Synthesis of Organophosphorus Compounds through Copper-Catalyzed Annulation Involving C-O and C-P Bond Formations

Article abstract of DOI:10.1021/acs.joc.7b01947

A novel copper(II) trifluoromethanesulfonate-catalyzed, high-efficiency, and atom-economical synthesis of valuable organophosphorus compounds via cascade annulation of propargylic alcohols with diphenylphosphine oxide is described. This protocol, which has a good functional-group compatibility and insensitivity to an ambient atmosphere, provides a simple and direct pathway to the products, organophosphorus compounds, in good yields under mild conditions. The method could be efficiently scaled up to gram scale, thus highlighting a potential application of this methodology.

Full text of DOI:10.1021/acs.joc.7b01947

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Note
Synthesis of Organophosphorus Compounds through Copper-
Catalyzed Annulation Involving C-O and C-P Bond Formation
Xue-Song Li, Ya-Ping Han, Xin-Yu Zhu, Ming Li, Wan-Xu Wei, and Yong-Min Liang
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.7b01947 • Publication Date (Web): 13 Oct 2017
Downloaded from http://pubs.acs.org on October 13, 2017
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Synthesis of Organophosphorus Compounds through Copper-
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Catalyzed Annulation Involving C−O and C−P Bond Formation
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Xue-Song Li, Ya-Ping Han, Xin-Yu Zhu, Ming Li, Wan-Xu Wei, Yong-Min Liang*
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State Key Laboratory of Applied Organic Chemistry, Lanzhou University, Lanzhou 730000,
China Fax: +86-931-8912582; e-mail: liangym@lzu.edu.cn;
ABSTRACT:
A novel Copper (II) trifluoromethanesulfonate-catalyzed, high-efficiency, and atom-
economical synthesis of valuable organophosphorus compounds via cascade annulation of
propargylic alcohols with diphenylphosphine oxide is described. This protocol, which has good
functional-group compatibility and insensitivity to an ambient atmosphere, provides a simple
and direct pathway to the products organophosphorus compounds in good yields under mild
conditions. The method could be efficiently scaled up to gram scale, thus highlighting a
potential application of this methodology.
Organophosphorus compounds, as an important class of organic products, have received
considerable attention from the synthetic community because they have broad applications in
the field of material science,1 medicinal chemistry,2 organic synthesis,3 natural products,4 and
ligand chemistry.5 In light of their importance, the construction of C(sp2)−P bond is one of the
most important and fundamental reactions to synthesize the organophosphorus compounds.
The classical synthetic strategies for the formation of C−P bond rely on the transition-metal
catalyzed cross-coupling reactions and reactions of phosphines reagents with an electrophilic
C(sp2)-(pseudo)halides.6 An Ag-mediated C−H/P−H functionalization method to construct
benzo[b]-phosphole oxides by employing arylphosphine oxides and internal alkynes as the
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substrates was disclosed by the Duan group and Ackermann group independently. (Scheme
1a).7 In the meantime, Studer and coworkers reported a novel protocol for the synthesis of 6-
phosphorylated phenanthridines starting from readily available 2-isocyanobiphenyls and the
commercially available diphenylphosphine oxides (Scheme 1b).8 Recently, our group also
developed an Ag-catalyzed cascade difunctionalization of N-(p-methoxyaryl)-propiolamides
with diphenylphosphine oxides to regiospecifically generate a large amount of phosphorylated
azadecenones (Scheme 1c).9 In spite of much attention have been paid toward the C−P bond
construction and various utilized routes have been investigated and established, the
development of new reliable synthetic strategy for the formation of C−P bond from easy
preparation starting materials is still attractive yet challenging task.
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Scheme 1. Summary of previous studies and our new anticipation toward organophosphorus
compounds
Recently, the rapid development of transition-metal-catalyzed cascade cycloaddition of
propargylic alcohols with various nucleophiles or electrophiles provides a new and powerful
synthetic strategy to synthesize meritorious heterocycles, carbocycles, and bridged rings.
Propargylic alcohols, due to its high reactivity and lower cost, have extensively been used as
organic synthons for the construction of different compounds such as indoles,10 indenes,11
furans,12 pyridines,13 azoles,14 and azepines.15 Stimulated by these fascinating research and
our continuing interest on the transformation of propargylic alcohols, we herein report a facile
copper-catalyzed cycloaddition of propargylic alcohols with diphenylphosphine oxides, which
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enables atom-economy and environmental sustainability synthesis of organophosphorus
compounds under base-free, ligand-free conditions (Scheme 1d).
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Initially, our investigation focused on the reaction of alkynol substrate 1a with
diphenylphosphine oxide 2a to optimize the reaction conditions. To our delight, in the
presence of 20 mol % of Y(OTf)3 as catalyst in toluene at 60 °C for 6 h under an air
atmosphere, the expected product 3a was obtained in a yield of 37% (Table 1, entry 1). The
structure of product 3a was further confirmed by NMR spectroscopy and X-ray crystal
diffraction analysis (see the Supporting Information). Subsequently, examination of several
catalysts indicated that Cu(OTf)2 was optimal, which furnished 42% yield of the product
(entries 2−5). A subsequent survey on the effect of temperature indicated that 90°C was the
most favored temperature for this transformation (entries 6−8). To advance the process further,
we further optimized the cascade reaction by adding additives. The desired product was
obtained in 78% yield in the presence of 50 mol % of Ag2CO3 (entries 9−11). The loading of
catalyst was investigated, yet, decreasing the amount of Cu(OTf)2 to 15 mol % slightly
reduced the yield to 71% (entries 12−13). Other solvents such as CH3CN, DCE, CH3NO2, and
THF were further evaluated, indicating that DCE was the optimal choice for this transformation
and could increase the product yield up to 75% (entries 14−17). Ultimately, the optimal
conditions for the generation of 3a were settled as 1a (1.2 equiv.), diphenylphosphine oxide 2a
(0.1 mmol) in the presence of Cu(OTf)2 (15 mol %) and Ag2CO3 (0.5 equiv.) in DCE (2.0 mL)
at 90°C for 6 h.
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With the optimized conditions established, the substrate scope of this transformation of
diphenylphosphine oxides 2 with various propargylic alcohols 1 was then investigated. As
shown in Scheme 2, a variety of alkynols bearing electron-rich groups (Me, OMe, 3a−3e) and
electron-deficient groups (F, Cl, Ph, 3f−3i) at any position of the aryl ring (R1 or R2) were
compatible with the cascade annulation reaction, giving the corresponding products 3a−3i with
yields ranging from 32% to 78%. It is worth noting that halo-substituted organophosphorus
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Table 1. Optimization of the reaction conditions of 1a with diphenylphosphine oxide a, b
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entry
catalyst
(mol %)
additive (50
solvent temp yield
mol %)
(°C)
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(%)b
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Y(OTf)3 (20)
Yb(OTf)3 (20)
Bi(OTf)3 (20)
Zn(OTf)2 (20)
Cu(OTf)2 (20)
Cu(OTf)2 (20)
Cu(OTf)2 (20)
Cu(OTf)2 (20)
Cu(OTf)2 (20)
Cu(OTf)2 (20)
/
/
/
/
/
/
/
/
PhCH3
PhCH3
PhCH3
PhCH3
PhCH3
PhCH3
PhCH3
PhCH3
PhCH3
PhCH3
PhCH3
PhCH3
PhCH3
CH3CN
DCE
AgOAc
Ag2CO3
Cu(OTf)2 (20) CF3COOAg
Cu(OTf)2 (10)
Cu(OTf)2 (15)
Cu(OTf)2 (15)
Cu(OTf)2
(15)
Cu(OTf)2 (15)
Cu(OTf)2 (15)
Ag2CO3
Ag2CO3
Ag2CO3
Ag2CO3
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Ag2CO3
Ag2CO3
CH3NO2
THF
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90
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aUnless otherwise noted, all reactions were performed with 1a (1.2 equiv.) and
b
diphenylphosphine oxide 2a (0.1 mmol) in solvent (2.0 mL) for 6 h. Yields are given for
isolated products.
compounds could be further utilized for C−C or C−N bond formation (3f−3h). Symmetrical
propargylic alcohols 1j and 1k were tested, and they proceeded smoothly in the annulation to
furnish the corresponding products 3j and 3k in 51 and 54% yields, illustrating that the
electronic effect of substituents on the phenyls (R1 and R2) is not evident for this
transformation. Indeed, propargylic alcohol 1l with two different substituents methoxy group
and F also efficiently furnish the expected product 3l in 61% yield. Next, we sought to
investigate the scope with respect to the diphenylphosphine oxide 2, H-phosphine oxides such
as 2n and 2o were suitable substrates for this transformation, and the corresponding products
3n and 3o were obtained in 73% and 52% yields, respectively. Unfortunately, secondary
propargylic alcohol 2-(3-hydroxy-3-phenylprop-1-yn-1-yl)phenol 1p was not compatible with
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Scheme 2 Transformation of propargylic alcohols to benzofuran-3-yldiphenylphosphine oxides
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aUnless otherwise noted, all reactions were performed with 1 (1.2 equiv.) and 2 (0.1 mmol) in
the presence of Cu(OTf)2 (15 mol %), Ag2CO3 (0.5 equiv.) in DCE (2.0 mL) at 90 °C for 6 h.
bYields are given for isolated products.
the reaction under the standard conditions due to the fact that only a aryl group is difficult to
stabilize the intermediate A generated by the substrate alkynol 1 (see Scheme 5).
To extend the applicability of this reaction, we sought to investigate the scope of various
substituted 3-(2-aminophenyl)-1,1-diphenylprop-2-yn-1-ols 4 with diphenylphosphine oxide 2a
(Scheme 3). Symmetrical propargylic alcohols 4a and 4b reacted with diphenylphosphine
oxide smoothly with moderate to good yields. For the unsymmetrical substituted propargylic
alcohols containing either electron-donating (Me, OMe, 4c−4e) or electron-withdrawing groups
(Cl, Ph, 4f−4g), the reactions proceeded smoothly to provide the desired products in 38−82%
yields.
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Scheme 3. Transformation of propargylic alcohols to diphenyl(propa-1,2-dien-1-yl)phosphine
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oxides a b
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aUnless otherwise noted, all reactions were performed with 4 (1.2 equiv.) and 2a (0.1 mmol) in
the presence of Cu(OTf)2 (15 mol %), Ag2CO3 (0.5 equiv.) in DCE (2.0 mL) at 90 °C for 6 h.
bYields are given for isolated products.
A noteworthy advantage of the cascade annulation reaction was that this transformation
could be efficiently scaled up to gram under the optimal conditions, thus highlighting a
potential application of this methodology in synthetic industry
To gain insight into the novel transformation, additional mechanistic studies have been
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conducted (Scheme 4). When 10.0 equivalent H2 O was added into the reactions under the
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standard conditions, the corresponding product 3a containing O was obtained in 62% yield,
thus indicating that the hydroxy of the desired product 3a is from the substrate propargylic
alcohol 1a. Furthermore, when the compound 6 (see the Supporting Information) was
investigated under the optimal conditions without diphenylphosphine oxide, the expected
product 3a was obtained in 82% yield, this result suggested that the compound 6 was the
intermediate in this novel transformation.
Scheme 4. Verification experiments for the mechanism
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On the basis of previously published literature and the above experimental results,16-17
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plausible mechanism is depicted in Scheme 5. Initially, the coordination of Lewis acid
Cu(OTf)2 to the propargyl alcohol 1a led to intermediate A, which could undergo a subsequent
intermolecular attack of the Ph2OP anion to produce the stabilized allenic intermediate B. The
protonation of intermediate B affords intermediate C. Subsequent nucleophilic attack of H2O
onto the intermediate C forms intermediate D. Then, the intramolecular nucleophilic addition of
intermediate D to the carbenium ion site produces intermediate E. Finally, the desired product
3a is afforded with release of a proton and the regenerated catalyst.
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Scheme 5. Proposed mechanism for the formation of organophosphorus compounds.
CONCLUSIONS
In summary, a novel Copper (II) trifluoromethanesulfonate-catalyzed cascade
cycloaddition of propargylic alcohols with substituted diphenylphosphine oxides has been
developed, furnishing the benzofuran-3-yldiphenylphosphine oxides and diphenyl(propa-1,2-
dien-1-yl)phosphine oxides with good yields in a simple, high-efficiency way. This protocol
demonstrates a facile and atom-economical access to the organophosphorus compound
derivatives, which acts as an important skeleton in a number of natural products and bioactive
molecules. The good functional group tolerance and operational simplicity of our developed
reaction system are to be ranked among the most versatile and efficient alternatives for the
synthesis of organophosphorus compound scaffolds.
EXPERIMENTAL SECTION
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General Remarks: Column chromatography was carried out on silica gel. H NMR spectra
were recorded on 400 MHz in CDCl3. 13C NMR spectra were recorded on 100 MHz in CDCl3.
Chemical shifts (ppm) were recorded with tetramethylsilane (TMS) as the internal reference
standard. Multiplicities are given as: s (singlet), d (doublet), t (triplet), dd (doublet of doublets),
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q (quartet) or m (multiplet). Copies of their H NMR and C NMR spectra are provided in the
Supporting Information. High-resolution mass spectra were measured on Orbitrap Elite with
electrospray ionization mode (ESI+). Solvents were dried under standard method.
Commercially available reagents were used with further purification. DCE was distilled
immediately before use from CaH.
General procedure for the synthesis of (2-(hydroxydiphenylmethyl)benzofuran-3-
yl)diphenylphosphine oxide (3a)
The reaction of propargylic alcohol 1a (1.2 equiv.), diphenylphosphine oxide 2a (0.1 mmol),
Cu(OTf)2 (15 mol %) and Ag2CO3 (0.5 equiv.) in DCE (2.0 mL) was conducted at 90 °C under
an air atmosphere. The reaction was completed within 6.0 h by TLC monitoring. The resulting
mixture was cooled down to room temperature and then diluted with ethyl acetate (2 × 10 mL),
washed with a saturated aqueous solution of brine, dried over Na2SO4, and evaporated under
reduced pressure. The residue was further purified by chromatography on silica gel (petroleum
ether/ethyl acetate, 5:1) to afford 37.5 mg of 3a.
General procedure for the synthesis of (1-(2-hydroxyphenyl)-3,3-diphenylpropa-1,2-
dien-1-yl)diphenylphosphine oxide (6)
The reaction of propargylic alcohol 1a (0.1 mmol), diphenylphosphine oxide 2a (2.0 equiv.),
Cu(OTf)2 (15 mol %) and in THF (2.0 mL) was conducted at 40 °C under an air atmosphere.
The reaction was completed within 2.0 h by TLC monitoring. The resulting mixture was cooled
down to room temperature and then diluted with ethyl acetate (2 × 10 mL), washed with a
saturated aqueous solution of brine, dried over Na2SO4, and evaporated under reduced
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pressure. The residue was further purified by chromatography on silica gel (petroleum
ether/ethyl acetate, 3:1) to afford 35.1 mg of 6 (72.5%).
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General procedure for the synthesis of 118
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Ethynylmagnesium bromide (0.5 mol/L in THF, 24 mL, 1.2 equiv) was added dropwise
into a stirred solution of benzophenone (10 mmol, 1.82 g) in THF (35 mL) under argon. The
mixture was allowed to stir for 4h at room temperature. After the completion of the reaction
determined by TLC, the reaction mixture was quenched by addition of an aqueous saturated
solution of NH4Cl (35 mL) and extracted with ethyl acetate (2×50 mL). The combined organic
layers were washed with brine, dried over Na2SO4, and concentrated under reduced pressure.
The resulting material 1,1-diphenylprop-2-yn-1-ol was directly used for the next step without
further purification.
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Pd(PPh3)2Cl2 (56.1 mg, 0.08 mmol, 1 mol %) and CuI (30.6 mg, 0.16mmol, 2 mol %) were
sequentially added to a stirred solution of 1,1-diphenylprop-2-yn-1-ol (8 mmol, 1.67 g) in
triethylamine (30 mL) under argon at room temperature. The mixture was allowed to stir for 10
min. Then tert-butyl(2-iodophenoxy)dimethylsilane (3.48 g, 10.4 mmol, 1.3 equiv) was added.
The mixture was allowed to stir overnight. The resulting mixture was poured into an aqueous
saturated solution of NH4Cl (30 mL) and the product was extracted with ethyl acetate (2×40
mL). The combined organic layers were washed with brine, dried over Na2SO4, and
concentrated under reduced pressure. The residue was purified by flash column
chromatography (silica gel, petroleum ether/ethyl acetate, 10:1) to give 3-(2-((tert-
butyldimethylsilyl)oxy) phenyl)-1,1-diphenylprop-2-yn-1-ol.
Tetrabutylammonium fluoride (1.57 g, 6 mmol, 1.2 equiv) was added to a stirred solution
of 3-(2-((tert-butyldimethylsilyl)oxy)phenyl)-1,1-diphenylprop-2-yn-1-ol (2.07 g, 5 mmol) in THF
(25 mL) at room temperature for 30 min. After the completion of the reaction determined by
TLC, the reaction mixture was quenched by addition of water (10 mL) and extracted with ethyl
acetate (2×30 mL). The combined organic layers were washed with brine, dried over Na2SO4,
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and concentrated under reduced pressure. The crude material was purified by column
chromatography (silica gel, petroleum ether/ethyl acetate/dichloromethane, 10:1:1) to give the
pure product 2-(3-hydroxy-3,3-diphenylprop-1-yn-1-yl)phenol 1a.
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General procedure for the synthesis of 418
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Pd(PPh3)2Cl2 (56.1 mg, 0.08 mmol, 1 mol %) and CuI (30.6 mg, 0.16 mmol, 2 mol %)
were sequentially added to a stirred solution of 1,1-diphenylprop-2-yn-1-ol (8 mmol, 1.67 g) in
triethylamine (30 mL) under argon at room temperature. The mixture was allowed to stir for 10
min. Then 2-iodoaniline (2.1 g, 9.6 mmol, 1.2 equiv) was added. The mixture was allowed to
stir overnight. The resulting mixture was poured into an aqueous saturated solution of NH4Cl
(35 mL) and the product was extracted with ethyl acetate (2×50 mL). The combined organic
layers were washed with brine, dried over Na2SO4, and concentrated under reduced pressure.
The residue was purified by flash column chromatography (silica gel, petroleum ether/ethyl
acetate/triethylamine, 100:10:1) to give 3-(2-aminophenyl)-1,1-diphenylprop-2-yn-1-ol.
TsCl (1.24 g, 6.5 mmol, 1.3 equiv) was added portion-wise to a solution of 3-(2-
aminophenyl)-1,1-diphenylprop-2-yn-1-ol 3-(2-aminophenyl)-1,1-diphenylprop-2-yn-1-ol (1.5 g,
5 mmol) in CH2Cl2 (25 mL) and pyridine (1.6 mL, 20 mmol, 4.0 equiv) under 0 °C. The mixture
was then warmed to room temperature and allowed to stir for 4 h. After the completion of the
reaction determined by TLC, the mixture was concentrated in vacuo, and the residue was
extracted with ethyl acetate (2×30 mL). The combined organic layers were washed with HCl
(aq, 5%, 20 mL) and brine, dried over Na2SO4, and concentrated under reduced pressure. The
residue was purified by flash column chromatography (silica gel, petroleum ether/ethyl
acetate/triethylamine, 100:5:1) to give N-(2-(3-hydroxy-3,3-diphenylprop-1-yn-1-yl)phenyl)-4-
methylbenzenesul fonamide 4a.
Characterization data of 3a–6
(2-(hydroxydiphenylmethyl)benzofuran-3-yl)diphenylphosphine oxide (3a):
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The resultant residue was purified by flash silica gel column chromatography to afford 3a as a
yellow solid (37.5 mg, 75%); m.p. 146-148 °C ; 1H NMR (400 MHz, CDCl3): 8.71 (s, 1H), 7.57–
7.52 (m, 6H), 7.42–7.37 (m, 5H), 7.32–7.30 (m, 4H), 7.24–7.21 (m, 7H), 7.00 (t, J = 7.6 Hz,
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1H), 6.57 (d, J = 8.0 Hz, 1H). C{H} NMR (100 MHz, CDCl3): δ 172.7, 172.5, 153.5, 153.3,
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144.9, 132.4, 132.4, 131.9, 131.8, 131.7, 130.8, 128.7, 128.6, 128.5, 128.3, 127.7, 127.6,
127.3, 124.7, 123.7, 121.0, 112.0, 106.9, 105.8, 79.2. IR (KBr) 3060, 2926, 1667, 1597, 1488,
1444, 1267, 1241, 1168, 1122, 910, 870, 751, 698cm-1. HRMS (ESI) m/z: [M + Na]+ Calcd for
C33H25O3PNa 523.1434; found 523.1432.
(2-(hydroxy(phenyl)(o-tolyl)methyl)benzofuran-3-yl)diphenylphosphine oxide (3b):
The resultant residue was purified by flash silica gel column chromatography to afford 3b as a
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yellow liquid (40.2 mg, 78%); H NMR (400 MHz, CDCl3): 8.64 (s, 1H), 7.69–7.64 (m, 2H),
7.59–7.55 (m, 1H), 7.47–7.44 (m, 3H), 7.42–7.41 (m, 2H), 7.39–7.37 (m, 3H), 7.35–7.32 (m,
2H), 7.26–7.23 (m, 4H), 7.20–7.18 (m, 1H), 7.16–7.11 (m, 2H), 7.01 (t, J = 7.6 Hz, 1H), 6.97–
6.93 (m, 1H), 6.67–6.61 (m, 2H), 2.15 (s, 3H). 13C{H} NMR (100 MHz, CDCl3): δ 173.2, 173.1,
153.3, 153.2, 144.7, 142.7, 138.5, 132.5, 132.5, 132.3, 132.2, 132.0, 131.8, 131.7, 131.6,
131.5, 130.7, 128.8, 128.7, 128.6, 128.5, 128.5, 128.3, 127.8, 127.3, 127.3, 124.7, 124.7,
123.7, 121.0, 112.0, 106.4, 105.2, 80.1, 21.0. IR (KBr) 3061, 1596, 1525, 1442, 1267, 1244,
1168, 1121, 1062, 872, 746, 698, 653 cm-1. HRMS (ESI) m/z: [M + Na]+ Calcd for
C34H27O3PNa 537.1590; found 537.1586.
(2-(hydroxy(phenyl)(m-tolyl)methyl)benzofuran-3-yl)diphenylphosphine oxide (3c):
The resultant residue was purified by flash silica gel column chromatography to afford 3c as a
yellow solid (29.3 mg, 57%); m.p. 118-120 °C ; 1H NMR (400 MHz, CDCl3): 8.67 (s, 1H), 7.57 (s,
1H), 7.55–7.52 (m, 5H), 7.41–7.37 (m, 5H), 7.33–7.30 (m, 2H), 7.24–7.20 (m, 4H), 7.14 (s, 1H),
7.12–7.08 (m, 1H), 7.06–6.98 (m, 3H), 6.57 (d, J = 8.0 Hz, 1H), 2.21 (s, 3H). 13C{H} NMR (100
MHz, CDCl3): δ 172.8, 172.7, 153.5, 153.3, 144.9, 137.2, 132.4, 132.3, 132.3, 132.0, 131.9,
131.8, 131.7, 131.7, 131.6, 130.9, 130.8, 128.7, 128.6, 128.6, 128.5, 128.4, 128.1, 128.1,
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127.6, 127.5, 127.3, 124.8, 124.6, 123.7, 121.0, 112.0, 106.8, 105.7, 79.2, 21.5. IR (KBr) 3397,
2922, 1740, 1605, 1518, 1446, 1263, 1130, 1075, 1026, 750, 699cm-1. HRMS (ESI) m/z: [M +
H]+ Calcd for C34H28O3P 515.1771; found 515.1771.
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(2-(hydroxy(phenyl)(p-tolyl)methyl)benzofuran-3-yl)diphenylphosphine oxide (3d):
The resultant residue was purified by flash silica gel column chromatography to afford 3d as a
yellow solid (31.9 mg, 62%); m.p. 146-148 °C ;1H NMR (400 MHz, CDCl3): 8.63 (s, 1H), 7.56–
7.51 (m, 6H), 7.40–7.36 (m, 5H), 7.33–7.31 (m, 2H), 7.23–7.19 (m, 5H), 7.17 (s, 1H), 7.01–
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6.97 (m, 3H), 6.55 (d, J = 8.0 Hz, 1H), 2.30 (s, 3H). C{H} NMR (100 MHz, CDCl3): δ 172.9,
172.8, 153.4, 153.3, 145.0, 142.1, 136.9, 132.4, 132.3, 132.3, 132.2, 132.1, 131.9, 131.8,
131.7, 130.9, 130.8, 128.7, 128.6, 128.5, 128.5, 128.4, 128.3, 127.6, 127.6, 127.5, 127.3,
124.6, 123.7, 121.0, 112.0, 106.8, 105.7, 79.1, 21.0. IR (KBr) 3059, 2922, 1731, 1647, 1606,
1513, 1442, 1265, 1241, 1169, 1125, 1071, 750, 697cm-1. HRMS (ESI) m/z: [M + Na]+ Calcd
for C34H27O3PNa 537.1590; found 537.1588.
(2-(hydroxy(4-methoxyphenyl)(phenyl)methyl)benzofuran-3-yl)diphenylphosphine oxide
(3e):
The resultant residue was purified by flash silica gel column chromatography to afford 3e as a
yellow solid (17.2 mg, 32%); m.p. 122-124 °C ; 1H NMR (400 MHz, CDCl3): 8.61 (s, 1H), 7.58–
7.51 (m, 6H), 7.43–7.37 (m, 5H), 7.32–7.29 (m, 2H), 7.23–7.19 (m, 6H), 7.00 (t, J = 7.6 Hz,
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1H), 6.74 (d, J = 8.8 Hz, 2H), 6.55 (d, J = 8.0 Hz, 1H), 3.78 (s, 3H). C{H} NMR (100 MHz,
CDCl3): δ 173.0, 172.9, 158.8, 153.5, 153.3, 145.1, 137.3, 132.4, 132.0, 132.0, 131.8, 131.8,
131.7, 130.9, 130.9, 128.8, 128.7, 128.7, 128.6, 128.4, 127.6, 127.6, 127.3, 124.6, 123.7,
121.0, 113.0, 112.0, 106.8, 105.7, 78.9, 55.2. IR (KBr) 3123, 2924, 1607, 1510, 1441, 1302,
1249, 1170, 1122, 1065, 912, 750, 698cm-1. HRMS (ESI) m/z: [M + Na]+ Calcd for
C34H27O4PNa 553.1539; found 553.1538.
(2-((4-fluorophenyl)(hydroxy)(phenyl)methyl)benzofuran-3-yl)diphenylphosphine oxide
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The resultant residue was purified by flash silica gel column chromatography to afford 3f as a
yellow solid (26.8 mg, 52%); m.p. 90-92 °C ; 1H NMR (400 MHz, CDCl3): 8.75 (s, 1H), 7.59–
7.50 (m, 6H), 7.44–7.36 (m, 5H), 7.30–7.26 (m, 4H), 7.24–7.20 (m, 4H), 7.01 (t, J = 7.6 Hz,
1H), 6.88 (t, J = 8.8 Hz, 2H), 6.57 (d, J = 8.0 Hz, 1H). 13C{H} NMR (100 MHz, CDCl3): δ 172.4,
172.2, 163.3, 160.8, 153.4, 153.3, 144.7, 140.7, 140.7, 132.5, 132.5, 132.4, 131.8, 131.7,
131.7, 131.6, 131.6, 130.7, 130.6, 129.4, 129.3, 128.7, 128.7, 128.6, 128.6, 128.4, 128.3,
127.7, 127.5, 127.4, 124.8, 123.8, 121.0, 114.5, 114.3, 111.9, 107.1, 105.9, 78.8. IR (KBr)
3397, 2922, 2852, 1733, 1601, 1506, 1442, 1227, 1161, 1127, 1074, 751, 697, 553cm-1.
HRMS (ESI) m/z: [M + H]+ Calcd for C33H25FO3P 519.1520; found 519.1517.
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(2-((4-chlorophenyl)(hydroxy)(phenyl)methyl)benzofuran-3-yl)diphenylphosphine oxide
(3g):
The resultant residue was purified by flash silica gel column chromatography to afford 3e as a
yellow solid (38.7 mg, 73%); m.p. 116-118 °C ; 1H NMR (400 MHz, CDCl3): 8.77 (s, 1H), 7.58–
7.50 (m, 6H), 7.43–7.37 (m, 5H), 7.30–7.28 (m, 2H), 7.25–7.21 (m, 6H), 7.15–7.13 (m, 2H),
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7.01 (t, J = 7.2 Hz, 1H), 6.57 (d, J = 8.0 Hz, 1H). C{H} NMR (100 MHz, CDCl3): δ 172.1,
172.0, 153.4, 153.3, 144.4, 143.5, 133.2, 132.5, 132.5, 132.4, 131.8, 131.7, 131.7, 131.6,
131.5, 130.7, 130.5, 129.0, 128.7, 128.6, 128.4, 128.3, 127.7, 127.7, 127.5, 127.4, 124.8,
123.9, 121.0, 112.0, 107.2, 106.1, 78.7. IR (KBr) 3061, 2924, 1525, 1487, 1441, 1267, 1245,
1168, 1121, 1015, 752, 698, 657, 553cm-1. HRMS (ESI) m/z: [M + Na]+ Calcd for
C33H24ClO3PNa 557.1044; found 557.1048.
(2-((3-chlorophenyl)(hydroxy)(phenyl)methyl)benzofuran-3-yl)diphenylphosphine oxide
(3h):
The resultant residue was purified by flash silica gel column chromatography to afford 3h as a
yellow solid (39.5 mg, 74%); m.p. 86-88 °C ; 1H NMR (400 MHz, CDCl3): 8.81 (s, 1H), 7.60–
7.49 (m, 6H), 7.44–7.39 (m, 5H), 7.33–7.32 (m, 1H), 7.30–7.28 (m, 2H), 7.24–7.18 (m, 6H),
7.16–7.14 (m, 1H), 7.04–7.00 (m, 1H), 6.58 (d, J = 8.0 Hz, 1H). 13C{H} NMR (100 MHz, CDCl3):
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δ 171.8, 171.6, 153.4, 153.3, 146.9, 144.3, 133.7, 132.6, 132.5, 132.5, 132.4, 131.7, 131.7,
131.6, 131.6, 128.9, 128.8, 128.7, 128.7, 128.6, 127.8, 127.6, 127.6, 127.4, 126.0, 124.9,
123.9, 121.0, 112.0, 107.3, 106.1, 78.8. IR (KBr) 3063, 1592, 1526, 1471, 1441, 1267, 1245,
1167, 1121, 1062, 871, 750, 698, 653cm-1. HRMS (ESI) m/z: [M + H]+ Calcd for C33H25ClO3P
535.1224; found 535.1222.
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(2-([1,1'-biphenyl]-4-yl(hydroxy)(phenyl)methyl)benzofuran-3-yl)diphenylphosphine
oxide (3i):
The resultant residue was purified by flash silica gel column chromatography to afford 3i as a
yellow solid (31.7 mg, 55%); m.p. 46-48 °C 1H NMR (400 MHz, CDCl3): 8.75 (s, 1H), 7.58–7.52
(m, 7H), 7.51–7.48 (m, 1H), 7.44–7.40 (m, 7H), 7.38–7.32 (m, 7H), 7.25–7.22 (m, 4H), 7.03–
6.99 (m, 1H), 6.58 (d, J = 8.0 Hz, 1H). 13C{H} NMR (100 MHz, CDCl3): δ 172.7, 172.5, 153.4,
144.7, 144.1, 140.9, 140.0, 132.4, 132.4, 132.3, 132.3, 131.8, 131.7, 131.7, 131.6, 128.7,
128.7, 128.6, 128.5, 128.5, 128.0, 127.7, 127.6, 127.4, 127.2, 127.1, 126.4, 124.7, 123.8,
121.0, 112.0, 107.0, 105.9, 79.1. IR (KBr) 3060, 2852, 1597, 1524, 1486, 1442, 1266, 1167,
1121, 1064, 750, 698, 650, 548cm-1. HRMS (ESI) m/z: [M + Na]+ Calcd for C39H29O3PNa
599.1747; found 599.1747.
(2-(hydroxydi-p-tolylmethyl)benzofuran-3-yl)diphenylphosphine oxide (3j):
The resultant residue was purified by flash silica gel column chromatography to afford 3j as a
yellow solid (26.8mg, 51%); m.p. 100-102 °C ; 1H NMR (400 MHz, CDCl3): 8.54 (s, 1H), 7.56–
7.51 (m, 6H), 7.42–7.36 (m, 5H), 7.22–7.17 (m, 5H), 7.01–6.97 (m, 5H), 6.52 (d, J = 8.0 Hz,
1H), 2.30 (s, 6H). 13C{H} NMR (100 MHz, CDCl3): δ 173.2, 173.1, 153.4, 153.3, 142.1, 136.8,
132.2, 132.2, 132.1, 131.8, 131.7, 131.0, 129.0, 128.6, 128.5, 128.3, 127.5, 124.5, 123.6,
120.9, 112.0, 106.8, 105.6, 79.0, 21.1. IR (KBr) 3135, 2857, 1587, 1514, 1440, 1245, 1170,
1121, 1071, 698, 650, 580, 553cm-1. HRMS (ESI) m/z: [M + H]+ Calcd for C35H30O3P 529.1927;
found 529.1927.
(2-(bis(4-chlorophenyl)(hydroxy)methyl)benzofuran-3-yl)diphenylphosphine oxide (3k):
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The resultant residue was purified by flash silica gel column chromatography to afford 3k as a
yellow solid (31.0 mg, 54%); m.p. 110-112 °C ; 1H NMR (400 MHz, CDCl3): 8.80 (s, 1H), 7.59–
7.54 (m, 3H), 7.53–7.51 (m, 2H), 7.49 (s, 1H), 7.44–7.39 (m, 5H), 7.25 (s, 1H), 7.22–7.20 (m,
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4H), 7.16–7.14 (m, 4H), 7.03 (t, J = 8.0 Hz, 1H), 6.55 (d, J = 7.6 Hz, 1H). C{H} NMR (100
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MHz, CDCl3): δ 171.6, 171.4, 153.3, 153.2, 143.0, 133.5, 132.6, 132.5, 131.7, 131.6, 131.5,
130.4, 128.9, 128.8, 128.7, 128.4, 128.2, 127.9, 125.0, 124.0, 121.0, 112.0, 107.6, 106.4, 78.3.
IR (KBr) 3080, 2924, 1525, 1488, 1439, 1267, 1245, 1167, 1121, 1095, 828, 751, 579cm-1.
HRMS (ESI) m/z: [M + H]+ Calcd for C33H24Cl2O3P 569.0835; found 569.0833.
(2-((4-fluorophenyl)(hydroxy)(4-methoxyphenyl)methyl)benzofuran-3-
yl)diphenylphosphine oxide (3l):
The resultant residue was purified by flash silica gel column chromatography to afford 3l as a
yellow solid (33.4 mg, 61%); m.p. 126-128 °C ; 1H NMR (400 MHz, CDCl3): 8.65 (s, 1H), 7.58–
7.51 (m, 6H), 7.44–7.38 (m, 5H), 7.28–7.27 (m, 1H), 7.25–7.24 (m, 1H), 7.23–7.20 (m, 1H),
7.19–7.17 (m, 2H), 7.01 (t, J = 7.6 Hz, 1H), 6.88 (t, J = 8.8 Hz, 2H), 6.73 (d, J = 8.8 Hz, 2H),
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6.54 (d, J = 8.0 Hz, 1H), 3.78 (s, 3H). C{H} NMR (100 MHz, CDCl3): δ 172.7, 172.6, 163.3,
160.9, 158.9, 153.4, 153.3, 140.9, 137.1, 132.5, 132.4, 132.4, 132.4, 131.9, 131.8, 131.7,
131.7, 131.6, 130.8, 129.4, 129.3, 128.7, 128.7, 128.7, 128.6, 128.6, 128.5, 128.4, 124.8,
123.8, 121.0, 114.5, 114.3, 113.1, 112.0, 107.0, 105.8, 78.5, 55.2. IR (KBr) 3438, 2925, 1607,
1507, 1439, 1249, 1166, 1121, 1069, 833, 751, 698, 650, 581 cm-1. HRMS (ESI) m/z: [M +
Na]+ Calcd for C34H26FO4PNa 571.1445; found 571.1443.
(2-(hydroxydiphenylmethyl)-5-methylbenzofuran-3-yl)diphenylphosphine oxide (3m):
The resultant residue was purified by flash silica gel column chromatography to afford 3m as a
colourless liquid (30.9 mg, 60%); 1H NMR (400 MHz, CDCl3): 8.63 (s, 1H), 7.69–7.63 (m, 2H),
7.60–7.56 (m, 1H), 7.48–7.45 (m, 3H), 7.43–7.42 (m, 2H), 7.39–7.36 (m, 3H), 7.35–7.33 (m,
2H), 7.26–7.24 (m, 4H), 7.16–7.13 (m, 2H), 7.03–6.99 (m, 1H), 6.97–6.93 (m, 1H), 6.67–6.65
(m, 1H), 6.62 (d, J = 8.0 Hz, 1H), 2.15 (s, 3H). 13C{H} NMR (100 MHz, CDCl3): δ 173.3, 173.1,
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153.4, 153.3, 144.7, 142.7, 138.5, 132.5, 132.5, 132.3, 132.2, 132.0, 131.9, 131.8, 131.8,
131.6, 131.5, 130.7, 128.8, 128.7, 128.6, 128.5, 128.5, 127.8, 127.4, 127.3, 124.7, 124.7,
123.7, 121.0, 112.0, 106.4, 105.3, 80.1, 21.0. IR (KBr) 3061, 1595, 1442, 1267, 1244, 1168,
1121, 1062, 873, 747, 698, 653, 558 cm-1. HRMS (ESI) m/z: [M + Na]+ Calcd for C34H27O3PNa
537.1590; found 537.1591.
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(2-(hydroxydiphenylmethyl)benzofuran-3-yl)(4-methoxyphenyl)(phenyl)phosphine oxide
(3n):
The resultant residue was purified by flash silica gel column chromatography to afford 3n as a
yellow solid (38.9 mg, 73%); m.p. 102-104 °C ; 1H NMR (400 MHz, CDCl3): 8.81 (s, 1H), 7.56–
7.54 (m, 1H), 7.53–7.44 (m, 4H), 7.39–7.36 (m, 3H), 7.34–7.32 (m, 2H), 7.31–7.29 (m, 2H),
7.24–7.23 (m, 3H), 7.21–7.20 (m, 4H), 7.01 (t, J = 7.6 Hz, 1H), 6.91–6.88 (m, 2H), 6.62 (d, J =
8.0 Hz, 1H), 3.82 (s, 3H). 13C{H} NMR (100 MHz, CDCl3): δ 172.4, 172.2, 162.8, 162.8, 153.4,
153.3, 145.0, 145.0, 133.8, 133.6, 132.3, 132.2, 132.2, 131.7, 131.6, 131.2, 128.6, 128.5,
128.5, 128.4, 127.6, 127.5, 127.3, 124.6, 123.6, 123.1, 122.0, 121.1, 114.3, 114.2, 111.9,
107.3, 106.1, 79.2, 55.3. IR (KBr) 3063, 1597, 1502, 1446, 1298, 1261, 1122, 1059, 1027, 800,
751, 699, 665 cm-1. HRMS (ESI) m/z: [M + Na]+ Calcd for C34H27O4PNa 553.1539; found
553.1538.
(2-(hydroxydiphenylmethyl)benzofuran-3-yl)bis(4-methoxyphenyl)phosphine oxide (3o):
The resultant residue was purified by flash silica gel column chromatography to afford 3o as a
yellow solid (29.1 mg, 52%); m.p. 108-110 °C ; 1H NMR (400 MHz, CDCl3): 8.91 (s, 1H), 7.49–
7.43 (m, 4H), 7.38–7.36 (m, 1H), 7.33–7.31 (m, 4H), 7.24–7.22 (m, 6H), 7.20–7.18 (m, 1H),
7.04–7.00 (m, 1H), 6.89–6.87 (m, 4H), 6.66 (d, J = 8.0 Hz, 1H), 3.82 (s, 6H). 13C{H} NMR (100
MHz, CDCl3): δ 172.1, 171.9, 162.7, 162.7, 153.4, 153.3, 145.1, 133.7, 133.6, 128.6, 128.5,
127.6, 127.6, 127.2, 124.5, 123.6, 123.5, 122.3, 121.1, 114.2, 114.1, 111.9, 107.6, 106.5, 79.2,
55.3. IR (KBr) 3442, 2840, 1597, 1501, 1448, 1296, 1259, 1156, 1120, 1059, 1026, 802, 751,
701, 551 cm-1. HRMS (ESI) m/z: [M + H]+ Calcd for C35H30O5P 561.1825; found 561.1824.
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methylbenzenesulfonamide (5a):
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The resultant residue was purified by flash silica gel column chromatography to afford 5a as a
colourless liquid (46.0 mg, 72%); 1H NMR (400 MHz, CDCl3): 10.90 (s, 1H), 7.79 (d, J = 8.4 Hz,
2H), 7.69–7.64 (m, 4H), 7.44–7.40 (m, 2H), 7.35–7.30 (m, 10H), 7.29–7.28 (m, 1H), 7.20–7.18
(m, 1H), 7.12–7.08 (m, 1H), 7.05–7.04 (m, 4H), 7.02–7.00 (m, 2H), 6.96–6.93 (m, 1H), 2.27 (s,
3H). 13C{H} NMR (100 MHz, CDCl3): δ 212.2, 212.1, 142.8, 138.2, 137.0, 134.1, 134.0, 132.3,
132.3, 131.9, 131.8, 131.7, 131.6, 130.6, 129.5, 129.4, 129.3, 128.6, 128.5, 128.4, 128.3,
128.3, 127.3, 124.4, 121.5, 111.8, 111.6, 102.6, 101.7, 21.4. IR (KBr) 3436, 3058, 1630, 1596,
1492, 1440, 1379, 1335, 1160, 1120, 1091, 730, 697, 544 cm-1. HRMS (ESI) m/z: [M + Na]+
Calcd for C40H32NO3PSNa 660.1733; found 660.1731.
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N-(2-(3,3-bis(4-chlorophenyl)-1-(diphenylphosphoryl)propa-1,2-dien-1-yl)phenyl)-4-
methylbenzenesulfonamide (5b):
The resultant residue was purified by flash silica gel column chromatography to afford 5b as a
colourless liquid (28.9 mg, 41%); 1H NMR (400 MHz, CDCl3): 10.81 (s, 1H), 7.84 (d, J = 8.4 Hz,
2H), 7.68–7.63 (m, 4H), 7.49–7.45 (m, 2H), 7.34–7.32 (m, 8H), 7.29–7.27 (m, 1H), 7.15–7.10
(m, 4H), 6.97–6.95 (m, 5H), 2.35 (s, 3H). 13C{H} NMR (100 MHz, CDCl3): δ 211.6, 143.0,
138.7, 137.1, 134.5, 132.6, 132.6, 132.2, 132.2, 131.7, 131.6, 130.3, 129.6, 129.6, 129.5,
129.2, 129.0, 128.6, 128.5, 127.2, 125.3, 124.7, 122.2, 109.9, 103.6, 102.7, 21.5. IR (KBr)
3439, 2924, 1925, 1637, 1490, 1438, 1335, 1160, 1120, 1092, 732, 700, 660, 547cm-1. HRMS
(ESI) m/z: [M + Na]+ Calcd for C40H30Cl2NO3PSNa 728.0953; found 728.0950.
N-(2-(1-(diphenylphosphoryl)-3-phenyl-3-(p-tolyl)propa-1,2-dien-1-yl)phenyl)-4-
methylbenzenesulfonamide (5c):
The resultant residue was purified by flash silica gel column chromatography to afford 5c as a
colourless liquid (52.2 mg, 80%); 1H NMR (400 MHz, CDCl3): 10.91 (s, 1H), 7.79 (d, J = 8.4Hz,
2H), 7.69–7.64 (m, 4H), 7.43–7.42 (m, 2H), 7.38–7.36 (m, 1H), 7.33–7.30 (m, 7H), 7.20–7.14
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(m, 3H), 7.12–7.08 (m, 1H), 7.04–7.02 (m, 2H), 7.00–6.98 (m, 2H), 6.96–6.92 (m, 3H), 2.38 (s,
3H), 2.27 (s, 3H). 13C{H} NMR (100 MHz, CDCl3): δ 212.4, 212.3, 142.8, 138.2, 137.0, 134.3,
132.3, 132.3, 131.9, 131.9, 131.7, 131.6, 131.1, 131.0, 130.7, 130.6, 129.6, 129.6, 129.3,
129.3, 128.6, 128.5, 128.4, 128.3, 128.2, 127.3, 125.2, 125.2, 124.3, 121.4, 111.7, 111.6,
102.7, 101.4, 21.4, 21.2. IR (KBr) 3437, 1924, 1633, 1492, 1440, 1335, 1160, 1093, 935, 698,
550 cm-1. HRMS (ESI) m/z: [M + Na]+ Calcd for C41H34NO3PSNa 674.1889; found 674.1888.
N-(2-(1-(diphenylphosphoryl)-3-phenyl-3-(m-tolyl)propa-1,2-dien-1-yl)phenyl)-4-
methylbenzenesulfonamide (5d):
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The resultant residue was purified by flash silica gel column chromatography to afford 5d as a
colourless liquid (39.4 mg, 61%); 1H NMR (400 MHz, CDCl3): 10.85 (s, 1H), 7.78 (d, J = 8.0 Hz,
2H), 7.71–7.64 (m, 4H), 7.44–7.43 (m, 2H), 7.36–7.30 (m, 8H), 7.23–7.17 (m, 2H), 7.15–7.08
(m, 2H), 7.07–7.05 (m, 2H), 7.01–6.99 (m, 2H), 6.96–6.93 (m, 1H), 6.84–6.82 (m, 2H), 2.34 (s,
3H), 2.28 (s, 3H). 13C{H} NMR (100 MHz, CDCl3): δ 212.3, 212.2, 142.8, 138.3, 138.3, 137.0,
134.3, 134.2, 133.9, 133.9, 132.3, 131.8, 131.7, 131.7, 131.6, 129.3, 129.1, 128.6, 128.5,
128.3, 128.2, 127.3, 125.6, 125.5, 124.4, 121.5, 21.4, 21.4. IR (KBr) 3438, 1923, 1630, 1491,
1440, 1379, 1335, 1160, 1119, 1092, 732, 698, 545 cm-1. HRMS (ESI) m/z: [M + H]+ Calcd for
C41H35NO3PS 652.2070; found 652.2065.
N-(2-(1-(diphenylphosphoryl)-3-(4-methoxyphenyl)-3-phenylpropa-1,2-dien-1-yl)phenyl)-
4-methylbenzenesulfonamide (5e):
The resultant residue was purified by flash silica gel column chromatography to afford 5e as a
colourless liquid (25.2 mg, 38%); 1H NMR (400 MHz, CDCl3): 10.88 (s, 1H), 7.80 (d, J = 8.4 Hz,
2H), 7.69–7.64 (m, 4H), 7.45–7.41 (m, 2H), 7.34–7.31 (m, 8H), 7.19–7.17 (m, 1H), 7.13–7.09
(m, 1H), 7.05–7.02 (m, 4H), 6.98–6.95 (m, 3H), 6.89–6.86 (m, 2H), 3.84 (s, 3H), 2.29 (s, 3H).
13C{H} NMR (100 MHz, CDCl3): δ 212.5, 159.7, 142.8, 138.3, 137.0, 132.3, 131.9, 131.8,
131.7, 129.7, 129.7, 129.4, 128.6, 128.5, 128.5, 128.4, 128.3, 127.3, 124.4, 121.5, 114.1, 55.4,
21.5. IR (KBr) 3437, 1634, 1509, 1440, 1335, 1251, 1159, 1093, 1030, 935, 730, 698, 551cm-1.
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HRMS (ESI) m/z: [M + Na]+ Calcd for C41H34NO4PSNa 690.1838; found 690.1835.
N-(2-(3-(4-chlorophenyl)-1-(diphenylphosphoryl)-3-phenylpropa-1,2-dien-1-yl)phenyl)-4-
methylbenzenesulfonamide (5f):
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The resultant residue was purified by flash silica gel column chromatography to afford 5f as a
colourless liquid (28.5 mg, 42%); 1H NMR (400 MHz, CDCl3): 10.86 (s, 1H), 7.82 (d, J = 8.4 Hz,
2H), 7.69–7.64 (m, 4H), 7.46–7.43 (m, 2H), 7.38–7.36 (m, 2H), 7.33–7.29 (m, 8H), 7.16–7.12
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(m, 2H), 7.09–7.07 (m, 2H), 7.05–7.03 (m, 2H), 6.98–6.95 (m, 3H), 2.31 (s, 3H). C{H} NMR
(100 MHz, CDCl3): δ 211.9, 211.9, 142.9, 138.5, 137.0, 134.2, 133.8, 132.5, 132.5, 131.8,
131.7, 131.7, 131.6, 131.6, 129.6, 129.6, 129.5, 129.4, 128.8, 128.8, 128.6, 128.5, 128.4,
128.4, 127.2, 124.6, 121.9, 110.8, 110.7, 103.1, 102.2, 21.5. IR (KBr) 3439, 3060, 1923, 1595,
1490, 1440, 1269, 1235, 1160, 1120, 1093, 1016, 732, 699, 660 cm-1. HRMS (ESI) m/z: [M +
Na]+ Calcd for C40H31ClNO3PSNa 694.1343; found 694.1340.
N-(2-(3-([1,1'-biphenyl]-4-yl)-1-(diphenylphosphoryl)-3-phenylpropa-1,2-dien-1-
yl)phenyl)-4-methylbenzenesulfonamide (5g):
The resultant residue was purified by flash silica gel column chromatography to afford 5g as a
colourless liquid (59.2 mg, 82%); 1H NMR (400 MHz, CDCl3): 10.92 (s, 1H), 7.80 (d, J = 8.4 Hz,
2H), 7.72–7.66 (m, 4H), 7.64–7.58 (m, 4H), 7.47–7.42 (m, 4H), 7.38–7.36 (m, 4H), 7.34–7.31
(m, 5H), 7.22–7.20 (m, 1H), 7.13–7.10 (m, 5H), 7.02–7.00 (m, 2H), 6.98–6.94 (m, 1H), 2.26 (s,
3H). 13C{H} NMR (100 MHz, CDCl3): δ 212.3, 212.3, 142.8, 141.0, 140.2, 138.3, 137.0, 134.1,
133.0, 132.9, 132.4, 131.9, 131.9, 131.8, 131.7, 131.7, 131.6, 130.5, 129.6, 129.4, 129.3,
128.8, 128.7, 128.6, 128.5, 128.5, 128.4, 127.6, 127.3, 127.0, 125.2, 124.4, 121.5, 111.5,
111.4, 102.8, 101.8, 21.4. IR (KBr) 3434, 3058, 1630, 1598, 1489, 1440, 1378, 1234, 1160,
1120, 731, 697, 661, 546 cm-1. HRMS (ESI) m/z: [M + Na]+ Calcd for C46H36NO3PSNa
736.2046; found 736.2046.
(1-(3-hydroxyphenyl)-3,3-diphenylpropa-1,2-dien-1-yl)diphenylphosphine oxide (6):
The resultant residue was purified by flash silica gel column chromatography to afford 6 as a
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yellow solid; 1H NMR (400 MHz, CDCl3): 10.72 (s, 1H), 7.69–7.64 (m, 4H), 7.46–7.42 (m, 2H),
7.32–7.30 (m, 10H), 7.24–7.22 (m, 1H), 7.17–7.13 (m, 1H), 7.03–7.01 (m, 4H), 6.97–6.94 (m,
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1H), 6.79 (t, J = 7.6 Hz, 1H). C{H} NMR (100 MHz, CDCl3): δ 213.0, 212.9, 155.7, 155.7,
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134.1, 134.1, 132.5, 132.5, 131.8, 131.7, 131.6, 131.6, 130.4, 130.3, 129.3, 128.6, 128.5,
128.4, 128.2, 128.2, 128.1, 120.1, 119.5, 111.6, 111.5, 103.4, 102.4.
ASSOCIATED CONTENT
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Supporting Information
The Supporting Information is available free of charge on the ACS Publications website.
1H and 13C NMR spectra for all products (PDF)
X-ray crystallographic data for product 3a and 6 (CIF)
AUTHOR INFORMATION
Corresponding Author
*E-mail: liangym@lzu.edu.cn.
ORCID
Yong-Min Liang: 0000-0001-8280-8211
Notes
The authors declare no competing financial interest
ACKNOWLEDGMENTS
We thank the National Science Foundation (NSF 21472073 and 21532001)
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