Transition-metal-free C-P bond formation via decarboxylative phosphorylation of cinnamic acids with P(O)H compounds

Article abstract of DOI:10.1021/acs.joc.8b00187

A novel, transition-metal-free phosphorylation of cinnamic acids with P(O)H compounds has been developed via radical-promoted decarboxylation under mild conditions. This method provides simple, efficient, and versatile access to valuable (E)-alkenylphosphine oxides in satisfactory yields with a wide variety of substrates.

Full text of DOI:10.1021/acs.joc.8b00187

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Note
Transition-Metal-Free C–P Bond Formation via Decarboxylative
Phosphorylation of Cinnamic Acids with P(O)H Compounds
Lixin Liu, Dan Zhou, Jianyu Dong, Yongbo Zhou, Shuang-Feng Yin, and Li-Biao Han
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.8b00187 • Publication Date (Web): 02 Mar 2018
Downloaded from http://pubs.acs.org on March 2, 2018
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Transition-Metal-Free C–P Bond Formation via Decarboxylative
Phosphorylation of Cinnamic Acids with P(O)H Compounds
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Lixin Liu,† Dan Zhou,† Jianyu Dong,*,† Yongbo Zhou,*,† ShuangꢀFeng Yin† and LiꢀBiao Han‡
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†State Key Laboratory of Chemo/Biosensing and Chemometrics, College of Chemistry and Chemical Engineering,
Hunan University, Changsha 410082, China
‡National Institute of Advanced Industrial Science and Technology (AIST), Tsukuba, Ibaraki 305ꢀ8565, Japan
Eꢀmail: djyustc@hotmail.com; zhouyb@hnu.edu.cn.
Abstract: A novel, transitionꢀmetalꢀfree phosphorylation of cinnamic acids with P(O)H
compounds has been developed via radicalꢀpromoted decarboxylation under mild conditions.
This method provides simple, efficient and versatile access to valuable (E)ꢀalkenylphosphine
oxides in satisfactory yields with a wide variety of substrates.
Alkenylphosphorus compounds, an important class of C–P bondꢀcontaining
chemicals, are the primary building blocks of phosphorusꢀcontaining materials1 and
biologically active compounds.2 They are also extensively used as key precursors for
the preparation of valuable phosphine ligands.3 In addition, these Pꢀfunctionalized
vinyl compounds serve well as substrates to construct synthetically useful bifunctional
adducts by the addition of carbanion species,4 carbonꢀcentered radicals5 and
heteroatom nucleophiles6 to the C–C double bonds. Traditionally, the preparation of
alkenylphosphorus compounds relies on a transitionꢀmetalꢀcatalyzed crossꢀcoupling of
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P(O)H compounds with vinyl halides,7 Heckꢀtype coupling of vinylphosphonates with
various aryl partners8 or olefin crossꢀmetathesis.9 Since we reported an efficient
Pdꢀcatalyzed addition of P(O)H to alkynes,10 this reaction, catalyzed by Pd, Ni, and Cu
etc., has become one of the most straightforward and frequently used tools for the
synthesis of alkenylphosphorus compounds.11
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Alkenyl acids are commercially available and structurally diverse, which are widely
used as alternatives to halides and organometal reagents for the formation of C–C and
C–heteroatom bonds by decarboxylative synthetic strategies.12 In this regard, a few
methods towards C–P bond formation by decarboxylation of cinnamic acids with
P(O)–H bonds have been developed. In 2011, Yang’s group explored a Cuꢀcatalyzed
decarboxylative coupling of alkenyl acids with secondary phosphine oxides for the
synthesis of alkenyl phosphine oxides (Scheme 1).13 Gao and coworkers subsequently
reported
a
Niꢀcatalyzed decarboxylative coupling of alkenyl acids with
)ꢀalkenylphosphonates.14 Very recently these compounds
H
ꢀphosphonates to give (
E
have also been prepared by replacement of the Niꢀcatalytic system with Cu.15
Despite the usefulness of the above methods, common problems, such as relatively
strict reaction conditions, lack of stereoselectivity and the requirement of wellꢀdefined
ligands, increased the cost and complexity of these strategies and limited their
applications. Moreover, transition metals are required in these reactions, which are
difficult to remove from the alkenylphosphorus products due to their coordination
interactions. Therefore, a simple and transitionꢀmetalꢀfree method for the preparation
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of alkenylphosphorus compounds is highly desirable, especially for the phosphine
ligand precursors.
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Scheme 1. Decarboxylative Phosphorylation of Alkenyl Acids with P(O)H Compounds
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Herein, we report
a
novel, facile and transitionꢀmetalꢀfree synthesis of
(E)ꢀalkenylphosphine oxides by radicalꢀpromoted decarboxylative phosphorylation of
cinnamic acids with P(O)H compounds at room temperature. To our knowledge,
transitionꢀmetalꢀfree decarboxylative phosphorylation has not been realized. This mild and
transitionꢀmetalꢀfree procedure is greener, more attractive and more economical than existing
methods.
We commenced our studies with the reaction of cinnamic acid (1a, 0.2 mmol) and
diphenylphosphine oxide (2a, 0.28 mmol) in the presence of tertꢀbutyl hydroperoxide (TBHP,
2.0 equiv), KOAc (1.0 equiv) in dimethyl sulfoxide (DMSO) under nitrogen at room
temperature for 12 h. Gratifyingly, the desired decarboxylative phosphorylation product
(E)ꢀalkenyldiphenylphosphine oxide 3a was obtained in 26% yield (Table 1, entry 1). Next,
oxidants such as cumyl hydroperoxide (CHP), tertꢀbutyl peroxybenzoate (TBPB), K2S2O8,
H2O2 (30 wt.% in H2O) and O2 were examined (Table 1, entries 2–6), TBPB was remarkably
superior to the others, and a respectable yield (72%) of the desired product was gained (Table
1, entry 3). Other solvents including 1ꢀmethylꢀ2ꢀpyrrolidinone (NMP), acetonitrile, and
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N,Nꢀdimethylformamide (DMF) were inferior to DMSO (Table 1, entries 7–9). A series of
bases (NaOAc, LiOAc, CsOAc, Cs2CO3, K2HPO4 and Et3N) were also screened (Table 1,
entries 10–15), and the best yield was obtained with K2HPO4 (74%, Table 1, entry 14). In the
absence of base, the transformation did not proceed (Table 1, entry 16). The addition of KI to
the reaction mixture improved the performance of the reaction, giving 3a in 84% yield (Table
1, entry 17, vide infra). When other iodine reagents were examined, there was no obvious
improvement in the yield (Table 1, entries 18–20). Decreasing the loading of TBPB did not
give a satisfactory result (79% yield, entry 21). Increasing the temperature did not
significantly enhance the yield of this reaction (Table 1, entries 22 and 23).
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Table 1. Optimization of the Reaction Conditionsa
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aReaction conditions: 1a (0.2 mmol), 2a (0.28 mmol, 1.4 equiv), oxidant (2.0 equiv), base (1.0 equiv)
and additive (5 mol %) in solvent (0.5 mL) at room temperature under N2 for 12 h. b31P NMR yield
using tributyl phosphate as an internal standard. cIsolated yields. d1.7 equiv of TBPB. e50 °C
With the optimized conditions in hand, we then investigated the scope and generality of the
reaction. As shown in Table 2, this decarboxylative phosphorylation reaction worked for a
wide variety of substrates and had outstanding functional group tolerance, producing various
(E)ꢀalkenyl phosphine oxides in good to high yields with the stereoꢀconfiguration unchanged.
For cinnamic acids, functional groups such as methyl, phenyl, methoxyl, halogen, cyano,
trifluoromethyl and trifluoromethoxyl were all tolerated, and the corresponding products
(3a–l) were obtained in 66–83% yields, regardless of the electronic effect of substituent
groups. This phenomenon is probably dueto the different performance of the substituent
groups in the steps of free radical addition and decarboxylation in which the electronꢀdonating
groups facilitate the addition of Pꢀradical to cinnamic acids but disfavor the subsequent
decarboxylation reaction (vide infra). Versatile functional groups such as carboxyl, ester, and
acetoxyl were also compatible in this reaction system, albeit in moderate yields (3m–3o,
50–55%).
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Notably, the cinnamic acid moiety represented an absolute chemoselectivity over the
chlorine and bromine as leaving groups, producing the corresponding halogenated products
3h and 3i in 81 and 78% yields, respectively. Thus, this chemoselectivity may be applied for
further functionalization toward more complex targets via stepwise coupling reactions.
Sterically hindered naphthyl propenoic acids could also be used as substrates and gave
naphthyl alkenylphosphine oxides 3r and 3s in 50 and 48% yields, respectively. Compared
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with the reported transitionꢀmetalꢀcatalyzed decarboxylative C−P crossꢀcoupling reaction,13–15
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heterocyclicpropenoic acids containing
a pyridine ring were compatible for the
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transitionꢀmetalꢀfree reaction, which is probably due to the avoidance of detrimental
interactions between the N atom and the metal catalysts. The good yields of the corresponding
products 3t and 3u (66 and 70% yields, respectively) demonstrated the potential of this
protocol to access nitrogenꢀcontaining phosphine ligands. The sulfurꢀcontaining substrates
including methylthio and thiophene also worked well and gave the corresponding products 3p
and 3v in 53 and 47% yields, respectively. (E)ꢀ2ꢀMethylꢀ3ꢀphenylacrylic acid (1w) and
(E)ꢀ3ꢀmethylꢀ3ꢀphenylacrylic acid (1x), with a methyl on the alkenyl group, could also be
employed as substrates in the reaction to afford the expected products, albeit low yields were
attained (35% yield for 3w and 22% yield for 3x). Aliphatic alkenyl acids were not suited for
the reaction. For example, the reaction of 2ꢀcyclohexylideneacetic acid 1y with 2a gave
reductive product 3y in 18% yield (by 31P NMR); the low yield is probably attributedto the
instability of the radical of intermediate C (vide infra). As for the P(O)H compounds, both
phenyl and naphthyl secondary phosphine oxides worked well as the substrates.
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Di(4ꢀmethylphenyl)phosphine
oxide,
di(4ꢀmethoxyphenyl)phosphine
oxide,
di(4ꢀfluorophenyl)phosphine oxide and di(2ꢀnaphthyl)phosphine oxide were found to
smoothly react with cinnamic acids, leading to the corresponding (E)ꢀalkenylphosphine
oxides compounds 3z–zc in 63–80% yields. The aliphatic dicyclohexylphosphine oxide and
dibutylphosphine oxide also showed good reactivity (3zd and 3ze) when the reaction
temperature increased to 50 °C. In addition, Hꢀphosphinate as exemplified by
dibenzo[c,e][1,2]oxaphosphinine 6ꢀoxide, reacted smoothly in this catalytic system to
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generate the alkenyl phosphinate 3zf in 40% yield. Unfortunately, the decarboxylative
phosphorylation of diethyl phosphonate proceeded sluggishly (3zg, yield: 13%) under similar
reaction conditions.
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Table 2. Decarboxylative Phosphorylation of Alkenyl Acids with P(O)H Compoundsa
TBPB (2.0 equiv)
O
P R2
R2
2
O
R1
KI (5.0 mol %)
K2HPO4 (1.0 equiv)
DMSO, rt, N2
R1
+
H
P
R2
COOH
R2
1
3
3a, R = 4-H, 80% 3i, R= 3-Br,
3b, R = 4-Me, 72% 3j, R = 4-CN,
3c, R = 3-Me, 79% 3k, R = 4-CF3,
3d, R = 2-Me, 76% 3l, R = 4-CF3O,
78%
82%
83%
78%
O
P
Ph
Ph
3e, R = 4-Ph 66% 3m, R = 4-COOH, 55%
3f, R = 3-OMe, 73% 3n, R = 4-COOMe, 50%
3g, R = 4-F, 80% 3o, R = 4-OC(O)Me, 52%
R
3a-p
3h, R = 4-Cl, 81% 3p, R = 4-SMe,
53%
O
O
Ph
Ph
P
O
P
O
Ph
Ph
P
O
Ph
Ph
3s,48%
3q 71%
3r, 50%
O
O
O
Ph
Ph
Ph
P
P
P
Ph
Ph
Ph
N
S
N
3t, 66%
3u, 70%
3v, 47%
O
O
Ph
Ph
O
P
P
P
Ph
Ph
3y, 18%b
Ph
Ph
3w, 35%
3x, 22%
O
P
O
C6H4-Me-p
C6H4-Me-p
C6H4-OMe-p
C6H4-OMe-p
P
3z, 80%
3za, 76%
O
P
O
C6H4-F-p
C6H4-F-p
naphthyl-2
P
naphthyl-2
3zb, 70%
3zc, 63%
O
O
P
cyclohexyl
Bu-n
Bu-n
P
cyclohexyl
3zd, 48%c
3ze, 46%c
O
P
OEt
OEt
P
O
O
3zg, 13%b
3zf, 40%
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aReaction conditions: 1 (0.2 mmol), 2 (0.28 mmol), KI (5 mol%), K2HPO4 (1.0 equiv), TBPB (2.0
equiv) in DMSO (0.5 mL) at roomꢀtemperature under N2 for 12 h. b31P NMR yield using tributyl
phosphate as an internal standard. c50 °C.
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To further extend the scope of this reaction, the decarboxylative phosphorylation was
carried out on much larger scales (1 mmol and 10 mmol). The comparable yields (0.24 g, 78%
yield for 1 mmol scale and 2.13 g, 70% yield for 10 mmol scale) of the product clearly
demonstrated the synthetic value of the procedure in organic synthesis (Scheme 2).
Scheme 2. Preparation of Alkenylphosphorus Compounds at 1 and 10 mmol Scale
It is worth noting that this transitionꢀmetalꢀfree reaction can be applied to modify highly
functionalized molecules, further demonstrating the potential application of this method in
drug discovery and the synthesis of natural products. For example, the estrone derivative 1zh,
a clinic steroidal progestin with estrogenic activity, was successfully phosphorylated under
the present reaction conditions, producing the corresponding phosphorylation product 3zh in
50% yield (Scheme 3).
Scheme 3. Application in the Late-stage Modification of Bioactive Estrone Derivative
To gain insight into the reaction mechanism, several control experiments were carried out
under standard conditions. First, the radical inhibitors 2,2,6,6ꢀtetramethylpiperidine Nꢀoxide
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(TEMPO) and 2,6ꢀdiꢀtertꢀbutylꢀ4ꢀmethylphenol (BHT) blocked this reaction, suggesting that
a freeꢀradical mechanism was probably involved in this reaction (Scheme 4, eq. 1). Indeed,
the radical adduct 1ꢀ(tertꢀbutylperoxy)ꢀ2,2,6,6ꢀtetramethylpiperidine 4 was observed by the
treatment of 2.0 equiv of TEMPO under standard conditions for 2 h (Scheme 4, eq. 2). In
addition, conducting the reaction in the presence of the radical trap 1,1ꢀdiphenylethylene gave
(2ꢀ(tertꢀbutoxy)etheneꢀ1,1ꢀdiyl)dibenzene 5 and triphenylethylene 6 (Scheme 4, eq. 3; for
details, see the SI), indicating the formation of tertꢀbutoxyl and phenyl radicals (from the
decarboxylation of the benzoyloxyl radical).
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Scheme 4. Control Experiments
On the basis of the experimental results above and literature precedent,15,16 a general
mechanism is illustrated in Scheme 5. Initially, tertꢀbutoxyl and benzoyloxyl radicals are
generated from the decomposition of TBPB, which is promoted with the assistance of the
iodide anion.16c Then, the tertꢀbutoxyl or benzoyloxyl radical snatches the hydrogen of
H(O)PPh2 to form the phosphorus radical A, followed by radical addition to the cinnamic acid
anion B (formed from the reaction of cinnamic acid with a base), which leads to the radical
intermediate C. Finally, decarboxylation of C, followed by singleꢀelectron oxidation of the
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radical anion, affords the final products (E)ꢀalkenylphosphine oxides 3 (Scheme 5a). As
outlined in Scheme 5b, the excellent E/Z selectivity might originate from stereoelectronic and
steric effects in the radical anion.16e
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Scheme 5. Possible Reaction Mechanism and Explanation for Z/E Selectivity
In summary, we have successfully developed a transitionꢀmetalꢀfree synthesis of
alkenylphosphorus compounds under simple and mild conditions through radicalꢀpromoted
decarboxylative phosphorylation of cinnamic acids with P(O)H compounds. This reaction
provides a new and highly efficient pathway for the formation of Csp2–P bonds and produced
a broad spectrum of (E)ꢀalkenylphosphine oxides in satisfactory yields. The advantages of
this method (simplicity, lack of transition metals, efficient scalability and the synthesis of a
highly modified estrone derivative) clearly demonstrate its potential as a superior synthetic
method for both academia and industry.
EXPERIMENTAL SECTION
General Information
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The reactions were carried out in 10ꢀmL Schlenk tubes under N2. Reagents were used as received
unless otherwise noted, and solvents were purified according to standard operating procedures. Column
chromatography was performed using Silica Gel 60 (300‒400 mesh). The reactions were monitored by
GC and GCꢀMS; GCꢀMS results were recorded on a GCꢀMS QP2010, and GC analyses were
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performed on a GC 2014 plus. The H, 13C NMR, 31P NMR and 19F NMR spectra were recorded on a
Brucker ADVANCE III spectrometer operating at 400 MHz, 100 MHz, 162 MHz and 372 MHz,
respectively; chemical shifts were reported in parts per million (ppm). The electron ionization (EI)
method was used as the ionization method for HRMS measurements, and TOF was the mass analyzer
type for EI.
Synthesis of Starting Materials
α,βꢀUnsaturated carboxylic acids (1e, 1m, 1n, 1s, 1x, 1y) were prepared according to the literature
procedure.17a Piperidine (0.15 mL, 1.5 mmol) was added to a solution of the appropriate aldehyde (10
mmol) and malonic acid (1.35 g, 13 mmol) in pyridine (10 mL). The mixture was refluxed for 5 h,
cooled to room temperature and neutralized with 1M hydrochloric acid in an ice bath. The resulting
precipitate was filtered, washed with cold water and dried.
The estrone derivative acids 1zh were prepared in accordance with methods described in the
references.17b
General Experimental Procedure for the Synthesis of (E)-alkenylphosphinate oxides
An ovenꢀdried 10ꢀmL Schlenk tube, equipped with a magnetic stir bar and charged with cinnamic
acids 1 (0.2 mmol), KI (1.7 mg, 0.01 mmol, 5 mol% ), K2HPO4 (34.8 mg, 0.2 mmol, 1.0 equiv), and 2
(0.28 mmol, 1.4 equiv), was evacuated and backfilled with N2 three times. A premixed solution of
DMSO (0.5 mL) and tertꢀButyl peroxybenzoate (0.4 mmol, 2.0 equiv) was then added. The reaction
mixture was stirred at room temperature for 12 h and monitored by GC or GCꢀMS. Upon completion,
the reaction mixture was diluted with EtOAc and washed with H2O. The organic layer was dried with
anhydrous Na2SO4, filtered and concentrated in vacuo. The residue was purified by column
chromatography over silica gel using petroleum ether/ethyl acetate (2:1) to afford the pure products 3.
Preparation of (E)-alkenylphosphinate oxides at gram-scales
1 mmol gram-scales: an ovenꢀdried 25ꢀmL Schlenk tube, equipped with a magnetic stir bar and
charged with cinnamic acids 1a (148 mg, 1.0 mmol), KI (8.5 mg, 5 mol%), K2HPO4 (174 mg, 1.0
equiv), and diphenylphosphine oxide 2a (283 mg, 1.4 equiv), was evacuated and backfilled with N2
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three times. A premixed solution of DMSO (2.5 mL) and tertꢀButyl peroxybenzoate (380 ꢁL, 2.0 equiv)
was then added. The reaction mixture was stirred at room temperature for 16 h. Upon completion, the
reaction mixture was diluted with EtOAc and washed with H2O. The organic layer was dried with
anhydrous Na2SO4, filtered and concentrated in vacuo. The crude product was purified by column
chromatography on silica gel with ethyl acetate/petroleum ether (1:2) to afford white solid (E)ꢀstyryl
diphenylphosphine oxide 3a in 78% yield (0.24 g).
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10 mmol gram-scales: an ovenꢀdried 100ꢀmL Schlenk tube, equipped with a magnetic stir bar and
charged with cinnamic acids 1a (1.48 g, 10 mmol), KI (85 mg, 5 mol% ), K2HPO4 (1.74 g, 1.0 equiv),
and diphenylphosphine oxide 2a (2.83 g, 1.4 equiv), was evacuated and backfilled with N2 three times.
A premixed solution of DMSO (25 mL) and tertꢀButyl peroxybenzoate (3.80 mL, 2.0 equiv) was then
added. The reaction mixture was stirred at room temperature for 24 h. Upon completion, the reaction
mixture was diluted with EtOAc and washed with H2O. The organic layer was dried with anhydrous
Na2SO4, filtered and concentrated in vacuo. The crude product was purified by column
chromatography on silica gel with ethyl acetate/petroleum ether (1: 2) to afford white solid (E)ꢀstyryl
diphenylphosphine oxide 3a in 70% yield (2.13 g).
1H, 13C and 31PNMR Spectral Data of the Products
(E)ꢀStyryl diphenylphosphine oxide (3a).18a White solid; yield: 48.6 mg, 80%. 1H NMR (400 MHz,
CDCl3): δ 7.77‒7.72 (m, 4H), 7.53‒7.45 (m, 9H), 7.37‒7.36 (m, 3H), 6.83 (dd, J = 18.0, 22.4 Hz, 1H).
13C{1H} NMR (100 MHz, CDCl3): δ 147.5 (d, JCꢀP = 3.8 Hz), 135.1 (d, JCꢀP = 17.7 Hz), 132.9 (d, JCꢀP
=
105.9 Hz), 131.8 (d, JCꢀP = 2.7 Hz), 131.3 (d, JCꢀP = 10.0 Hz), 130.0, 128.8, 128.6 (d, JCꢀP = 12.1 Hz),
127.7, 119.2 (d, JCꢀP = 104.3 Hz). 31P NMR (162 MHz, CDCl3): δ 24.52.
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(E)ꢀ(4ꢀMethylstyryl)diphenylphosphine oxide (3b).18a White solid; yield: 45.8 mg, 72%. H NMR
(400 MHz, CDCl3): δ 7.77‒7.72 (m, 4H), 7.54‒7.40 (m, 9H), 7.17 (d, J = 7.6 Hz, 2H), 6.77 (d, J = 17.6,
22.4 Hz, 1H), 2.35 (s, 3H). 13C{1H} NMR (100 MHz, CDCl3): δ 147.5 (d, JCꢀP = 3.8 Hz), 140.4, 133.0
(d, JCꢀP = 105.8 Hz), 132.4 (d, JCꢀP = 18.0 Hz), 131.7 (d, JCꢀP = 2.6 Hz), 131.3 (d, JCꢀP = 10.0 Hz), 129.5,
128.5 (d, JCꢀP = 12.1 Hz), 127.7, 117.8 (d, JCꢀP = 105.5 Hz), 21.3. 31P NMR (162 MHz, CDCl3): δ 24.83.
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(E)ꢀ(3ꢀMethylstyryl)diphenylphosphine oxide (3c).18a White solid; yield: 50.2 mg, 79%. H NMR
(400 MHz, CDCl3): δ 7.79‒7.75 (m, 4H), 7.56‒7.44 (m, 7H), 7.35‒7.27 (m, 3H), 7.19 (d, J = 7.2 Hz,
1H), 6.84 (dd, J = 17.4, 22.4 Hz, 1H), 2.37 (s, 3H). 13C{1H} NMR (100 MHz, CDCl3): δ 147.6 (d, JCꢀP
= 3.7 Hz), 138.4, 134.9 (d, JCꢀP = 17.9 Hz), 132.8 (d, JCꢀP = 105.8 Hz), 131.7 (d, JCꢀP = 2.7 Hz), 131.2 (d,
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JCꢀP = 9.9 Hz), 130.8, 128.6, 128.5 (d, JCꢀP = 12.1 Hz), 128.2, 124.9, 118.8 (d, JCꢀP = 104.8 Hz), 21.2.
31P NMR (162 MHz, CDCl3): δ 24.70.
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(E)ꢀ(2ꢀMethylstyryl)diphenylphosphine oxide (3d).18a White solid; yield: 48.3 mg, 76%. H NMR
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(400 MHz, CDCl3): δ 7.81‒7.71 (m, 5H), 7.59‒7.46 (m, 7H), 7.27‒7.17 (m, 3H), 6.77 (d, J = 17.2, 23.2
Hz, 1H), 2.37 (s, 3H). 13C{1H} NMR (100 MHz, CDCl3): δ 145.4 (d, JCꢀP = 3.9 Hz), 137.2, 134.2 (d,
JCꢀP = 17.3 Hz), 133.0 (d, JCꢀP = 105.6 Hz), 131.8 (d, JCꢀP = 2.7 Hz), 131.3 (d, JCꢀP = 9.9 Hz), 130.7,
129.7, 128.5 (d, JCꢀP = 12.1 Hz), 126.2, 126.1, 120.5 (d, JCꢀP = 104.0 Hz), 19.6. 31P NMR (162 MHz,
CDCl3): δ 24.61.
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(E)ꢀ(4ꢀPhenylstyryl)diphenylphosphine oxide (3e). White solid; yield: 50.1 mg, 66%; mp
171−172 °C. 1H NMR (400 MHz, CDCl3): δ 7.79‒7.73 (m, 4H), 7.60‒7.56 (m, 6H), 7.54‒7.42 (m, 9H),
7.37‒7.34 (m, 1H), 6.87 (d, J = 17.2, 22.0 Hz, 1H). 13C{1H} NMR (100 MHz, CDCl3): δ 147.0 (d, JCꢀP
= 3.6 Hz), 142.8, 140.1, 134.0 (d, JCꢀP = 17.9 Hz), 132.9 (d, JCꢀP = 105.9 Hz), 131.8 (d, JCꢀP = 2.7 Hz),
131.3 (d, JCꢀP = 10.0 Hz), 130.6 (d, JCꢀP = 11.4 Hz), 128.8, 128.6 (d, JCꢀP = 12.1 Hz), 127.8 (d, JCꢀP
=
77.1 Hz), 127.7, 127.0, 119.0 (d, JCꢀP = 104.5 Hz). 31P NMR (162 MHz, CDCl3): δ 24.80. HRMS (ESI)
m/z: [M]+ calcd for C26H21OP 380.1330; found 380.1334.
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(E)ꢀ(3ꢀMethoxystyryl)diphenylphosphine oxide (3f).13 White solid; yield: 48.7 mg, 73%. H NMR
(400 MHz, CDCl3): δ 7.79‒7.74 (m, 4H), 7.54‒7.40 (m, 7H), 7.30‒7.27 (m, 1H), 7.12 (d, J = 8.0 Hz,
1H), 7.05 (s, 1H), 6.92‒6.79 (m, 2H), 3.80 (s, 3H). 13C{1H} NMR (100 MHz, CDCl3): δ 159.8, 147.5
(d, JCꢀP = 3.7 Hz), 136.3 (d, JCꢀP = 18.0 Hz), 132.5 (d, JCꢀP = 106.4 Hz), 131.8 (d, JCꢀP = 2.6 Hz), 131.3
(d, JCꢀP = 10.0 Hz), 129.7, 128.5 (d, JCꢀP = 12.2 Hz), 120.3, 119.2 (d, JCꢀP = 104.5 Hz), 115.8, 112.7,
55.2. 31P NMR (162 MHz, CDCl3): δ 25.12.
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(E)ꢀ(4ꢀFluorostyryl)diphenylphosphine oxide (3g).18a White solid; yield: 51.5 mg, 80%. H NMR
(400 MHz, CDCl3): δ 7.76‒7.71 (m, 4H), 7.56‒7.41 (m, 9H), 7.34 (t, J =8.0 Hz, 2H), 6.75 (d, J = 17.6,
22.0 Hz, 1H). 13C{1H} NMR (100 MHz, CDCl3): δ 163.7 (d, JCꢀF = 251.0 Hz), 146.2 (d, JCꢀP = 3.7 Hz),
132.8 (d, JCꢀP = 106.0 Hz), 131.8 (d, JCꢀF = 2.7 Hz), 131.4 (d, JCꢀP = 3.3 Hz), 131.3 (d, JCꢀP = 10.0 Hz),
129.5 (d, JCꢀF = 8.5 Hz), 128.6 (d, JCꢀP = 12.2 Hz), 118.9 (d, JCꢀF = 104.4 Hz), 115.9 (d, JCꢀP = 21.9 Hz).
31P NMR (162 MHz, CDCl3): δ 24.41. 19F NMR (376 MHz, CDCl3): δ ꢀ109.98.
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(E)ꢀ(4ꢀChlorostyryl)diphenylphosphine oxide (3h).18a White solid; yield: 54.7 mg, 81%. H NMR
(400 MHz, CDCl3): δ 7.76‒7.71 (m, 4H), 7.56‒7.41 (m, 9H), 7.34 (d, J = 7.6 Hz, 2H), 6.81 (d, J = 17.6,
22.0 Hz, 1H). 13C{1H} NMR (100 MHz, CDCl3): δ 146.0 (d, JCꢀP = 3.8 Hz), 135.9, 133.5 (d, JCꢀP = 18.0
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Hz), 132.6 (d, JCꢀP = 106.1 Hz), 131.9 (d, JCꢀP = 2.7 Hz), 131.3 (d, JCꢀP = 10.0 Hz), 129.0, 128.9, 128.6
(d, JCꢀP = 12.2 Hz), 119.9 (d, JCꢀP = 103.7 Hz). 31P NMR (162 MHz, CDCl3): δ 24.26.
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(E)ꢀ(3ꢀBromostyryl)diphenylphosphine oxide (3i).13 White solid; yield: 59.6 mg, 78%. H NMR
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(400 MHz, CDCl3): δ 7.77‒7.67 (m, 5H), 7.55‒7.22 (m, 9H), 7.26‒7.22 (m, 1H), 6.86 (d, J = 17.6, 22.0
Hz, 1H). 13C{1H} NMR (100 MHz, CDCl3): δ 145.8 (d, JCꢀP = 3.7 Hz), 137.1 (d, JCꢀP = 18.0 Hz), 132.9,
132.8, 132.0 (d, JCꢀP = 2.7 Hz), 131.8, 131.2 (d, JCꢀP = 10.0 Hz), 130.25 (d, JCꢀP = 16.8 Hz), 128.65 (d,
JCꢀP = 12.3 Hz), 126.6, 122.9, 121.0 (d, JCꢀP = 103.0 Hz). 31P NMR (162 MHz, CDCl3): δ 24.30.
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(E)ꢀ(4ꢀCyano)styryl diphenylphosphine oxide (3j).18a White solid; yield: 53.9 mg, 82%. H NMR
(400 MHz, CDCl3): δ 7.50‒7.70 (m, 4H), 7.64‒7.52 (m, 7H), 7.48‒7.46 (m, 4H), 6.97 (dd, J = 17.6,
21.6 Hz, 1H). 13C{1H} NMR (100 MHz, CDCl3): δ 145.0 (d, JCꢀP = 3.6 Hz), 139.1 (d, JCꢀP = 18.0 Hz),
132.5, 132.12 (d, JCꢀP = 2.7 Hz), 132.1 (d, JCꢀP = 106.5 Hz), 131.2 (d, JCꢀP = 10.1 Hz), 128.7 (d, JCꢀP
12.2 Hz), 128.1, 123.7 (d, JCꢀP = 101.0 Hz), 118.2, 113.1. 31P NMR (162 MHz, CDCl3): δ 23.59.
=
(E)ꢀ(4ꢀ(Trifluoromethyl)styryl)diphenylphosphine oxide (3k).18a Yellow oil; yield: 61.7 mg, 83%.
1H NMR (400 MHz, CDCl3): δ 7.70‒7.65 (m, 4H), 7.52 (m, 4H), 7.48‒7.37 (m, 7H), 6.89 (d, J = 17.6,
22.0 Hz, 1H). 13C{1H} NMR (100 MHz, CDCl3): δ 145.7 (d, JCꢀP = 3.5 Hz), 138.2 (d, JCꢀP = 17.6 Hz),
132.2 (d, JCꢀP = 106.6 Hz), 132.0 (q, JCꢀF = 34.0 Hz), 131.2 (d, JCꢀP = 10.1 Hz), 128.8 (d, JCꢀP = 174.7
Hz), 128.6 (d, JCꢀP = 12.3 Hz), 127.8, 125.7 (q, JCꢀF = 3.5 Hz), 123.72 (d, JCꢀF = 272.2 Hz), 122.26 (d,
JCꢀP = 102.3 Hz). 31P NMR (162 MHz, CDCl3): δ 24.28. 19F NMR (376 MHz, CDCl3): δ ꢀ62.77.
(E)ꢀ(4ꢀ(Trifluoromethoxy)styryl)diphenylphosphine oxide (3l).18a Yellow oil; yield: 60.5 mg, 78%.
1H NMR (400 MHz, CDCl3): δ 7.78‒7.74 (m, 4H), 7.56‒7.47 (m, 9H), 7.21 (d, J = 8.0 Hz, 2H), 6.86
(dd, J = 17.6, 21.6 Hz, 1H). 13C{1H} NMR (100 MHz, CDCl3): δ 150.1, 145.6 (d, JCꢀP = 3.6 Hz), 133.6
(d, JCꢀP = 18.1 Hz), 132.4 (d, JCꢀP = 106.4 Hz), 131.9 (d, JCꢀP = 2.6 Hz), 131.2 (d, JCꢀP = 10.0 Hz), 129.1,
128.5 (d, JCꢀP = 12.2 Hz), 120.9, 120.3 (d, JCꢀP = 103.4 Hz), 120.2 (d, JCꢀF = 257.8 Hz). 31P NMR (162
MHz, CDCl3): δ 24.31. 19F NMR (376 MHz, CDCl3): δ ꢀ57.77.
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(E)ꢀ4ꢀ(2ꢀ(diphenylphosphoryl)vinyl)benzoic acid (3m).18a Yellow solid; yield: 38.3 mg, 55%. H
NMR (400 MHz, d6ꢀDMSO): δ 13.06 (br, 1H), 7.93 (d, J = 7.6 Hz, 2H), 7.83 (d, J = 7.6Hz, 2H),
7.77‒7.72 (m, 4H), 7.67‒7.61 (m, 1H), 7.56‒7.44 (m, 7H). 13C{1H} NMR (100 MHz, d6ꢀDMSO): δ
166.8, 144.7 (d, JCꢀP = 2.8 Hz), 139.0 (d, JCꢀP = 17.9 Hz), 133.8 (d, JCꢀP = 103.8 Hz), 131.82 (d, JCꢀP
=
2.1 Hz), 131.7, 130.70 (d, JCꢀP = 9.8 Hz), 129.7, 128.7 (d, JCꢀP = 11.8 Hz), 128.1, 123.4 (d, JCꢀP = 99.5
Hz). 31P NMR (162 MHz, d6ꢀDMSO): δ 27.70.
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(E)ꢀ(4ꢀmethoxylcarbonyl)styryl diphenylphosphine oxide (3n).7d White solid; yield: 36.2 mg, 50%.
1H NMR (400 MHz, CDCl3): δ 8.02 (d, J = 8.0 Hz, 2H), 7.77‒7.72 (m, 4H), 7.59‒7.45 (m, 9H), 6.96
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(dd, J =17.6, 21.6 Hz, 1H). 3.89 (s, 3H). 13C{1H} NMR (100 MHz, CDCl3): δ 166.3, 146.1 (d, JCꢀP
3.6 Hz), 139.1 (d, JCꢀP = 17.9 Hz), 132.3 (d, JCꢀP = 106.4 Hz), 132.0 (d, JCꢀP = 2.5 Hz), 131.30 (d, JCꢀP
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10.0 Hz), 131.1, 130.0, 128.6 (d, JCꢀP = 12.2 Hz), 127.6, 122.0 (d, JCꢀP = 102.4 Hz), 52.2. 31P NMR (162
MHz, CDCl3): δ 24.35.
(E)ꢀ(4ꢀAcetoxylstyryl)diphenylphosphine oxide (3o). White solid; yield: 37.6 mg, 52%; mp
157−158 °C. 1H NMR (400 MHz, CDCl3): δ 7.75‒7.70 (m, 4H), 7.53‒7.46 (m, 9H), 7.10 (d, J = 8.0Hz,
2H), 6.78 (dd, J =17.6, 22.0 Hz, 1H), 2.29 (s, 3H). 13C{1H} NMR (100 MHz, CDCl3): δ 169.1, 151.8,
146.3 (d, JCꢀP = 3.7 Hz), 132.8 (d, JCꢀP = 18.1 Hz), 132.7 (d, JCꢀP = 106.1 Hz), 131.8 (d, JCꢀP = 2.6 Hz),
131.3 (d, JCꢀP = 10.0 Hz), 128.8, 128.59 (d, JCꢀP = 12.1 Hz), 122.0, 119.4 (d, JCꢀP = 104.1 Hz), 21.0. 31
P
NMR (162 MHz, CDCl3): δ 24.35. HRMS (ESI) m/z: [M]+ calcd for C22H19O3P 362.1072; found
380.1070.
(E)ꢀ(4ꢀ(Methylthio)styryl)diphenylphosphine oxide (3p). White solid; yield: 37.1 mg, 53%; mp
162−163 °C. 1H NMR (400 MHz, CDCl3): δ 7.76‒7.71 (m, 4H), 7.54‒7.38 (m, 9H), 7.20 (d, J = 8.0 Hz,
2H), 6.76 (dd, J = 17.6, 22.0 Hz, 1H), 2.47 (s, 3H). 13C{1H} NMR (100 MHz, CDCl3): δ 146.8 (d, JCꢀP
= 3.8 Hz), 141.5, 132.9 (d, JCꢀP = 105.9 Hz), 131.8 (d, JCꢀP = 2.6 Hz), 131.6 (d, JCꢀP = 18.4 Hz), 131.3 (d,
JCꢀP = 10.0 Hz), 128.5 (d, JCꢀP = 12.1 Hz), 128.0, 125.9, 117.9 (d, JCꢀP = 105.2 Hz), 15.1. 31P NMR (162
MHz, CDCl3): δ 24.70. HRMS (ESI) m/z: [M]+ calcd for C21H19OPS 350.0894; found 350.0897.
(E)ꢀ(2ꢀ(benzo[d][1,3]dioxolꢀ5ꢀyl)vinyl)diphenylphosphine oxide (3q).13 White solid; yield: 49.4 mg,
71%. 1H NMR (400 MHz, CDCl3): δ 7.75‒7.71 (m, 4H), 7.54‒7.42 (m, 6H), 7.36 (d, J = 18.4 Hz, 1H),
7.04 (s, 1H), 6.97 (d, J = 8.0 Hz, 1H), 6.78 (d, J = 8.0 Hz, 1H), 6.62 (dd, J = 17.6, 22.0 Hz, 1H), 5.98 (s,
2H). 13C{1H} NMR (100 MHz, CDCl3): δ 149.3, 148.2, 147.0 (d, JCꢀP = 4.0 Hz), 133.0 (d, JCꢀP = 105.7
Hz), 131.7 (d, JCꢀP = 2.6 Hz), 131.3 (d, JCꢀP = 9.9 Hz), 129.6 (d, JCꢀP = 18.5 Hz), 128.5 (d, JCꢀP = 12.1
Hz), 123.8 , 116.6 (d, JCꢀP = 105.8 Hz), 108.4, 106.3, 101.4. 31P NMR (162 MHz, CDCl3): δ 24.67.
(E)ꢀ(2ꢀ(Naphthalenꢀ1ꢀyl)vinyl)diphenylphosphine oxide (3r).18a White solid; yield: 35.4 mg, 50%.
1H NMR (400 MHz, CDCl3): δ 8.39‒8.30 (m, 1H), 8.12 (d, J = 8.0Hz, 1H), 7.87‒7.76 (m, 7H),
7.57‒7.45 (m, 9H), 6.96 (dd, J = 17.2, 23.2 Hz, 1H). 13C{1H} NMR (100 MHz, CDCl3): δ 144.9 (d, JCꢀP
= 4.0 Hz), 133.5, 132.8 (d, JCꢀP = 105.7 Hz), 132.7 (d, JCꢀP = 17.5 Hz), 131.9 (d, JCꢀP = 2.7 Hz), 131.3 (d,
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JCꢀP = 10.0 Hz), 131.0, 130.2, 128.6 (d, J = 12.3 Hz). 126.7, 126.1, 125.3, 124.71, 124.70, 123.2,
122.40 (d, JCꢀP = 102.9 Hz). 31P NMR (162 MHz, CDCl3): δ 24.49.
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(E)ꢀ(2ꢀ(Naphthalenꢀ2ꢀyl)vinyl)diphenylphosphine oxide (3s).13 White solid; yield: 34.0 mg, 48%.
1H NMR (400 MHz, CDCl3): δ 7.90 (s, 1H), 7.84‒7.61 (m, 9H), 7.56‒7.39 (m, 8H), 6.95 (dd, J = 17.6,
22.0 Hz, 1H). 13C{1H} NMR (100 MHz, CDCl3): δ 147.6 (d, JCꢀP = 3.8 Hz), 134.0, 133.2 (d, JCꢀP = 15.4
Hz), 132.4 (d, JCꢀP = 18.2 Hz), 132.3, 131.8 (d, JCꢀP = 2.6 Hz), 131.3 (d, JCꢀP = 10.0 Hz), 129.3, 128.6,
128.56 (d, JCꢀP = 6.3 Hz), 128.55, 127.7, 127.1, 126.6, 123.3, 119.2 (d, JCꢀP = 104.7 Hz). 31P NMR (162
MHz, CDCl3): δ 24.96.
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(E)ꢀ(2ꢀ(Pyridinꢀ2ꢀyl)vinyl)diphenylphosphine oxide (3t).7d Pale yellow solid; yield: 40.3 mg, 66%.
1H NMR (400 MHz, d6ꢀDMSO): δ 7.64 (d, J = 4.0 Hz, 1H), 6.87‒6.71 (m, 7H), 6.61‒6.47 (m, 7H),
6.40‒6.37 (m, 1H). 13C{1H} NMR (100 MHz, d6ꢀDMSO): δ 152.6 (d, JCꢀP = 18.4 Hz), 149.8, 145.6 (d,
JCꢀP = 3.5 Hz), 137.3, 133.4 (d, JCꢀP = 104.1 Hz), 131.9, 130.7 (d, JCꢀP = 9.8 Hz), 128.8 (d, JCꢀP = 11.8
Hz), 124.6 (d, JCꢀP = 99.8 Hz), 124.5, 124.0. 31P NMR (162 MHz, d6ꢀDMSO): δ 20.97.
(E)ꢀ(2ꢀ(Pyridinꢀ3ꢀyl)vinyl)diphenylphosphine oxide (3u). White solid; yield: 42.7 mg, 70%; mp
190−191 °C. 1H NMR (400 MHz, CDCl3): δ 8.74 (s, 1H), 8.58 (d, J = 4.0 Hz, 1H), 7.83 (d, J = 8.0 Hz,
1H), 7.77‒7.72 (m, 4H), 7.54‒7.47 (m, 7H), 7.33‒7.30 (m, 1H), 6.94 (dd, J = 17.6, 21.6 Hz, 1H).
13C{1H} NMR (100 MHz, CDCl3): δ 150.7, 149.2, 143.8 (d, JCꢀP = 3.8 Hz), 134.1, 132.3 (d, JCꢀP
=
106.5 Hz), 132.1 (d, JCꢀP = 2.7 Hz), 131.3 (d, JCꢀP = 10.0 Hz), 128.7 (d, JCꢀP = 12.2 Hz), 123.6, 122.5,
121.5. 31P NMR (162 MHz, CDCl3): δ 23.90. HRMS (ESI) m/z: [M]+ calcd for C19H16NOP 305.0970;
found 305.0973.
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(E)ꢀ(2ꢀ(Thiophenꢀ2ꢀyl)vinyl)diphenylphosphine oxide (3v).18a White solid; yield: 29.1 mg, 47%. H
NMR (400 MHz, CDCl3): δ 7.75‒7.71 (m, 4H), 7.62‒7.46 (m, 7H), 7.34 (d, J = 4.4 Hz, 1H), 7.10 (s,
1H), 7.01 (m, 1H), 6.57 (dd, J = 17.2, 21.2 Hz, 1H). 13C{1H} NMR (100 MHz, CDCl3): δ 140.8, 140.6,
139.8 (d, JCꢀP = 4.3 Hz), 132.8 (d, JCꢀP = 106.5 Hz), 131.8 (d, JCꢀP = 2.7 Hz), 131.3 (d, JCꢀP = 10.0 Hz),
130.0, 128.6 (d, JCꢀP = 12.2 Hz), 128.0, 117.67 (d, JCꢀP = 105.9 Hz). 31P NMR (162 MHz, CDCl3): δ
24.22.
(E)ꢀdiphenyl(1ꢀphenylpropꢀ1ꢀenꢀ2ꢀyl)phosphine oxide (3w).18b White solid; yield: 22.3 mg, 35%.
1H NMR (400 MHz, CDCl3): δ 7.78‒7.73 (m, 4H), 7.58‒7.47 (m, 6H), 7.38‒7.26 (m, 5H), 7.22 (d, J =
22.0 Hz, 1H), 2.11 (d, J = 14.0 Hz, 3H). 13C{1H} NMR (100 MHz, CDCl3): δ 142.6 (d, JCꢀP = 10.8 Hz),
135.7 (d, JCꢀP = 19.0 Hz), 132.0 (d, JCꢀP = 9.6 Hz), 131.9 (d, JCꢀP = 2.7 Hz), 131.1 (d, JCꢀP = 102.3 Hz),
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130.1 (d, JCꢀP = 97.0 Hz), 129.3, 128.6, 128.5, 128.3 (d, JCꢀP = 3.2 Hz), 15.03 (d, JCꢀP = 10.8 Hz). 31P
NMR (162 MHz, CDCl3): δ 33.62.
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(E)ꢀdiphenyl(2ꢀphenylpropꢀ1ꢀenꢀ1ꢀyl)phosphine oxide (3x).7d Colorless oil; yield: 14.0 mg, 22%.
1H NMR (400 MHz, CDCl3): δ 7.80‒7.75 (m, 4H), 7.49‒7.34 (m, 11H), 6.39 (d, J = 23.6 Hz, 1H), 2.48
(s, 3H). 13C{1H} NMR (100 MHz, CDCl3): δ 159.4, 142.1 (d, JCꢀP = 17.0 Hz), 134.6 (d, JCꢀP = 105.0
Hz), 131.5 (d, JCꢀP = 2.6 Hz), 130.9 (d, JCꢀP = 9.8 Hz), 129.2, 128.7, 128.5 (d, JCꢀP = 5.9 Hz), 126.0,
118.3 (d, JCꢀP = 104.7 Hz), 19.6 (d, JCꢀP = 7.5 Hz).31P NMR (162 MHz, CDCl3): δ 21.78.
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(E)ꢀstyryldiꢀpꢀtolylphosphine oxide (3z).18a White solid; yield: 53.1 mg, 80%. H NMR (400 MHz,
CDCl3): δ 7.67‒7.62 (m, 4H), 7.52‒7.48 (m, 3H), 7.36‒7.34 (m, 3H), 7.27 (d, J = 7.2 Hz, 4H), 6.83 (dd,
J = 17.6, 22.0 Hz, 1H), 2.39 (s, 6H). 13C{1H} NMR (100 MHz, CDCl3): δ 147.1 (d, JCꢀP = 3.8 Hz),
142.2 (d, JCꢀP = 2.7 Hz), 135.1 (d, JCꢀP = 18.0 Hz), 131.3 (d, JCꢀP = 10.4 Hz), 129.8, 129.48 (d, J = 108.6
Hz), 129.2 (d, JCꢀP = 12.6 Hz), 128.7, 127.6, 119.4 (d, JCꢀP = 104.8 Hz), 21.4. 31P NMR (162 MHz,
CDCl3): δ 25.42.
(E)ꢀbis(4ꢀMethoxyphenyl)(styryl)phosphine oxide (3za). Colorless oil; yield: 55.3 mg, 76%. 1H
NMR (400 MHz, CDCl3): δ 7.66‒7.62 (m, 4H), 7.49‒7.40 (m, 3H), 7.35‒7.33 (m, 3H), 6.96 (d, J = 8.8
Hz, 4H), 6.78 (dd, J = 17.6, 21.2 Hz, 1H), 3.81 (s, 6H). 13C{1H} NMR (100 MHz, CDCl3): δ 162.3 (d,
JCꢀP = 2.8 Hz), 146.6 (d, JCꢀP = 3.8 Hz), 135.1 (d, JCꢀP = 17.9 Hz), 133.1 (d, JCꢀP = 11.3 Hz), 129.8 ,
128.7, 127.6, 124.2 (d, JCꢀP = 112.4 Hz), 120.1 (d, JCꢀP = 105.1 Hz), 114.0 (d, JCꢀP = 13.2 Hz), 55.2. 31
P
NMR (162 MHz, CDCl3): δ 24.48. HRMS (ESI) m/z: [M]+ calcd for C22H21O3P 364.1228; found
364.1226.
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(E)ꢀbis(4ꢀFluorophenyl)(styryl)phosphine oxide (3zb). Pale yellow oil; yield: 47.6 mg, 70%. H
NMR (400 MHz, CDCl3): δ 7.78‒7.72 (m, 4H), 7.54‒7.45 (m, 3H), 7.38‒7.37 (m, 3H), 7.18 (t, J = 8.0
Hz, 4H), 6.81 (dd, J = 17.2, 22.8 Hz, 1H). 13C{1H} NMR (100 MHz, CDCl3): δ, 164.99 (dd, JCꢀF
253.7, JCꢀP = 3.2 Hz), 148.0 (d, JCꢀP = 3.8 Hz), 134.7 (d, JCꢀP = 18.2 Hz), 133.7 (dd, JCꢀF = 11.5, JCꢀP
=
=
8.8 Hz), 130.2, 128.8, 128.5 (dd, JCꢀF = 109.3, JCꢀF = 3.3 Hz), 127.7, 118.4 (d, JCꢀP = 106.3 Hz), 116.02
(dd, JCꢀF = 21.4, JCꢀP = 13.4 Hz). 31P NMR (162 MHz, CDCl3): δ 24.46. 19F NMR (376 MHz, CDCl3): δ
ꢀ106.29. HRMS (ESI) m/z: [M]+ calcd for C20H15F2OP 340.0829; found 340.0828.
(E)ꢀdi(Naphthalenꢀ2ꢀyl)(styryl)phosphine oxide (3zc). White solid; yield: 50.9 mg, 63%; mp
177−178 °C. 1H NMR (400 MHz, CDCl3): δ 7.66‒7.62 (m, 4H), 7.49‒7.40 (m, 3H), 7.35‒7.33 (m, 3H),
6.96 (d, J = 8.8 Hz, 4H), 6.78 (dd, J = 17.6, 21.2 Hz, 1H), 3.81 (s, 6H). 13C{1H} NMR (100 MHz,
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CDCl3): δ 147.8 (d, JCꢀP = 3.7 Hz), 135.1 (d, JCꢀP = 17.9 Hz), 134.6 (d, JCꢀP = 2.3 Hz), 133.2 (d, JCꢀP
=
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9.4 Hz), 132.5 (d, JCꢀP = 13.3 Hz), 130.5, 130.0, 129.4, 128.8, 128.8, 128.4 (d, JCꢀP = 12.0 Hz), 128.1,
127.7 (d, JCꢀP = 0.6 Hz), 126.9, 126.2 (d, J = 10.9 Hz), 119.0 (d, J = 104.8 Hz). 31P NMR (162 MHz,
CDCl3): δ 24.81. HRMS (ESI) m/z: [M]+ calcd for C28H21OP 404.1330; found 404.1332.
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(E)ꢀdicyclohexyl(styryl)phosphine oxide (3zd). White solid; yield: 30.3 mg, 48%; mp 183−184 °C.
1H NMR (400 MHz, CDCl3): δ 7.50‒7.40 (m, 3H), 7.37‒7.30 (m, 3H), 6.25 (dd, J = 17.6, 25.2 Hz, 1H),
2.00 (d, J = 13.6 Hz, 2H), 1.79‒1.68 (m, 10H), 1.40‒1.20 (m, 10H). 13C{1H} NMR (100 MHz, CDCl3):
δ 148.3, 135.51 (d, JCꢀP = 15.4 Hz), 129.6, 128.8, 127.4, 116.1 (d, JCꢀP = 87.3 Hz), 35.5 (d, JCꢀP = 69.3
Hz), 26.6, 26.47, 26.42, 26.2, 25.9, 25.8 (d, JCꢀP = 2.2 Hz), 24.7 (d, JCꢀP = 3.2 Hz). 31P NMR (162 MHz,
CDCl3): δ 43.89. HRMS (ESI) m/z: [M]+ calcd for C20H29OP 316.1956; found 316.1959.
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(E)ꢀdibutyl(styryl)phosphine oxide (3ze). Colorless oil; yield: 24.3 mg, 46%. H NMR (400 MHz,
CDCl3): δ 7.48 (d, J = 6.4 Hz, 2H), 7.44‒7.34 (m, 4H), 6.25 (dd, J = 17.6, 25.2 Hz, 1H), 1.81‒1.55 (m,
7H), 1.42‒1.37 (m, 5H), 0.89(t, J = 7.2 Hz, 6H). 13C{1H} NMR (100 MHz, CDCl3): δ 147.2, 135.2 (d,
JCꢀP = 16.3 Hz), 129.8, 128.8, 127.5, 118.7 (d, JCꢀP = 92.6 Hz), 29.4 (d, JCꢀP = 70.1 Hz), 24.1 (d, JCꢀP
=
14.6 Hz), 23.7 (d, JCꢀP = 4.0 Hz), 13.6. 31P NMR (162 MHz, CDCl3): δ 39.43. HRMS (ESI) m/z: [M]+
calcd for C16H25OP 264.1643; found 264.1644.
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(E)ꢀ6ꢀStyryldibenzo[c,e][1,2]oxaphosphinine 6ꢀoxide (3zf).18a White solid; yield: 25.4 mg, 40%. H
NMR (400 MHz, CDCl3): δ 8.02‒7.95 (m, 2H), 7.84‒7.68 (m, 3H), 7.53‒7.39 (m, 7H), 7.28‒7.26 (m,
2H), 6.50 (dd, J = 17.6, 21.6 Hz, 1H). 13C{1H} NMR (100 MHz, CDCl3): δ 150.3 (d, JCꢀP = 6.2 Hz),
149.0 (d, JCꢀP = 8.2 Hz), 135.5 (d, JCꢀP = 5.6 Hz), 134.4 (d, JCꢀP = 21.0 Hz), 133.0 (d, JCꢀP = 2.3 Hz),
130.6, 130.5, 130.4, 128.8, 128.3 (d, JCꢀP = 14.0 Hz), 128.0, 125.0 (d, JCꢀP = 130.4 Hz), 125.0, 124.5,
123.7 (d, JCꢀP = 9.6 Hz), 122.1 (d, JCꢀP = 11.3 Hz), 120.6 (d, JCꢀP = 6.0 Hz), 115.1 (d, JCꢀP = 144.0 Hz).
31P NMR (162 MHz, CDCl3): δ 23.86.
(8R,9S,13S,14S)ꢀ2ꢀ((E)ꢀ2ꢀ(Diphenylphosphoryl)vinyl)ꢀ3ꢀ(methoxymethoxy)ꢀ13ꢀmethylꢀ6,7,8,9,11,1
2,13,14,15,16ꢀdecahydroꢀ17Hꢀcyclopenta[α]phenanthrenꢀ17ꢀone (3zh). White solid; yield: 54.0 mg,
50%; mp 174−175 °C. 1H NMR (400 MHz, CDCl3): δ 7.81‒7.72 (m, 5H), 7.51‒7.45 (m, 7H),
6.88‒6.78 (m, 2H), 5.15 (s, 2H), 3.40 (s, 3H), 2.90‒2.89 (m, 2H), 2.52‒2.38 (m, 2H), 2.22‒1.94 (m,
5H), 1.66‒1.39 (m, 6H), 0.89 (s, 3H). 13C{1H} NMR (100 MHz, CDCl3): δ 220.6, 153.6, 142.8 (d, JCꢀP
= 4.7 Hz), 140.5, 133.35 (d, JCꢀP = 105.4 Hz), 133.30, 131.6 (d, JCꢀP = 2.6 Hz), 131.3 (d, JCꢀP = 9.9 Hz),
128.4 (d, JCꢀP = 12.1 Hz), 124.8, 122.3 (d, JCꢀP = 17.7 Hz), 118.2 (d, JCꢀP = 105.3 Hz), 114.9, 94.5, 56.2,
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50.3, 47.8, 43.7, 38.1, 35.7, 31.4, 29.7, 26.3, 25.8, 21.5, 13.7. 31P NMR (162 MHz, CDCl3): δ 25.13.
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HRMS (ESI) m/z: [M]+ calcd for C34H37O4P 540.2429; found 540.2430.
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Supporting Information.
The Supporting Information is available free of charge on the ACS Publications website at
http://pubs.acs.org. GCꢀMS analysis of the control experiments and copies of H, 31P, 19F and 13C
1
NMR spectra for all products (PDF)
AUTHOR INFORMATION
ORCID
Jianyu Dong: 0000ꢀ0003ꢀ2161ꢀ1372; Yongbo Zhou: 0000ꢀ0002ꢀ3540ꢀ8618
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENT
Financial support by the National NSF of China (Grant Nos. 21706058, 21573065, and 21273066), and
the NSF of Hunan Province (Grant No. 2016JJ1007) is appreciated.
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