Supporting information

for

Rhodium-catalyzed Triarylphosphine Synthesis via Cross-coupling of

Aryl Iodides and Acylphosphines

Jiefang Yang, Hongyu Wu and Zhiqian Wang*

State Key Laboratory of Chemical Resource Engineering, College of Science, Beijing University

of Chemical Technology, Beijing 100029, China

*Corresponding author’s e-mail: wangzhq@mail.buct.edu.cn

Table of Contents:
General Information..................................................................................................S2

Experimental Procedures and Compound Characterizations…………...………S2

NMR Spectra..............................................................................................................S2
General Information

Unless otherwise noted, all commercial materials were purchased from Energy Chemical and used

without further purification. Tetrahydrofuran (THF), toluene and 1,4-dioxane were freshly distilled over Na, N-

dimethylformamide (DMF) were driedby filtration through two columns of activated molecular

sieves.Reaction temperatures are reported as the temperatures of the bath surrounding the vessel. Sensitive

reagents and solvents were transferred under nitrogen in a glove-box using standard techniques. Proton nuclear

magnetic resonance (1H NMR) and carbon nuclear magnetic resonance ( 13C NMR) spectra were acquired in

CDCl3 unless otherwise noted. Chemical shifts are reported in parts per million (ppm, δ), downfield from

tetramethylsilane (TMS, δ = 0.00 ppm) and are referenced to residual solvent (CDCl 3, δ = 7.26 ppm (1H) and

77.16 ppm (13C)).Coupling constants (J) are reported in hertz (Hz) and the resonance multiplicity

abbreviations used are: s, singlet; d, doublet; t, triplet; q, quartet; dt, doublet of triplets; td, triplet of doublets;

dd, doublet of doublets; ddd, doublet of doublet of doublets; m, multiplet. Infrared (IR) spectra were obtained

with a FT-IR series spectrometer as thin films on sodium bromide plates. Thin-layer chromatography (TLC)

was performed on GF254 silica gel coated plates and were visualized using one or more of the following

methods: UV light (254 nm) and staining with basic potassium permanganate (KMnO 4). Flash chromatography

was performed using glass columns and carried out on SiO2(silica gel 200-300 mesh).
Experimental Procedures and Compound Characterizations

General procedure A for preparation of acylphosphine 2 in Table 2 :1,2

O O
Et3N, THF
Ar Cl HPPh2 Ar PPh2
0Cr.t.

A: At 0℃, under nitrogen, triethylamine (CAS : 121-44-8) (0.64 g, 6.3 mmol) was added into a solution of

diphenylphosphine (CAS : 829-85-6) 2 (0.98 g, 5.25 mmol) in 10 mL Et 2O, followed by dropwise addition of

benzoyl chloride 1 (1 g, 5.25 mmol). The mixture was stirred at 0℃for 20 min, then allowed to warm up to

room temperature and stirred for another 6 h. The mixture was quenched with H 2O (10 mL) and the mixture

was extracted with CH2Cl2 (2×50 mL). The combined organic phasewas washed with brine (20 mL), dried over

Na2SO4, and evaporated to give the crude product as a yellow oil. The crude product was recrystallized with

MeOH to afford pure product.

O Diphenyl benzoylphosphine. According to the general procedure A, reaction with

PPh2
diphenylphosphine (0.98 g, 5.25 mmol), triethylamine (0.64 g, 6.3 mmol) and benzoyl

chloride (0.77 g, 5.5 mmol) afforded 1.17 g of product in a yield of 77% as a yellow solid. 1H

31
NMR (400 MHz, CDCl3)δ:7.98-7.96 (m, 1 H), 7.47-7.32 (m, 13H); P (162 MHz, CDCl3)δ:13.50; HRMS

(ESI-QTOF) m/z: ([M+H]+) Calcd for C19H15OP : 291.0933 Found 291.0933; IR(film): 1643, 1433, 1201,

1180, 1141,1075, 740, 692 cm-1.

O .

PPh2 Diphenyl 1-naphthoyl phosphine. According to the general procedure A, reaction with
diphenylphosphine (0.98 g, 5.25 mmol), triethylamine (0.64 g, 6.3mmol) and 1-Naphthoyl chloride (CAS :

879-18-5)(1.05 g, 5.5 mmol) afforded 1.48 g of product in a yield of 83% as a yellow solid. 1H NMR (400

MHz, CDCl3)δ: 8.59(d, J=8.0 Hz, 1 H), 8.35-8.32 (m, 1 H), 7.87(d, J=8.0 Hz, 1 H), 7.79(d, J=8.0 Hz, 1 H),

31
7.56-7.37(m, 8 H), 7.31-7.29(m, 5 H); P (162 MHz, CDCl3)δ: 22.44, 18.24; HRMS (ESI-QTOF) m/z:

([M+H]+) Calcd for C23H17OP : 341.1090 Found 341.1084.

O Diphenyl 2-naphthoyl phosphine. According to the general procedure A, reaction

Ph
P
with diphenylphosphine (0.98 g, 5.25 mmol) , triethylamine (0.64 g, 6.31mmol) and 2-
Ph

Naphthoyl chloride (CAS : 2243-83-6)(1.00 g, 5.25 mmol) afforded 1.013 g of product L3 in a yield of 57%as

a yellow solid. m. p. 134-136 oC; 1H NMR (400 MHz, CDCl3) δ: 8.61 (s, 1 H), 7.98 (d,J=8.0 Hz,1 H), 7.87

(d,J=8.0 Hz,1 H),7.80-7.78 (m, 2 H), 7.57-7.43 (m, 6 H), 7.35 (m, 6 H); 13C NMR (100 MHz, CDCl3) : 212.8,

212.4, 135.0, 134.8, 130.8, 130.7, 129.8, 129.5, 128.8, 128.7, 128.5, 128.5, 127.8, 126.7, 125.4, 123.6; 31P (162

MHz, CDCl3) 12.83; HRMS (ESI-QTOF) m/z: ([M+H]+) Calcd for C23H17OP : 341.1090 Found 341.1084.

O Diphenyl p-methylbenzoylphosphine. According to the general procedure A, reaction

PPh2
with diphenylphosphine (0.98 g, 5.25 mmol), triethylamine (0.64 g, 6.3mmol) and 4-
Me

methylbenzoyl chloride(CAS : 874-60-2)(0.85 g, 5.5 mmol) afforded 1.24 g of product

in a yield of 78% as a yellow solid. 1H NMR (400 MHz, CDCl3) δ : 7.90-7.87(m, 2 H), 7.42-7.40(m, 5 H),

7.38-7.34(m, 5 H), 7.14(d, J=8.0 Hz, 2 H), 2.33(s, 3 H); 31P (162 MHz, CDCl3) δ : 22.61, 12.64; HRMS (ESI-

QTOF) m/z: ([M+H]+) Calcd for C20H18OP:305.1090 Found 305.1088.

O Diphenyl p-chlorobenzoylphosphine. According to the general procedure A, reaction

PPh2

Cl
with diphenylphosphine (0.98 g, 5.25 mmol), triethylamine (0.64 g, 6.3mmol) and 4-chlorobenzoyl chloride

(CAS : 122-01-0)(0.96 g, 5.5 mmol) afforded 1.03 g of product in a yield of 67% as a yellow solid. 1H NMR

(400 MHz, CDCl3)δ: 8.09-8.06(m, 1 H), 7.91-7.83(m, 2 H), 7.58-7.56(m, 1 H), 7.52-7.50(m, 2 H), 7.46-

31
7.35(m, 7 H), 7.31(d, J=8.0 Hz, 1 H); P (162 MHz, CDCl3) δ : 22.81, 13.64; HRMS (ESI-QTOF) m/z:

([M+H]+) Calcd for C19H15ClOP : 325.0544 Found 325.0541.

O Diphenyl p-methoxylbenzoylphosphine. According to the general procedure A,

PPh2
reaction with diphenylphosphine (0.98 g, 5.25 mmol), triethylamine (0.98 g, 5.25
MeO

mmol) and 4-methoxylbenzoyl chloride (CAS : 100-07-2)(0.93 g, 5.5 mmol) afforded

1.0 g of product in a yield of 60% as a yellow solid. 1H NMR (400 MHz, CDCl 3) δ: 8.00-7.97(m, 2 H), 7.43-

7.33 (m, 10 H), 6.83 (d, J = 8.0 Hz,2 H), 3.81 (s, 3 H); 31P (162 MHz, CDCl3)δ: 11.36; HRMS (ESI-QTOF)

m/z: ([M+H]+) Calcd for C20H18O2P : 321.1044 Found 321.1041.

Di-p-tolyl p-methoxybenzoyl Phosphine was prepared by follow method:1,2

O O
H
Cl P Et3N, THF P
O 0Cr.t. O

At0℃, triethylamine(0.38mL, 2.8 mmol)was added intoa solution of di-p-methylphenylphosphine(0.5

g, 2.3 mmol, 10 wt% in n-hexane) in 5 mL THF, followed by dropwise addition of aryl chloride (0.33mL, 2.45
mmol). The mixture was stirred at 0℃for 20 min, then allowed to warm up to room temperature and stirred

for overnight. The mixture was quenched with H2O (10 mL) and the mixture was extracted with CH2Cl2 (2×50

mL). The combined organic phasewas washed with brine (20 mL), dried over Na 2SO4, and evaporated to give

the crude product as a yellow oil.The crude product was used as such in the next step.

General procedure B for preparation of 3a-3y in Table 3:

P I 2.5 mol%[RhCl(coe)2]2 R
O P
R Dioxane,CsOpiv,
130C,12h

In a sealed vial, under nitrogen, diphenyl p-methoxylbenzoylphosphine (96 mg, 0.30 mmol, 1.5 equiv),

[RhCl(coe)2]2(3.6 mg, 5 mol % of Rh), iodobenzene (0.2 mmol), CsOPiv ( 93mg, 0.4 mmol) and dioxane (0.4

mL) were mixed and stirred at 130 oC for 12 h. After the reation completed, 2 mL H 2O was added, the mixture

was extracted with ethyl acetate (3×5mL). The combined organic phasewas washed with brine and dried over

Na2SO4. After removal of the solvent under reduced pressure, the organic phase was concentrated, and the

residue was purified by flash chromatography through silica-gel eluted with petroleum ether to give the desired

product.

triphenylphosphine (3a). According to the general procedure B, reaction with diphenyl p-

PPh2

methoxylbenzoylphosphine(96 mg, 0.30 mmol, 1.5 equiv), [RhCl(coe)2]2 (3.6 mg, 5 mol % of

Rh), iodobenzene (CAS : 591-50-4)(0.2 mmol), CsOPiv (93mg, 0.4 mmol) and dioxane (0.4
mL) afforded 45mg of product 3a in a yield of 86%as white solid; 1H NMR (400 MHz, CDCl3)  : 7.34-7.25

(m, 15 H). 31P NMR (162 MHz, CDCl3)  : -5.36. MS (ESI) m/z : ([M+H]+) Calcd for C18H16P : 263, Found

263. IR (film) : 3067, 1474, 1431, 1087, 741, 694, 510,494 cm-1.

(4-fluorophenyl)diphenylphosphine (3b). According to the general procedure B, reaction with diphenyl p-

PPh2

methoxylbenzoylphosphine(96 mg, 0.30 mmol), [RhCl(coe)2]2 (3.6 mg, 5 mol % of Rh),

F

4- fluoroiodobenzene (CAS : 352-34-1) (0.2 mmol), CsOPiv (93mg, 0.4 mmol) and

dioxane (0.4 mL) afforded 31mg of product 3b in a yield of 55%aswhite solid; 1H NMR (400 MHz, CDCl3)  :

7.35-7.25 (m, 12 H), 7.06-7.01 (m, 2 H). 31P NMR (162 MHz, CDCl3)  : -6.67. 19F NMR (376 MHz, CDCl3) 

: -112.43. MS (ESI) m/z : ([M+H]+) Calcd for C18H15FP : 281.09, Found 281.27.

(4-chlorophenyl)diphenylphosphine (3c). According to the general procedure B,

PPh2

reaction with diphenyl p-methoxylbenzoylphosphine(96 mg, 0.30 mmol),

Cl

[RhCl(coe)2]2 (3.6 mg, 5 mol % of Rh), 1-chloro-4-iodobenzene (CAS : 637-87-6)(0.2

mmol), CsOPiv (93mg, 0.4 mmol) and dioxane (0.4 mL) afforded 53mg of product 3c in a yield of

95%aswhite solid; 1H NMR (400 MHz, CDCl3) : 7.46 (m, J = 8.0 Hz,2 H), 7.35-7.28 (m,10 H), 7.17-7.13 (m,

2 H). 31P NMR (162 MHz, CDCl3): -6.14.MS (ESI) m/z : ([M+H]+) Calcd for C18H15ClP : 297, Found 297.

diphenyl(4-(trifluoromethyl)phenyl)phosphine (3d).According to the general

PPh2

procedure B, reaction with diphenyl p-methoxylbenzoylphosphine(96 mg, 0.30 mmol),

F3C

[RhCl(coe)2]2 (3.6 mg, 5 mol % of Rh), 1-trifluoromethyl-4-iodobenzene (CAS : 455-

13-0)(0.2 mmol), CsOPiv (93mg, 0.4 mmol) and dioxane (0.4 mL) afforded 44mg of product 3d in a yield of

66%as colorless oil; 1H NMR (400 MHz, CDCl3) : 7.56 (d, J = 8.0 Hz, 2 H), 7.39-7.29 (m, 12 H). 31P NMR

(162 MHz, CDCl3) : -5.35. 19

F NMR (376 MHz, CDCl3) : -62.75. MS (ESI) m/z: ([M+H]+) Calcd for

C19H15F3P: 331, Found 331.

PPh2 (4-methoxyphenyl)diphenylphosphine (3e). According to the general procedure B,

MeO reaction with diphenyl p-methoxylbenzoylphosphine(96 mg, 0.30 mmol), [RhCl(coe)2]2

(3.6 mg, 5 mol % of Rh), 1-iodo-4-methoxybenzene (CAS : 696-62-8)(0.2 mmol),

CsOPiv (93mg, 0.4 mmol) and dioxane (0.4 mL) afforded 59mgof product3e in a yield of 98% aswhite solid;

1
H NMR (400 MHz, CDCl3) : 7.33-7.26 (m, 12 H), 6.89 (d, J = 8.0 Hz, 2 H), 3.81 (s, 3 H). 31P NMR (162

MHz, CDCl3) : -6.99.MS (ESI) m/z : ([M+H]+) Calcd for C19H18OP : 293, Found 293.

diphenyl(p-tolyl)phosphine (3f). According to the general procedure B, reaction with

PPh2

diphenyl p-methoxylbenzoylphosphine(96 mg, 0.30 mmol), [RhCl(coe)2]2 (3.6 mg, 5

Me

mol % of Rh), 1-iodo-4-methylbenzene (CAS : 624-31-7)(0.2 mmol), CsOPiv (93mg,

0.4 mmol) and dioxane (0.4 mL) afforded 50mg of product 3f in a yield of 97%as white solid; 1H NMR (400

MHz, CDCl3) : 7.34-7.14 (m, 14 H), 2.35 (s, 3 H). 31P NMR (162 MHz, CDCl3) : -6.22.MS (ESI) m/z :

([M+H]+) Calcd for C19H18P : 277, Found 277.

[1,1'-biphenyl]-4-yldiphenylphosphine (3g). According to the general procedure B, reaction with diphenyl p-

PPh2

Ph
methoxylbenzoylphosphine(96 mg, 0.30 mmol), [RhCl(coe)2]2 (3.6 mg, 5 mol % of Rh), 4-phenyliodobenzene

(CAS : 1591-31-7)(0.2 mmol), CsOPiv (93mg, 0.4 mmol) and dioxane (0.4 mL) afforded 48mg of product 3g

in a yield of 70%as white solid; 1H NMR ( 400 MHz, CDCl 3) : 7.58 (t, J = 8.0 Hz, 4 H), 7.50-7.32 (m, 15 H).

31
P NMR (162 MHz, CDCl3) : -6.05.MS (ESI) m/z : ([M+H]+) Calcd for C24H20P : 339.13, Found 339.44. IR

(film) : 3052, 1479, 1433, 832, 761, 743, 695, 502 cm-1.

naphthalen-1-yldiphenylphosphine (3h). According to the general procedure B, reaction

PPh2

with diphenyl p-methoxylbenzoylphosphine(96 mg, 0.30 mmol), [RhCl(coe)2]2 (3.6 mg, 5

mol % of Rh), 1-iodonaphthalene (CAS : 90-14-2)(0.2 mmol), CsOPiv (93mg, 0.4 mmol)

and dioxane (0.4 mL) afforded 61mg of product 3h in a yield of 98%as white solid; 1H NMR ( 400 MHz,

CDCl3) : 8.41(dd, J = 8.0, 4.0 Hz, 1 H), 7.85 (t, J = 8.0 Hz, 2 H), 7.50-7.42 (m, 2 H), 7.37-7.28 (m, 11 H),

7.02-6.98 (m, 1 H). 31P NMR (162 MHz, CDCl3) : -14.18.MS (ESI) m/z : ([M+H]+) Calcd for C22H18P : 313,

Found 313.

Me PPh2
diphenyl(m-tolyl)phosphine (3i). According to the general procedure B, reaction with

diphenyl p-methoxylbenzoylphosphine(96 mg, 0.30 mmol), [RhCl(coe)2]2 (3.6 mg, 5 mol

% of Rh), 1-iodo-3-methylbenzene (CAS : 625-95-6)(0.2 mmol), CsOPiv (93mg, 0.4 mmol) and dioxane (0.4

mL) afforded 37mg of product 3i in a yield of 67% as white solid; 1H NMR ( 400 MHz, CDCl3) : 7.32-7.30

(m, 10 H), 7.25-7.14 (m, 3 H), 7.07 (t,J = 8.0 Hz, 1 H), 2.30 (s, 3 H). 31P NMR (162 MHz, CDCl3) : -5.33.MS

(ESI) m/z : ([M+H]+) Calcd for C19H18P : 277.11, Found 277.35.

 PPh2 diphenyl(o-tolyl)phosphine (3j). According to the general procedure B, reaction with

Me
diphenyl p-methoxylbenzoylphosphine(96 mg, 0.30 mmol), [RhCl(coe)2]2 (3.6 mg, 5 mol % of

Rh), 1-iodo-2-methylbenzene (CAS : 615-37-2)(0.2 mmol), CsOPiv (93mg, 0.4 mmol) and dioxane (0.4 mL)

afforded 24mg of product 3j in a yield of 44%as white solid; 1H NMR ( 400 MHz, CDCl3) : 7.35-7.19 (m, 12

H), 7.08 (t, J = 8.0 Hz, 1 H), 6.78-6.75 (m,1 H), 2.39 (s, 3 H). 31P NMR (162 MHz, CDCl3) : -13.30.MS (ESI)

m/z : ([M+H]+) Calcd for C19H18P : 277.11, Found 277.35.

(3-chlorophenyl)diphenylphosphine (3k). According to the general procedure B, reaction with diphenyl p-

Cl PPh2

methoxylbenzoylphosphine(96 mg, 0.30 mmol), [RhCl(coe)2]2 (3.6 mg, 5 mol % of Rh),

1-chloro-3-iodobenzene (CAS : 625-99-0)(0.2 mmol), CsOPiv (93mg, 0.4 mmol) and

dioxane (0.4 mL) afforded 55mg of product 3k in a yield of 93%as colorless oil; 1H NMR ( 400 MHz, CDCl 3)

: 7.36-7.23 (m, 13 H), 7.19-7.15 (m,1 H). 31P NMR (162 MHz, CDCl3) : -4.95.MS (ESI) m/z : ([M+H]+)

Calcd for C18H15ClP : 297.06, Found 297.32.

PPh2 (2-chlorophenyl)diphenylphosphine (3l). According to the general procedure B, reaction

Cl with diphenyl p-methoxylbenzoylphosphine(96 mg, 0.30 mmol), [RhCl(coe)2]2 (3.6 mg, 5 mol

% of Rh), 1-chloro-2-iodobenzene (CAS : 615-41-8)(0.2 mmol), CsOPiv (93mg, 0.4 mmol) and dioxane (0.4

mL) afforded 45mg of product 3l in a yield of 75%as white solid; 1H NMR ( 400 MHz, CDCl3) : 7.41-7.25

(m, 12 H), 7.17-7.13 (m,1 H), 6.77-6.73 (m, 1 H). 31

P NMR (162 MHz, CDCl3) : -10.94.MS (ESI) m/z :

([M+H]+) Calcd for C18H15ClP : 297.06, Found 297.25.

 (1,1'-biphenyl)-2-yldiphenylphosphine (3m). According to the general procedure B, reaction
PPh2

with diphenyl p-methoxylbenzoylphosphine(96 mg, 0.30 mmol), [RhCl(coe)2]2(3.6 mg, 5 mol

Ph

% of Rh), 2-phenyliodobenzene (CAS : 2113-51-1)(0.2 mmol), CsOPiv (93mg, 0.4 mmol) and

dioxane (0.4 mL) afforded 63 mg of product 3m in a yield of 93%as white solid; 1H NMR ( 400 MHz, CDCl3)

: 7.45-7.21 (m, 18 H), 7.11-7.08 (m,1 H). 31P NMR (162 MHz, CDCl3) : -13.43.MS (ESI) m/z : ([M+H] +)

Calcd for C24H20P : 339.13 Found 339.44. IR (film) : 3051, 1582, 1461, 1433, 1088, 746, 698, 496 cm-1.

(4-bromophenyl)diphenylphosphine (3n). According to the general procedure B,

PPh2

reaction with diphenyl p-methoxylbenzoylphosphine(96 mg, 0.30 mmol), [RhCl(coe)2]2

Br

(3.6 mg, 5 mol % of Rh), 1-bromo-4-iodobenzene (CAS : 591-18-4)(0.2 mmol), CsOPiv

(93mg, 0.4 mmol) and dioxane (0.4 mL) afforded 43mg of product 3n in a yield of 67%as white solid; 1H

NMR ( 400 MHz, CDCl3) : 7. 45 (d, J = 8.0 Hz, 2 H), 7.35-7.25 (m,10 H), 7.15 (t, J = 8.0 Hz, 2 H). 31P NMR

(162 MHz, CDCl3) : -6.41.MS (ESI) m/z : ([M+H]+) Calcd for C18H15BrP : 341.01, Found 341.31.

4-(diphenylphosphino)benzonitrile (3o). According to the general procedure B, reaction with diphenyl p-

PPh2

methoxylbenzoylphosphine(96 mg, 0.30 mmol), [RhCl(coe)2]2 (3.6 mg, 5 mol % of Rh),

NC

4-iodobenzonitrile (CAS : 3058-39-7)(0.2 mmol), CsOPiv (93mg, 0.4 mmol) and

dioxane (0.4 mL) afforded 58mg of product 3o in a yield of 98%as white solid; 1H NMR ( 400 MHz, CDCl 3)

: 7.57 (d,J = 8 Hz,2 H), 7.39-7.31 (m,12 H). 31P NMR (162 MHz, CDCl3) : -4.27.MS (ESI) m/z : ([M+H] +)

Calcd for C19H15NP : 288.09, Found 288.33. IR (film) : 3048, 2221, 1488, 1433, 822, 693, 745, 549cm-1.
 PPh2 1-(4-(diphenylphosphino)phenyl)ethanone (3p). According to the

Me generalprocedure B, reaction with diphenyl p-methoxylbenzoylphosphine(96 mg,

O
0.30 mmol), [RhCl(coe)2]2 (3.6 mg, 5 mol % of Rh), 1-(4-iodophenyl)ethanone (CAS

: 39730-66-0)(0.2 mmol), CsOPiv (93mg, 0.4 mmol) and dioxane (0.4 mL) afforded 35mg of product 3p in a

yield of 57%as white solid; 1H NMR ( 400 MHz, CDCl 3) : 7.88 (d,J = 8.0, 2 H), 7.37-7.26 (m,12 H), 2.58 (s,

3 H). 31P NMR (162 MHz, CDCl 3) : -5.04.MS (ESI) m/z : ([M+H] +) Calcd for C20H18OP : 305.11, Found

305.30.

PPh2 methyl 4-(diphenylphosphino)benzoate (3q). According to the general procedure

MeO
B, reaction with diphenyl p-methoxylbenzoylphosphine(96 mg, 0.30 mmol),
O
[RhCl(coe)2]2 (3.6 mg, 5 mol % of Rh), 4-iodo-benzoic acid methyl ester (CAS :

619-44-3)(0.2 mmol), CsOPiv (93mg, 0.4 mmol) and dioxane (0.4 mL) afforded 62mg of product 3q in a yield

of 96% as white solid; 1H NMR ( 400 MHz, CDCl3) : 7.96 (d,J = 8.0, 2 H), 7.37-7.25 (m,12 H), 3,90 (s, 3 H).

31
P NMR (162 MHz, CDCl3) : -5.02.MS (ESI) m/z : ([M+H]+) Calcd for C20H18O2P : 321.10, Found 321.34.

PPh2
ethyl 4-(diphenylphosphino)benzoate (3r). According to the general
EtO
procedure B, reaction with diphenyl p-methoxylbenzoylphosphine(96 mg,
O

0.30 mmol), [RhCl(coe)2]2 (3.6 mg, 5 mol % of Rh), 4-iodo-benzoic acid

ethyl ester (CAS : 51934-41-9)(0.2 mmol), CsOPiv (93mg, 0.4 mmol) and dioxane (0.4 mL) afforded
 40mg of product 3r in a yield of 60% aswhite solid; 1H NMR ( 400 MHz, CDCl3) : 7.975 (dd,J = 4.0, 4.0

Hz ,2 H), 7.37-7.31 (m,12 H), 4.37 (q, 2 H), 1.37 (t, 3 H). 31P NMR (162 MHz, CDCl3) : -5.06.MS (ESI)

m/z : ([M+H]+) Calcd for C21H20O2P : 335.12, Found 335.44. IR (film) : 3052, 2980, 1717, 1593, 1276,

1109, 745, 696 cm-1.

3-(diphenylphosphino)pyridine (3s). According to the general procedure B, reaction with

PPh2

diphenyl p-methoxylbenzoylphosphine(96 mg, 0.30 mmol), [RhCl(coe)2]2 (3.6 mg, 5 mol % of

N
Rh), 3-iodopyridine (CAS : 1120-90-7)(0.2 mmol), CsOPiv (93mg, 0.4 mmol,) and dioxane

(0.4 mL) afforded 41mg of product 3s in a yield of 78%as white solid; 1H NMR ( 400 MHz, CDCl3) : 8.56

(d,J = 4.0 Hz, 1 H), 8.52 (s,1 H), 7.56-7.54 (m, 1 H), 7.37-7.33 (m, 9 H), 7.31-7.24 (m, 2 H). 31P NMR (162

MHz, CDCl3) : -11.80.MS (ESI) m/z : ([M+H]+) Calcd for C17H15NP : 264.09, Found 264.29.

4-(diphenylphosphino)pyridine (3t). According to the general procedure B, reaction with diphenyl p-

PPh2

N methoxylbenzoylphosphine(96 mg, 0.30 mmol), [RhCl(coe)2]2 (3.6 mg, 5 mol % of Rh), 4-

iodopyridine (CAS : 15854-87-2)(0.2 mmol), CsOPiv (93mg, 0.4 mmol) and dioxane (0.4

mL) afforded 48mg of product 3t in a yield of 91%as white solid; 1H NMR ( 400 MHz, CDCl 3) : 8.51(t, J =

4.0 Hz, 2 H), 7.41-7.33 (m,10 H), 7.12-7.09 (m, 2 H). 31P NMR (162 MHz, CDCl 3) : -6.95.MS (ESI) m/z:

([M+H]+) Calcd for C17H15NP : 264.09, Found 264.34. IR (film) : 3051, 1571, 1475, 1405, 806, 745, 697, 522

cm-1.

diphenyl(thiophen-2-yl)phosphine (3u). According to the general procedure B, reaction with diphenyl p-

PPh2

S
methoxylbenzoylphosphine(96 mg, 0.30 mmol), [RhCl(coe)2]2 (3.6 mg, 5 mol % of Rh), 2-

iodothiophene(CAS : 3437-95-4)(0.2 mmol), CsOPiv (93mg, 0.4 mmol) and dioxane (0.4 mL) afforded 43mg

of product 3u in a yield of 80%as white solid; 1H NMR ( 400 MHz, CDCl 3) : 7.575 (d, J = 4.0 Hz,1 H), 7.40-

7.29 (m,11 H), 7.12 (m, 1 H). 31P NMR (162 MHz, CDCl3) : -19.91.MS (ESI) m/z : ([M+H]+) Calcd for

C16H14PS : 269.06, Found 269.29.

6-(diphenylphosphino)quinoline (3v). According to the general procedure B, reaction with diphenyl p-

PPh2

methoxylbenzoylphosphine(96 mg, 0.30 mmol), [RhCl(coe)2]2 (3.6 mg, 5 mol % of Rh),

N

6-iodoquinoline(CAS : 13327-31-6)(0.2 mmol), CsOPiv (93mg, 0.4 mmol) and dioxane

(0.4 mL) afforded 52mg of product 3v in a yield of 83%as white solid; 1H NMR ( 400 MHz, CDCl3) : 8.91 (d,

J = 4.0 Hz,1 H), 8.07-8.04 (m,2 H), 7.74 (dd, J = 4.0, 4.0 Hz, 1 H), 7.625 (dd, J = 4.0, 4.0, Hz,1 H), 7.40-7.34

(m, 11 H). 31P NMR (162 MHz, CDCl3) : -5.09.13C NMR (100 MHz, CDCl3)  :151.08, 148.34, 136.61 (d, J =

11.0 Hz), 136.30 (d, J = 13.0 Hz), 136.10, 133.98, 133.79, 133.74, 133.58 (d, J = 1.0 Hz), 129.45 (d, J = 7.0

Hz), 129.05, 128.70 (d, J = 7.0 Hz), 128.15 (d, J = 8.0 Hz), 121.47. HRMS (ESI-QTOF) m/z : ([M+H]+) Calcd

for C21H17NP : 314.1099 Found 314.1099.

tri-p-tolyl-phosphine (3w). According to the general procedure B, reaction with di-p-

methylphenyl p-methoxylbenzoylphosphine(104 mg, 0.3 mmol), [RhCl(coe)2]2 (3.6 mg,

P 5 mol % of Rh), 1-iodonaphthalene (CAS : 90-14-2)(0.2 mmol), CsOPiv (94 mg, 0.4
mmol) and dioxane (0.4 mL) afforded 38mg of product 3y in a yield of 57%as white solid; 1H NMR ( 400

MHz, CDCl3) : 8.40-8.36 (m, 1 H), 7.835 (dd, J=8, 12 Hz, 2 H), 7.48-7.40 (m, 2 H), 7.36-7.32 (m, 1 H), 7.21-

7.16 (m, 8 H), 7.14-6.98 (m, 1 H), 2.34 (s, 6 H). P NMR (162 MHz, CDCl3) : -15.88.MS (ESI) m/z :
31

([M+H]+) Calcd for C24H22P : 341,14, Found 341.30.

tri-p-tolyl-phosphine (3x). According to the general procedure B, reaction with di-p-

P methylphenyl p-methoxylbenzoylphosphine(52 mg, 0.15 mmol), [RhCl(coe)2]2 (1.8

mg, 5 mol % of Rh), 1-iodo-4-methylbenzene (CAS : 624-31-7)(0.1 mmol), CsOPiv

(47 mg, 0.4 mmol) and dioxane (0.2 mL) afforded 25mg of product 3w in a yield of

82%as white solid; 1H NMR ( 400 MHz, CDCl 3) : 7.25-7.17 (m, 6 H), 7.14-7.12 (m, 6 H), 2.34 (s, 9 H). 31P

NMR (162 MHz, CDCl3) : -7.87.MS (ESI) m/z : ([M+H]+) Calcd for C21H22P : 305.14, Found 305.30.

Methyl 4-(di-p-tolylphosphanyl)benzoate(3y). According to the general

COOMe

P procedure B, reaction with di-p-methylphenyl p-

methoxylbenzoylphosphine(52 mg, 0.15 mmol), [RhCl(coe)2]2 (1.8 mg, 5 mol

% of Rh), 4-iodo-benzoic acid methyl ester (CAS : 619-44-3)(0.1 mmol),

CsOPiv (47 mg, 0.4 mmol) and dioxane (0.2 mL) afforded 24mg of product 3x in a yield of 73%as white solid;

1
H NMR ( 400 MHz, CDCl3) : 7.94 (d, J= 8 Hz, 2 H), 7.33-7.15 (m, 10 H), 3.90(s, 3 H), 2.36 (s, 6 H). 31P

NMR (162 MHz, CDCl3) : -6.57.13C NMR (100 MHz, CDCl3)  :167.0, 145.0, 139.2, 134.1, 133.9, 133.0,

132.9, 132.8, 129.7, 129.5, 129.4, 129.2, 129.1, 127.1, 52.1, 21 3. HRMS (ESI-QTOF) m/z: ([M+H] +) Calcd

for C22H22O2P :349.1357 Found 349.1347.

Reference:

(1) Yang, J. Chen, X. Wang, Z. Tetrahedron Lett. 2015, 56, 5673.

(2) Hayashi, M. Ishitobi, H. Matsuura, Y. Matsuura, T. Watanabe, Y. Org. Lett.2014, 16, 5830.
NMR Spectra for Table2: