, J＝7.7 Hz), 128.8, 127.9 (d, J＝7.6
Hz), 127.5 (d, J＝2.0 Hz), 122.6, 53.5 (d, J＝6.8 Hz),
53.3 (d, J＝7.0 Hz), 50.3 (d, J＝138.0 Hz); 31P NMR
(162 MHz, CDCl3) δ: 26.55; IR (film) v: 1251, 1055,
1029, 826, 762, 729, 704 cm1; EI-MS (m/z, relative
intensity): 354 (26), 245 (100), 165 (96); HRMS (ESI)
calcd for C15H17BrO3P [(M ＋H)＋] 355.0093, found
355.0089.
1
Chin. J. Chem. 2016, XX, 1—7
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Zhou et al.
FULL PAPER
130.7, 129.6 (d, J＝7.4 Hz), 129.3 (d, J＝5.4 Hz), 128.5
(d, J＝1.4 Hz), 127.2 (d, J＝1.2 Hz), 127.1 (d, J＝2.4
Hz), 126.2 (d, J＝1.4 Hz), 53.3 (d, J＝7.1 Hz), 53.2 (d,
J＝6.9 Hz), 46.2 (d, J＝138.7 Hz), 19.9; 31P NMR (162
MHz, CDCl3) δ: 28.27; IR (film) v: 1495, 1453, 1252,
1054, 1028, 823, 737, 699 cm1; EI-MS (m/z, relative
intensity): 290 (42), 181 (100), 165 (51); HRMS (ESI)
calcd for C16H20O3P [(M ＋H) ＋ ] 291.1145, found
291.1149.
Dimethyl (naphthalen-2-yl(phenyl)methyl)phos-
phonate (3j) Colorless oil, yield 97% (63 mg), Rf＝
0.35 (petroleum ether∶EtOAc＝1∶1), m.p. 69－71 ℃;
1H NMR (400 MHz, CDCl3) δ: 8.02 (s, 1H), 7.77－7.84
(m, 3H), 7.57－7.63 (m, 3H), 7.41－7.48 (m, 2H), 7.33 (t,
J＝7.6 Hz, 2H), 7.22－7.26 (m, 1H), 4.63 (d, J＝25.2
Hz, 1H), 3.58 (d, J＝10.8 Hz, 3H), 3.55 (d, J＝10.8 Hz,
3H); 13C NMR (100 MHz, CDCl3) δ: 136.4 (d, J＝5.3
Hz), 134.0 (d, J＝5.4 Hz), 133.3 (d, J＝1.2 Hz), 132.4 (d,
J＝1.2 Hz), 129.4 (d, J＝8.0 Hz), 128.7 (d, J＝1.0 Hz),
128.3, 128.1 (d, J＝8.8 Hz), 128.0, 127.5, 127.4 (d, J＝
7.8 Hz), 127.3 (d, J＝2.0 Hz), 126.1, 126.0, 53.4 (d, J＝
7.1 Hz), 50.8 (d, J＝137.8 Hz); 31P NMR (162 MHz,
CDCl3) δ: 27.31; IR (film) v: 1250, 1056, 1030, 828, 730,
699 cm1; EI-MS (m/z, relative intensity): 326 (23), 277
(16), 236 (19), 217 (100), 202 (25); HRMS (ESI) calcd
for C19H20O3P [(M＋H)＋] 327.1145, found 327.1137.
Methyl 4-((dimethoxyphosphoryl)(phenyl)methyl)-
benzoate (3k) Colorless oil, yield 45% (30 mg), Rf＝
(31); HRMS (ESI) calcd for C16H20O3P [(M ＋H)＋]
291.1145, found 291.1153.
Dimethyl (di-p-tolylmethyl)phosphonate (4b)
Colorless oil, yield 89% (54 mg), Rf＝0.40 (petroleum
1
ether∶EtOAc＝1∶1); H NMR (400 MHz, CDCl3) δ:
7.39 (dd, J＝8.0, 1.6 Hz, 4H), 7.11 (d, J＝8.0 Hz, 4H),
4.39 (d, J＝24.8 Hz, 1H), 3.57 (d, J＝10.8 Hz, 6H), 2.30
(s, 6H); 13C NMR (100 MHz, CDCl3) δ: 136.8 (d, J＝2.3
Hz), 133.6 (d, J＝5.2 Hz), 129.3, 129.1 (d, J＝8.1 Hz),
53.3 (d, J＝6.9 Hz), 49.9 (d, J＝137.6 Hz), 21.0; 31P
NMR (162 MHz, CDCl3) δ: 27.87; IR (film) v: 1521,
1253, 1056, 1031, 864, 826, 750, 730 cm1; EI-MS (m/z,
relative intensity): 304 (22), 195 (100), 180 (34), 165
(44); HRMS (ESI) calcd for C17H22O3P [(M ＋H)＋]
305.1301, found 305.1297.
Dimethyl ((4-chlorophenyl)(p-tolyl)methyl)phos-
phonate (4c) Colorless oil, yield 77% (50 mg), Rf＝
0.40 (petroleum ether∶EtOAc＝1∶1); H NMR (400
1
MHz, CDCl3) δ: 7.44 (dd, J＝8.4, 2.0 Hz, 2H), 7.37 (dd,
J＝8.0, 2.0 Hz, 2H), 7.28 (d, J＝8.4 Hz, 2H), 7.13 (d,
J＝8.0 Hz, 2H), 4.39 (d, J＝25.2 Hz, 1H), 3.57 (t, J＝
10.4 Hz, 6H), 2.31 (s, 3H); 13C NMR (100 MHz, CDCl3)
δ: 137.2 (d, J＝2.1 Hz), 135.3 (d, J＝5.2 Hz), 133.1 (d,
J＝2.5 Hz), 132.9 (d, J＝5.3 Hz), 130.6 (d, J＝7.9 Hz),
129.5, 129.1 (d, J＝8.0 Hz), 128.8 (d, J＝1.1 Hz), 53.5
(d, J＝7.1 Hz), 53.3 (d, J＝7.2 Hz), 49.6 (d, J＝138.0
Hz), 21.0; 31P NMR (162 MHz, CDCl3) δ: 27.07; IR
(film) v: 1489, 1252, 1056, 1031, 827, 756, 730 cm1;
EI-MS (m/z, relative intensity): 324 (18), 215 (100), 180
(35), 165 (46), 109 (8); HRMS (ESI) calcd for C16H19-
ClO3P [(M＋H)＋] 325.0755, found 325.0759.
1
0.30 (petroleum ether∶EtOAc＝1∶1); H NMR (400
MHz, CDCl3) δ: 8.00 (d, J＝8.4 Hz, 2H), 7.61 (dd, J＝
8.4, 1.6 Hz, 2H), 7.50－7.52 (m, 2H), 7.34 (t, J＝7.6 Hz,
2H), 7.27－7.30 (m, 1H), 4.52 (d, J＝25.2 Hz, 1H), 3.89
(s, 3H), 3.58 (d, J＝10.8 Hz, 3H), 3.56 (d, J＝10.8 Hz,
3H); 13C NMR (100 MHz, CDCl3) δ: 166.7, 141.7 (d,
J＝5.2 Hz), 135.7 (d, J＝5.6 Hz), 129.9, 129.4 (d, J＝7.8
Hz), 129.3 (d, J＝7.8 Hz), 129.1 (d, J＝1.8 Hz), 128.8,
127.5 (d, J＝2.0 Hz), 53.6 (d, J＝6.8 Hz), 53.4 (d, J＝
7.2 Hz), 52.1, 50.8 (d, J＝137.7 Hz); 31P NMR (162
MHz, CDCl3) δ: 26.40; IR (film) v: 1722, 1282, 1253,
1109, 1056, 1030, 757, 733, 709 cm1; EI-MS (m/z, rel-
ative intensity): 334 (18), 225 (100), 207 (15), 165 (42);
HRMS (ESI) calcd for C17H20O5P [(M＋H)＋] 335.1043,
found 335.1054.
Dimethyl ((4-bromophenyl)(p-tolyl)methyl)phos-
phonate (4d) Colorless oil, yield 63% (46 mg), Rf＝
0.40 (petroleum ether∶EtOAc＝1∶1); H NMR (400
1
MHz, CDCl3) δ: 7.43 (d, J＝8.4 Hz, 2H), 7.35－7.40 (m,
4H), 7.13 (d, J＝8.0 Hz, 2H), 4.38 (d, J＝25.2 Hz, 1H),
3.57 (t, J＝10.8 Hz, 6H), 2.31 (s, 3H); 13C NMR (100
MHz, CDCl3) δ: 137.2 (d, J＝2.2 Hz), 135.9 (d, J＝5.1
Hz), 132.8 (d, J＝5.2 Hz), 131.7, 131.0 (d, J＝7.9 Hz),
129.5 (d, J＝1.0 Hz), 129.1 (d, J＝7.9 Hz), 121.3 (d, J＝
2.9 Hz), 53.5 (d, J＝6.9 Hz), 53.3 (d, J＝7.2 Hz), 49.7 (d,
J＝138.4 Hz), 21.0; 31P NMR (162 MHz, CDCl3) δ:
26.92; IR (film) v: 1486, 1251, 1054, 1032, 826, 754, 731
cm1; EI-MS (m/z, relative intensity): 368 (16), 259
(100), 180 (28), 165 (65); HRMS (ESI) calcd for
C16H19BrO3P [(M＋H)＋] 369.0250, found 369.0255.
Dimethyl (phenyl(p-tolyl)methyl)phosphonate (4a)
White solid, yield 93% (54 mg), Rf＝0.40 (petroleum
ether∶EtOAc＝1∶1); m.p. 63－65 ℃; H NMR (400
1
MHz, CDCl3) δ: 7.51 (d, J＝7.6 Hz, 2H), 7.41 (d, J＝6.8
Hz, 2H), 7.31 (t, J＝7.6 Hz, 2H), 7.21－7.25 (m, 1H),
7.13 (d, J＝7.6 Hz, 2H), 4.41 (d, J＝25.2 Hz, 1H), 3.56
(d, J＝10.8 Hz, 3H), 3.54 (d, J＝10.8 Hz, 3H), 2.30 (s,
3H); 13C NMR (100 MHz, CDCl3) δ: 136.8 (d, J＝2.2
Hz), 136.7 (d, J＝5.1 Hz), 133.5 (d, J＝5.2 Hz), 129.3 (d,
J＝1.1 Hz), 129.2 (d, J＝8.2 Hz), 129.1 (d, J＝8.1 Hz),
128.7 (d, J＝1.0 Hz), 127.1 (d, J＝2.1 Hz), 53.3 (d, J＝
7.2 Hz), 53.3 (d, J＝6.7 Hz), 50.4 (d, J＝137.4 Hz), 21.0;
31P NMR (162 MHz, CDCl3) δ: 27.65; IR (film) v: 1513,
1495, 1453, 1252, 1057, 1030, 824, 732, 699 cm1;
EI-MS (m/z, relative intensity): 290 (14), 181 (100), 165
Dimethyl
((4-methoxyphenyl)(p-tolyl)methyl)-
phosphonate (4e) Colorless oil, yield 84% (54 mg),
Rf＝0.30 (petroleum ether∶EtOAc＝1∶1); H NMR
1
(400 MHz, CDCl3) δ: 7.38－7.43 (m, 4H), 7.12 (d, J＝
8.0 Hz, 2H), 6.85 (d, J＝8.4 Hz, 2H), 4.37 (d, J＝25.6
Hz, 1H), 3.76 (s, 3H), 3.56 (d, J＝10.8 Hz, 6H), 2.30 (s,
3H); 13C NMR (100 MHz, CDCl3) δ: 158.6 (d, J＝2.1
Hz), 136.8 (d, J＝2.3 Hz), 133.8 (d, J＝4.8 Hz), 130.3 (d,
J＝8.0 Hz), 129.3 (d, J＝1.0 Hz), 129.1 (d, J＝8.0 Hz),
128.7 (d, J＝5.3 Hz), 114.0 (d, J＝1.1 Hz), 55.1, 53.3 (d,
J＝7.0 Hz), 53.3 (d, J＝7.2 Hz), 49.4 (d, J＝137.9 Hz),
21.0; 31P NMR (162 MHz, CDCl3) δ: 27.92; IR (film) v:
4
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© 2016 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Chin. J. Chem. 2016, XX, 1—7

Synthesis of Diarylmethylphosphonates
1511, 1252, 1181, 1057, 1030, 823, 754, 729 cm1;
EI-MS (m/z, relative intensity): 320 (9), 211 (100), 165
(5); HRMS (ESI) calcd for C17H22O4P [(M ＋H) ＋ ]
321.1250, found 321.1250.
cy (88% isolated yield), but it caused complicated prob-
lems for isolation of the product (Entry 8).[15]
Table 1 Optimization of reaction conditionsa
Methyl 4-((dimethoxyphosphoryl)(p-tolyl)methyl)
benzoate (4f) Colorless solid, yield 95% (66 mg), Rf
＝0.30 (petroleum ether∶EtOAc＝1∶1); m.p. 99－
1
102 ℃; H NMR (400 MHz, CDCl3) δ: 7.99 (d, J＝8.0
Hz, 2H), 7.59 (dd, J＝8.0, 1.6 Hz, 2H), 7.31 (dd, J＝8.0,
1.6 Hz, 2H), 7.14 (d, J＝8.0 Hz, 2H), 4.49 (d, J＝25.2
Hz, 1H), 3.89 (s, 3H), 3.57 (d, J＝10.8 Hz, 3H), 3.57 (d,
J＝10.8 Hz, 3H), 2.31 (s, 3H); 13C NMR (100 MHz,
CDCl3) δ: 166.7, 141.9 (d, J＝5.0 Hz), 137.2 (d, J＝2.2
Hz), 132.6 (d, J＝5.6 Hz), 129.8 (d, J＝0.9 Hz), 129.5 (d,
J＝1.0 Hz), 129.3 (d, J＝7.8 Hz), 129.1 (d, J＝8.0 Hz),
128.9 (d, J＝2.1 Hz), 53.5 (d, J＝7.1 Hz), 53.3 (d, J＝
7.2 Hz), 50.3 (d, J＝137.7 Hz), 20.9; 31P NMR (162
MHz, CDCl3) δ: 26.71; IR (film) v: 1722, 1609, 1436,
1281, 1253, 1189, 1112, 1031, 1022, 824, 745 cm1;
EI-MS (m/z, relative intensity): 348 (10), 239 (100), 180
(11), 165 (18); HRMS (ESI) calcd for C18H22O5P [(M＋
H)＋] 349.1199, found 349.1195.
Entry
Solvent
toluene
DMF
1,4-dioxane
DCE
MTBE
MTBE
MTBE
MTBE
Base (equiv) 1a∶2a Yieldb/%
1
2
3
4
5
6
7
8
KOtBu (2.0)
KOtBu (2.0)
KOtBu (2.0)
KOtBu (2.0)
KOtBu (2.0)
KOtBu (1.0)
1∶2
1∶2
1∶2
1∶2
1∶2
1∶1
trace
trace
trace
trace
90
85
93
88
KOtBu (1.1) 1∶1.1
K3PO4 (1.1) 1∶1.1
a If not otherwise noted, all the reactions were carried out with
0.20 mmol scale in the corresponding solvent (0.20 mol•L )
under N2 atmosphere for 12 h. b Isolated yield.
－
1
Dimethyl ((3-chlorophenyl)(p-tolyl)methyl)phos-
phonate (4g) Colorless oil, yield 86% (56 mg), Rf＝
1
With the optimized reaction conditions in hand, we
set out to explore the substrate scope of this protocol
(Scheme 2). A variety of readily accessible boronic ac-
ids were subjected to the standard conditions. Although
phenyl boronic acid afforded the coupling product in
excellent yield, the conversion of 1a is low when para-
chloro substrate was used. We postulated that the
transmetallation process was probably the turnover-
limiting step of this reaction, and electron-deficient bo-
ronic acids usually result in a slower transmetallation
compared to their electron-rich counterparts. To over-
come the problems associated with this key process, the
reaction was carried out at a higher temperature in some
cases. Gratifyingly, substrates with weak electron-
withdrawing groups (3b, 3e, 3f) and sterically hindered
substituents (3i) underwent the reaction smoothly, gen-
erating the corresponding diarylmethylphosphonate
scaffolds with satisfying results. However, switching the
substrate to 4-methoxycarbonylphenylboronic acid, the
yield decreased dramatically. The desired product was
only afforded in 45% isolated yield albeit 2 mol% rho-
dium catalyst and 2 equivalents of boronic acid were
employed (3k).
0.40 (petroleum ether∶EtOAc＝1∶1); H NMR (400
MHz, CDCl3) δ: 7.43－7.47 (m, 2H), 7.38 (dd, J＝8.0,
1.6 Hz, 2H), 7.20－7.27 (m, 2H), 7.14 (d, J＝8.4 Hz,
2H), 4.39 (d, J＝25.2 Hz, 1H), 3.60 (d, J＝10.8 Hz, 3H),
3.56 (d, J＝10.8 Hz, 3H), 2.31 (s, 3H); 13C NMR (100
MHz, CDCl3) δ: 138.7 (d, J＝5.0 Hz), 137.2 (d, J＝2.1
Hz), 134.3, 132.7 (d, J＝5.4 Hz), 129.8 (d, J＝1.2 Hz),
129.5, 129.3 (d, J＝8.4 Hz), 129.2 (d, J＝7.9 Hz), 127.5,
127.4, 53.6 (d, J＝6.9 Hz), 53.3 (d, J＝7.2 Hz), 50.0 (d,
J＝138.4 Hz), 21.0; 31P NMR (162 MHz, CDCl3) δ:
26.83; IR (film) v: 1252, 1056, 1031, 906, 830, 753, 729,
692 cm1; EI-MS (m/z, relative intensity): 324 (20), 215
(100), 180 (28), 165 (30); HRMS (ESI) calcd for
C16H19ClO3P [(M＋H)＋] 325.0755, found 325.0747.
Results and Discussion
We initiated our investigation by examining the
cross coupling reactions between diazo compound 1a
and boronic acid 2a under conditions similar to those
previously developed for the carboxylic acid ester ana-
logues (Table 1).[9e] When toluene was employed as the
solvent, only trace amount of coupling product was de-
tected by GC-MS analysis (Entry 1). Then several sol-
vents were screened (Entries 2－5). To our delight, alt-
hough most solvents tested were ineffective to promote
the reaction, methyl tert-butyl ether (MTBE) afforded
the desired diarylmethylphosphonate in excellent yield
(Entry 5). Further decreasing the substrate ratio to 1∶1
resulted in a slightly diminished yield (Entry 6), but 1.1
equivalents of boronic acid led to the full conversion of
diazo compound, giving the final product in 93% iso-
lated yield (Entry 7). Replacing the KOtBu with weak
base K3PO4 has little influence on the reaction efficien-
In efforts to extend the cross coupling procedure to
heteroaryl and alkenyl boronic acids, we found that only
trace amount of desired products were generated
(Scheme 3). The unsuccessful transformation may be
due to the deactivation of catalysts by the basic het-
eroatoms or carbon-carbon double bond. Alkyl boronic
acids, which are more reluctant to undergo the trans-
metallation and prone to undergo side reactions, were
also unsuitable for this protocol.
Subsequently, we turned our attention to the scope of
α-diazo phosphonate derivatives (Scheme 4). The diazo
Chin. J. Chem. 2016, XX, 1—7
© 2016 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.cjc.wiley-vch.de
5

Zhou et al.
FULL PAPER
Scheme 2 Substrate scope of boronic acidsa
Scheme 4 Substrate scope of α-diazo phosphonatesa
Me
Ph
N2
[Rh(COD)Cl]2
(1 mol%)
B(OH)2
OMe
OMe
OMe
OMe
X
N2
[Rh(COD)Cl]2
(1 mol%)
P
Ph
P
+
KOtBu
OMe
OMe
X
O
O
P
+
(1.1 equiv.)
B(OH)2
KOtBu
R
MTBE, 40 oC
OMe
P
O
3a 3k
1a
2b 2l
(1.1 equiv.)
OMe
O
R
MTBE, 40 oC
Me
1a 1g
2a
4a 4g
Ph
Ph
Ph
OMe
P
OMe
OMe
OMe
OMe
P
P
Ar = 4-MeC6H4
Ar
OMe
O
O
O
Ar
Ar
Cl
MeO
3b, 95%c
3c, 96%
3a, 92%b
Ph
OMe
OMe
OMe
OMe
P
P
P
OMe
O
OMe
O
O
Ph
Me
Ph
Cl
b
c
OMe
OMe
Br
OMe
OMe
MeO
OMe
4a
, 93%
4b
, 89%
4c
, 77%
P
P
P
OMe
O
O
O
Ar
Ar
Ph
OMe
OMe
OMe
3f, 79%c
3d, 68%c
P
3e
, 97%
P
OMe
O
O
MeO
Br
Ph
Ph
Me Ph
4e, 84%
Me
OMe
OMe
4d, 63%c
F3CO
P
P
OMe
OMe
OMe
P
O
O
Ar
OMe
Ar
O
OMe
OMe
Cl
OMe
Me
3h, 90%c
P
P
c
OMe
3i, 95%c
3g
, 88%
O
O
MeO2C
Ph
Ph
4g
, 86%
4f, 95%
OMe
OMe
OMe
OMe
P
P
O
O
a If not otherwise noted, all the reactions were carried out with 1
(0.20 mmol), 2a (0.22 mmol), [Rh(COD)Cl]2 (1 mol%), KOtBu
(0.22 mmol) in MTBE (1.0 mL) under N2 atmosphere at 40 ℃
for 12 h. b Isolated yield. c The reaction was carried out at 60 ℃.
MeO2C
3j, 97%c
3k, 45%c,d
a If not otherwise noted, all the reactions were carried out with 1a
(0.20 mmol), 2b－2k (0.22 mmol), [Rh(COD)Cl]2 (1 mol%),
KOtBu (0.22 mmol) in MTBE (1.0 mL) under N2 atmosphere at
b
c
40 ℃ for 12 h. Isolated yield. The reaction was carried out at
According to the previous study on Rh(I)-catalyzed
cross-coupling reaction with Rh(I) carbene intermedi-
ate,[8] we propose the following reaction mechanism
(Scheme 5). Firstly, aryl rhodium species A is generated
through transmetallation. The aryl rhodium species then
reacts with α-diazo phosphonate to afford the Rh(I)
carbene intermediate B, which is followed by migratory
insertion to generate intermediate C. Finally, protona-
tion of intermediate C delivers the coupling product and
regenerates Rh(I) catalyst.
60 ℃. [Rh(COD)Cl]2 (2 mol%), 2l (0.40 mmol), KOtBu (0.40
d
mmol) were used.
Scheme 3 Scope limitation of boronic acids
unsuccessful substrates:
AcHN
Cl
Cl
NC
B(OH)2
B(OH)2
B(OH)2
B(OH)2
2n
2m
2o
Scheme 5 Proposed reaction mechanism
B(OH)2
2q
B(OH)2
S
2r
2p
compounds bearing both electron-donating and elec-
tron-withdrawing substituents are efficient coupling
partners in this reaction, furnishing the desired products
in good to excellent yields. As mentioned before, bo-
ronic acids with electron-withdrawing groups show un-
desirable reactivity in this transformation. If we need to
synthesize a diarylmethylphosphonate with one elec-
tron-deficient aryl ring and one electron-rich aryl ring,
we can improve the efficiency by reasonably choosing
the starting substrates. Additionally, halogen atoms and
ester functionality were well tolerated under current
catalytic system.
6
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© 2016 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Chin. J. Chem. 2016, XX, 1—7

Synthesis of Diarylmethylphosphonates
dron 2003, 59, 4673; (b) Rajeshwaran, G. G.; Nandakumar, M.;
Sureshbabu, R.; Mohanakrishnan, A. K. Org. Lett. 2011, 13, 1270.
[5] Pallikonda, G.; Chakravarty, M. Eur. J. Org. Chem. 2013, 944.
[6] Montel, S.; Raffier, L.; He, Y.; Walsh, P. J. Org. Lett. 2014, 16, 1446.
[7] For selected publications, see: (a) Polozov, A. M.; Polezhaeva, N. A.;
Mustaphin, A. H.; Khotinen, A. V.; Arbuzov, B. A. Synthesis 1990,
515; (b) Miao, W.; Gao, Y.; Li, X.; Gao, Y.; Tang, G.; Zhao, Y. Adv.
Synth. Catal. 2012, 354, 2659; (c) Chen, Z.-S.; Zhou, Z.-Z.; Hua,
H.-L.; Duan, X.-H.; Luo, J.-Y.; Wang, J.; Zhou, P.-X.; Liang, Y.-M.
Tetrahedron 2013, 69, 1065.
[8] For selected reviews, see: (a) Yan, G.; Kuang, C.; Peng, C.; Wang, J.
Chin. J. Org. Chem. 2009, 29, 813; (b) Zhang, Y.; Wang, J. Eur. J.
Org. Chem. 2011, 1015; (c) Barluenga, J.; Valdés, C. Angew. Chem.,
Int. Ed. 2011, 50, 7486; (d) Shao, Z.; Zhang, H. Chem. Soc. Rev.
2012, 41, 560; (e) Xiao, Q.; Zhang, Y.; Wang, J. Acc. Chem. Res.
2013, 46, 236; (f) Xia, Y.; Zhang, Y.; Wang, J. ACS Catal. 2013, 3,
2586; (g) Liu, Z.; Wang, J. J. Org. Chem. 2013, 78, 10024; (h) Hu,
F.; Xia, Y.; Ma, C.; Zhang, Y.; Wang, J. Chem. Commun. 2015, 7986.
[9] For selected publications, see: (a) Peng, C.; Wang, Y.; Wang, J. J.
Am. Chem. Soc. 2008, 130, 1566; (b) Tsoi, Y.-T.; Zhou, Z.; Chan, A.
S. C.; Yu, W.-Y. Org. Lett. 2010, 12, 4506; (c) Zhao, X.; Jing, J.; Lu,
K.; Zhang, Y.; Wang, J. Chem. Commun. 2010, 46, 1724; (d) Tsoi,
Y.-T.; Zhou, Z.; Yu, W.-Y. Org. Lett. 2011, 13, 5370; (e) Ghorai, J.;
Anbarasan, P. J. Org. Chem. 2015, 80, 3455.
Conclusions
In conclusion, we have reported an efficient rhodium
catalyzed cross coupling reactions of α-diazo phospho-
nates[16] and boronic acids. Generally, a class of diaryl-
methylphosphonates with diverse functionality can be
readily accessed under the mild reaction conditions.
Further efforts concerning the expansion of organobo-
ron reagent scope and the development of asymmetric
version of this coupling reaction are underway in our
group.
Acknowledgement
The project is supported by the National Basic Re-
search Program of China (973 Program, No.
2015CB856600) and the National Natural Science
Foundation of China (Grant 21472004, 21332002).
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