Direct radical acetoxyphosphorylation of styrenes mediated by manganese(III)

Article abstract of DOI:10.1021/jo5023298

Direct radical acetoxyphosphorylation of styrenes mediated by Mn(OAc)₃ with diphenylphosphine oxide and dialkyl phosphites was described, and a new type of difunctionalization of alkenes was achieved.

Full text of DOI:10.1021/jo5023298

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Direct radical acetoxyphosphorylation of styrenes mediated by Manganese(III)
Shao-Fang Zhou, Da-Peng Li, Kui Liu, Jian-Ping Zou, and Olayinka Taiwo Asekun
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/jo5023298 • Publication Date (Web): 09 Dec 2014
Downloaded from http://pubs.acs.org on December 11, 2014
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Direct radical acetoxyphosphorylation of styrenes mediated by Manganese(III)
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ShaoꢀFang Zhou,a DaꢀPeng Li,a Kui Liu,a JianꢀPing Zou*a,b and Olayinka Taiwo Asekunc
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a Key Laboratory of Organic Synthesis of Jiangsu Province,,College of Chemistry and Chemical
Engineering, Soochow University, 199 Renai Street, Suzhou, Jiangsu 215123, China. jpzou@suda.edu.cn
b Key Laboratory of Synthetic Chemistry of Natural Substances, Shanghai Institute of Organic Chemistry,
Chinese Academy of Sciences, Shanghai 200032, China.
c Department of Chemistry, University of Lagos, Akoka, Yaba, Nigeria.
ABSTRACT: Direct radical acetoxyphosphorylation of styrenes mediated by Mn(OAc)3 with
diphenylphosphine oxide and dialkyl phosphites was described, a new type of difunctionalization of
alkenes was achieved.
Direct difunctionalization of alkenes is one of the most powerful transformations known in the
field of chemical synthesis,1 so it has gained increasing considerable attention, in which phosphorusꢀ
related difunctionalization of alkenes is still a challenge, although this strategy can easily transform
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alkenes to βꢀketo, βꢀamino, and βꢀhydroxyphosphonates. Recently, many CꢀP bond formation
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reports have been published,
however, phosphorusꢀrelated difunctionalization of alkenes is
limited.4 Ji group reported the Cu/Fe coꢀcatalyzed oxyphosphorylation of alkenes with dioxygen and
4a
Hꢀphosphonates ; Li group described the first example of fluorophosphonylation catalyzed by
AgNO3. 4b Mn(OAc)3 is a useful reagent for CꢀC, CꢀP and other bond formations,5 our laboratory
developed a novel Mn(OAc)3ꢀmediated monoꢀfunctionalization of αꢀsp2C–H bond of α,βꢀ
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unsaturated arylketones. Herein, we report a new type of direct difunctionalization of alkenes
mediated by Mn(OAc)3 with diphenylphosphine oxide and dialkyl phosphites.
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In our previous paper,
we disclosed a reaction of βꢀphenylethylene styrene and
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diphenylphosphine oxide afforded a tetrahydronaphthalene as major product through benzyl radical
cyclization intramolecularly, accompanied by one acetoxyphosphorylation byꢀproduct formed. To let
byꢀproduct become as major one, reaction conditions were improved, but the result remained
unchanged. It might be attributed to the presence of a βꢀphenyl moiety in styrene to facilitate the
radical cyclization. To confirm this hypothesis, the reaction of styrene and HP(O)Ph2/Mn(OAc)3 was
tried at 50°C for 20 minutes. To our delight, a major product was isolated, which was characterized
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to be 2ꢀ(diphenylphosphoryl)ꢀ1ꢀphenylethyl acetate (3a), an acetoxyphosphorylation product, by H
NMR, 13C NMR and HRMS spectral analyses (Table 1). Afterwards, the optimal reaction conditions
were screened and found that the reaction carried out in AcOH at 50°C for 0.5 h with ratio of
styrene/HP(O)Ph2/Mn(OAc)3 (1:1.5:2) gave the best result (Table 1, entry 5).
Table 1. Optimization of the reaction conditions
Subsequently, the above optimal reaction conditions were applied for the different styrenes. We
found that styrenes bearing electronꢀdonating groups like Me and OMe on the phenyl ring produced
the expected 2ꢀ(diphenylphosphoryl)ꢀ1ꢀarylethyl acetates in 65% and 73% yields (Table 2, 3bꢀc). On
the other hand, styrenes bearing halogens like F, Cl and Br on the phenyl ring formed the products in
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slightly lower yields (50~60%) (Table 2, 3dꢀg). It is noteworthy that styrenes bearing electronꢀ
withdrawing groups such as CF3 gave the low yield of acetoxyphosphorylation product (Table 2, 3h),
while CN and NO2 derivatives did not
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Table 2. Reactions of alkenes 1 and diphenylphosphine oxide 2 and dialkyl phosphites 4a,b
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afford the expected products (Table 2, 3iꢀj).
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Thereafter, dimethyl phosphites (4) was employed for the reaction under similar conditions to 2,
except the reaction temperature has to be raised to 70°C and the reaction time was prolonged to 60
minutes due to the lower reactivity of 4 than 2. The results showed that the styrenes bearing electronꢀ
donating groups like Me, OMe and halogens such as F, Cl and Br on the phenyl ring all formed
acetoxyphosphorylation products in moderate yields (up to 68%, Table 2, 5aꢀg). In contrast, electronꢀ
withdrawing groups like CF3, CN afforded the expected products (5h and 5i ) in low yields, and NO2
derivative did not give the expected product (Table 2, 5hꢀj).
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To know the effect of αꢀ or βꢀsubstituents of styrene on the reaction, CH3, Br and Ph substituted
styrenes were used for the reaction. Firstly, the reactions of αꢀmethylstyrene (1k) with 2 and 4 were
explored and found that they all afforded the acetoxyphosphorylation products 3k and 5k both in
67% yield, respectively (Table 3, entry 1). It revealed that αꢀmethyl of styrene has no impact on the
reaction. In contrast, the reactions of βꢀmethylstyrene (1l) with 2 and 4 afforded the mixture of
acetoxyphosphorylation products (3l, 5l) and hydroxyphosphorylation products (3l’, 5l’) (Table 3,
entry 2). The further experiments showed that the acetoxyl group of 3l and 5l were not able to leave
and transform to hydroxy group under the reaction conditions. Secondly, the reaction of αꢀ
bromostyrene (1m) with 2 was carried out, two products, viz 1ꢀ (diphenylphosphoryl)ꢀ2ꢀbromoꢀ2ꢀ
phenylꢀethylene (3m) and 2ꢀ(diphenylphosphoryl)ꢀ1ꢀphenylethanone (3m’) were isolated in 30%
and 50% yields, respectively (Table 3, entry 3). Instead the reaction of 1m with 4 gave the dimethyl
2ꢀbromoꢀ2ꢀphenylvinylphosphonate (5m) and dimethyl 2ꢀoxoꢀ2ꢀphenylethyl phosphonate (5m’) in
21% and 50% yields, respectively (Table 3, entry 3). Furthermore, the reactions of βꢀbromostyrene
(1n) with 2 and 4 were performed, they all gave the additionꢀelimination products 3n and 5n through
the phosphorusꢀcentred radical addition to the terminal C=C double bond, followed elimination of
Br• radical to form alkenylphosphorylation products (Table 3, entry 4). Thirdly, the reaction of αꢀ
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phenylstyrene (1o) with 2 was performed, hydroxyphosphorylation product 3o in 71% yield was
obtained (Table 3, entry 5); However, using 4 instead of 2 afforded dimethyl 2,2ꢀ
diphenylvinylphosphonate (5o’) in 78% yield, which was derived from 5o by loss of H2O (Table 3,
entry 5). Compared to αꢀphenylstyrene (1o), the reaction of βꢀphenylstyrene (1p) with 2 afforded a
sole acetoxyphosphorylation product 3p in 50% yield, while the reaction of 1p with 4 gave the
mixture of acetoxyꢀ and oxyphosphorylation (5p and 5p’) through similar way to 5l and 5l’ (Table 3,
entries 2, 6). Based on the results described above, using αꢀ or βꢀsubstituted (CH3, Br and Ph)
styrenes as substrates, diverse products were obtained, the structure of products depended on both of
the kind of substituents and their location. Finally, nonꢀconjugated terminal alkenes (1qꢀ1t) were
conducted for the reaction, the exclusive hydrophosphorylation products were obtained with up to
92% yield (Table 3, entries 7ꢀ10).
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The above acetoxyphosphorylation reaction proceeded through radical pathway, viz. phosphorusꢀ
centred radical selectively adds to the terminal C=C double bond of 1 to yield carbon radical
intermediate, it is oxidized by Mn(OAc)3 to form carbocation, followed by combinating with HOAc
and deprotonation to afford products 3 or 5. The carbocation intermediate is captured by adding
tetrabutylammonium bromide (TBAB) to the reaction of 1a and 2 to form 1ꢀ(diphenylphosphoryl)ꢀ2ꢀ
bromophenylethane (3a’).
In conclusion, a new type of difunctionalization of alkenes was developed from the reaction of
diphenylphosphine oxide and dialkyl phosphites with alkenes in the presence of Mn(OAc)3 through
tandem radical process. The reactions proceeded under mild conditions in air to afford
acetoxyphosphorylation products in moderate to good yields. This methodology has the advantages
of being straightforward, no need of additives and other oxidant, short reaction time, simple
manipulations and the acetoxyꢀphosphorylation products can be easily transformed to a variety of
useful functionalized compounds.
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Table 3. Reactions of αꢀ and βꢀsubstituted styrenes 1 with diphenylphosphine oxide 2
and dimethyl phosphite 4a, b
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EXPERIMENTAL SECTION
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General Methods. H NMR (400 MHz or 300 MHz) and 13C NMR (150, 100 or 75 MHz)
spectra were determined with CDCl3 or DMSOꢀd6 as solvent and tetramethylsilane (TMS) as internal
standard or 85% H3PO4 as external standard for 31P NMR (162 MHz). Chemical shifts were reported
in ppm from internal TMS (δ), all coupling constants (J values) were reported in Hertz (Hz). High
resolution mass spectra were recorded on a TOF machine (ESI). Column chromatography was
performed with 300ꢀ400 mesh silica gel using flash column techniques. All of the reagents were used
directly as obtained commercially unless otherwise noted. All alkenes were purified by flash column
chromatography (Al2O3) before use.
Preparation of 2ꢀ(diphenylphosphoryl)ꢀ1ꢀarylethyl acetates 3. Typical procedure for the
preparation of 2ꢀ(diphenylphosphoryl)ꢀ1ꢀphenylethyl acetate (3a). To a solution of acetic acid (10
mL), styrene (1.0 mmol) and diphenylphosphine oxide (1.5 mmol) was added Mn(OAc)3 (2.0 mmol)
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in 10 min at 50 C, about 30 min later the reaction was completed. The mixture was cooled to room
temperature and the solvent was removed under vacuum. To the residue was added water (20 mL)
and extracted with ethyl acetate (10 mL x 3). The combined organic fractions were dried over
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anhydrous Na2SO4, and concentrated under vacuum to yield the crude product, which was purified by
column chromatography (silica gel, petroleum ether/EtOAc/CH2Cl2 (8:1:1) ) to give pure 2ꢀ
(diphenylphosphoryl)ꢀ1ꢀphenylethyl acetate (3a).
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2ꢀ(Diphenylphosphoryl)ꢀ1ꢀphenylethyl acetate (3a). White solid; m.p. 150ꢀ151 C, 70% yield
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(254.9 mg). 1H NMR (400 MHz, CDCl3): δ 7.79ꢀ7.85 (m, 2H), 7.65ꢀ7.71 (m, 2H), 7.45ꢀ7.54 (m, 4H),
7.37ꢀ7.43 (m, 2H), 7.27ꢀ7.36 (m, 3H), 7.19ꢀ7.25 (m, 2H), 6.24 (td, J = 3.6, 9.0 Hz, 1H), 3.01ꢀ3.13 (m,
1H), 2.65ꢀ2.76 (m, 1H), 1.67 (s, 3H); 13C NMR (100 MHz, CDCl3): δ 169.2, 140.4 (d, J = 10.0 Hz),
133.1 (d, J = 99.8 Hz), 131.7 (d, J = 3.0 Hz), 131.6 (d, J = 2.8 Hz), 130.9 (d, J = 10.0 Hz), 130.6 (d,
J = 10.0 Hz), 128.7, 128.6, 128.5, 128.4 (d, J = 20.9 Hz), 126.2, 70.2 (d, J = 3.0 Hz), 37.5 (d, J =
68.6 Hz), 20.5; 31P NMR (162 MHz, CDCl3): δ 27.0. HRMS (ESIꢀTOF) m/z: (M+H)+ Calcd for
C22H22O3P 365.1307, found 365.1305.
(2ꢀBromoꢀ2ꢀphenylethyl)diphenylphosphine oxide (3a’) . This compound was obtained from the
Mn(OAc)3ꢀmediated reaction of styrene and diphenylphosphine oxide in HOAc in the presence of
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tetrabutylammonium bromide (TBAB) for mechanism investigation. White solid m.p. 153ꢀ154 C,
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30% yield (115.2 mg). H NMR (400 MHz, CDCl3): 7.74ꢀ7.82 (m, 2H), 7.43ꢀ7.58 (m, 5H), 7.24ꢀ
7.39 (m, 5H), 7.08ꢀ7.15 (m, 3H), 5.55ꢀ5.65 (m, 1H), 3.36ꢀ3.48 (m, 2H); 13C NMR (100 MHz,
CDCl3): δ 140.9 (d, J = 3.7 Hz), 132.1, 131.5, 130.8, 130.7 (d, J = 1.7 Hz), 130.6, 128.8 (d, J = 11.7
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Hz), 128.6, 128.5, 128.4 (d, J = 12, 2 Hz), 127.4, 46.4, 41.6 (d, J = 64.7 Hz); P NMR (162 MHz,
CDCl3): δ 26.9. HRMS (ESIꢀTOF) m/z: (M+H)+ Calcd for C20H19BrOP 385.0357, found 385.0387.
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2ꢀ(Diphenylphosphoryl)ꢀ1ꢀ(pꢀtolyl)ethyl acetate (3b). White solid; m.p. 174ꢀ175 C, 65% yield
(245.7 mg). 1H NMR (400 MHz, CDCl3): δ 7.79ꢀ7.87 (m, 2H), 7.64ꢀ7.74 (m, 2H), 7.46ꢀ7.55 (m, 4H),
7.37ꢀ7.44 (m, 2H), 7.22 (d, J = 7.9 Hz, 2H), 7.08 (d, J = 7.9 Hz, 2H), 6.23 (td, J = 3.8, 9.1 Hz, 1H),
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3.03ꢀ3.15 (m, 1H), 2.65ꢀ2.75 (m, 1H), 2.29 (s, 3H), 1.65 (s, 3H); C NMR (100 MHz, CDCl3): δ
169.3, 138.1, 137.5 (d, J = 9.6 Hz), 133.6 (d, J = 3.6 Hz), 132.6 (d, J = 3.5 Hz), 131.7 (d, J = 2.5 Hz),
131.0 (d, J = 9.4 Hz), 130.6 (d, J = 9.4 Hz), 129.3, 128.6 (d, J = 5.7 Hz), 128.5 (d, J = 5.8 Hz), 126.3,
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70.2 (d, J = 2.9 Hz), 37.4 (d, J = 68.4 Hz), 21.1, 20.6; P NMR (162 MHz, CDCl3): δ 27.5. HRMS
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(ESIꢀTOF) m/z: (M+Na)+ Calcd for C23H23NaO3P 401.1283, found 401.1279.
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2ꢀ(Diphenylphosphoryl)ꢀ1ꢀ(4ꢀmethoxyphenyl)ethyl acetate (3c). White solid; m.p. 165ꢀ166 C,
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73% yield (287.6 mg). H NMR (400 MHz, CDCl3): δ 7.77ꢀ7.85 (m, 2H), 7.63ꢀ7.72 (m, 2H), 7.35ꢀ
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7.53 (m, 6H), 7.20ꢀ7.25 (m, 2H), 6.76ꢀ6.84 (m, 2H), 6.16ꢀ6.28 (m, 1H), 3.74 (d, J = 4.4 Hz, 3H),
3.01ꢀ3.17 (m, 1H), 2.64ꢀ2.78 (m, 1H), 1.64 (d, J = 2.4 Hz, 3H); 13C NMR (100 MHz, CDCl3): δ
169.3, 159.5, 133.6, 132.6, 132.4, 132.3, 131.6 (d, J = 2.6 Hz), 130.9 (d, J = 9.4 Hz), 130.6 (d, J =
9.2 Hz), 128.6 (d, J = 3.7 Hz), 128.5 (d, J = 3.7 Hz), 127.8, 113.9, 70.2 (d, J = 2.6 Hz), 55.2, 37.2 (d,
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J = 69.0 Hz), 20.6; P NMR (162 MHz, CDCl3): δ 27.0. HRMS (ESIꢀTOF) m/z: (MꢀOAc)+ Calcd
for C21H20O2P 335.1201, found 335.1239.
2ꢀ(Diphenylphosphoryl)ꢀ1ꢀ(4ꢀfluorophenyl)ethyl acetate (3d). White solid; m.p. 134ꢀ135 oC, 61%
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yield (233.0 mg). H NMR (400 MHz, CDCl3): δ 7.79ꢀ7.84 (m, 2H), 7.62ꢀ7.71 (m, 2H), 7.46ꢀ7.58
(m, 5H), 7.37ꢀ7.45 (m, 2H), 7.28ꢀ7.33 (m, 1H), 6.90ꢀ7.00 (m, 2H), 6.18ꢀ6.28 (m, 1H), 3.01ꢀ3.14 (m,
1H), 2.63ꢀ2.78 (m, 1H), 1.70 (s, 3H); 13C NMR (100 MHz, CDCl3): δ 169.3, 162.4 (d, J = 245.5 Hz),
132.3 (d, J = 2.1 Hz), 132.2 (d, J = 9.6 Hz), 131.8 (d, J = 2.2 Hz), 131.1 (d, J = 9.6 Hz), 130.9 (d, J =
9.3 Hz), 130.6 (d, J = 9.3 Hz), 128.69 (d, J = 12.1 Hz), 128.68 (d, J = 2.3 Hz), 128.5 (d, J = 2.3 Hz),
128.3 (d, J = 8.3 Hz), 115.5 (d, J = 21.5 Hz), 69.8, 37.4 (d, J = 68.9 Hz), 20.6; 31P NMR (162 MHz,
CDCl3): δ 26.8. HRMS (ESIꢀTOF) m/z: (M+Na)+ Calcd for C22H20FNaO3P 405.1032, found
405.1047.
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1ꢀ(4ꢀChlorophenyl)ꢀ2ꢀ(diphenylphosphoryl)ethyl acetate (3e). White solid; m.p. 166ꢀ167 C,
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60% yield (238.8 mg). H NMR (400 MHz, CDCl3): δ 7.76ꢀ7.83 (m, 2H), 7.62ꢀ7.68 (m, 2H), 7.47ꢀ
7.60 (m, 4H), 7.37ꢀ7.45 (m, 2H), 7.20ꢀ7.25 (m, 4H), 6.22 (td, J = 4.8, 8.4 Hz, 1H), 3.00ꢀ3.10 (m, 1H),
2.65ꢀ2.74 (m, 1H), 1.68 (s, 3H); 13C NMR (100 MHz, CDCl3): δ 169.2, 138.7 (d, J = 9.0 Hz), 134.1,
131.8 (d, J = 2.0 Hz), 130.9 (d, J = 10.0 Hz), 130.6 (d, J = 9.0 Hz), 128.8, 128.7 (d, J = 3.0 Hz),
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128.6 (d, J = 4.0 Hz), 127.9, 69.8 (d, J = 4.0 Hz), 37.3 (d, J = 68.0 Hz), 20.6; P NMR (162 MHz,
CDCl3): δ 26.9. HRMS (ESIꢀTOF) m/z: (M+H)+ Calcd for C22H21ClO3P 399.0917, found 399.0933.
1ꢀ(3ꢀChlorophenyl)ꢀ2ꢀ(diphenylphosphoryl)ethyl acetate (3f). White solid; m.p. 172ꢀ173 oC, 58%
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yield (230.9 mg). H NMR (400 MHz, CDCl3): δ 7.77ꢀ7.84 (m, 2H), 7.62ꢀ7.70 (m, 2H), 7.45ꢀ7.59
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(m, 5H), 7.37ꢀ7.44 (m, 2H), 7.17ꢀ7.23 (m, 3H), 6.20 (td, J = 4.4, 8.8 Hz, 1H), 2.98ꢀ3.09 (m, 1H),
2.64ꢀ2.74 (m, 1H), 1.69 (s, 3H); 13C NMR (100 MHz, CDCl3): δ 169.2, 142.3 (d, J = 9.2 Hz), 134.5,
131.9 (d, J = 2.6 Hz), 131.8 (d, J = 2.7 Hz), 130.9 (d, J = 9.4 Hz), 130.6 (d, J = 9.4 Hz), 129.9, 128.7
(d, J = 3.8 Hz), 128.6 (d, J = 3.9 Hz), 128.5, 126.4, 124.7, 69.7 (d, J = 2.5 Hz), 37.6 (d, J = 68.5 Hz),
20.5; 31P NMR (162 MHz, CDCl3): δ 29.4. HRMS (ESIꢀTOF) m/z: (M+H)+ Calcd for C22H21ClO3P
399.0917, found 399.0922.
1ꢀ(4ꢀBromophenyl)ꢀ2ꢀ(diphenylphosphoryl)ethyl acetate (3g). White solid; m.p. 130ꢀ131 oC, 60%
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yield (265.2 mg). H NMR (400 MHz, CDCl3): δ 7.78ꢀ7.85 (m, 2H), 7.62ꢀ7.70 (m, 2H), 7.42ꢀ7.58
(m, 6H), 7.38 (d, J = 8.1 Hz, 2H), 7.20 (d, J = 8.1 Hz, 2H), 6.13ꢀ6.24 (m, 1H), 2.96ꢀ3.14 (m, 1H),
2.63ꢀ2.79 (m, 1H), 1.70 (s, 3H); 13C NMR (100 MHz, CDCl3): δ 169.2, 139.2 (d, J = 8.8 Hz), 131.7,
130.9 (d, J = 9.4 Hz), 130.6 (d, J = 9.3 Hz), 128.7 (d, J = 3.5 Hz), 128.6 (d, J = 3.7 Hz), 128.2, 122.3,
69.9, 37.2 (d, J = 68.5 Hz), 20.6; 31P NMR (162 MHz, CDCl3): δ 27.1. HRMS (ESIꢀTOF) m/z:
(M+Na)+ Calcd for C22H20BrNaO3P 465.0231, found 465.0252.
Mixture of 2ꢀ(diphenylphosphoryl)ꢀ1ꢀ(3ꢀ(trifluoromethyl)phenyl)ethyl acetate (3h) and 2ꢀ
(diphenylphosphoryl)ꢀ1ꢀ(3ꢀ(trifluoromethyl)phenyl)ethanone (3h’). White solid; 35% (3h) and 28%
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(3h’) yield (259.9 mg), respectively, 3h : 3h’ = 1 : 0.8, analyzed by H NMR spectrum. H NMR
(400 MHz, CDCl3): δ 8.28 (d, J = 7.9 Hz, 1H), 8.19 (s, 1H), 7.70ꢀ7.88 (m, 6H), 7.45ꢀ7.60 (m, 9H),
7.32ꢀ7.40 (m, 2H), 4.16 (d, J = 15.3 Hz, 2H), 2.95ꢀ3.06 (m, 1H), 2.52ꢀ2.62 (m, 1H), 1.28 (s, 3H); 13C
NMR (100 MHz, CDCl3): δ 191.7 (d, J = 5.6 Hz), 141.9 (d, J = 14.5 Hz), 137.4, 132.8, 132.4 (d, J =
2.8 Hz), 132.2, 131.9 (d, J = 2.6 Hz), 131.7, 131.1, 131.0, 130.8 (d, J = 9.3 Hz), 129.9 (d, J = 3.6 Hz),
129.3, 129.1, 128.8 (d, J = 12.0 Hz), 125.8 (d, J = 3.8 Hz), 124.8 (d, J = 3.8 Hz), 123.3 (d, J = 3.9
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Hz), 43.9 (d, J = 55.9 Hz), 29.7, 27.5; 31P NMR (162 MHz, CDCl3): δ 26.7, 31.2. HRMS (ESIꢀTOF)
of 3h m/z: (M+H)+ Calcd for C23H21F3O3P 433.1180, found 433.1193; HRMS (ESIꢀTOF) of 3h’ m/z:
(M+H)+ Calcd for C21H17F3O2P 389.0918, found 389.0927.
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4ꢀ(2ꢀ(Diphenylphosphoryl)acetyl)benzonitrile (3i’).White solid; m.p. 169ꢀ170 C, 48% yield
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(165.6 mg). 1H NMR (400 MHz, CDCl3): δ 8.13 (d, J = 8.2 Hz, 2H), 7.79 (dd, J = 7.5, 12.0 Hz, 4H),
7.72 (d, J = 8.2 Hz, 2H), 7.53ꢀ7.58 (m, 2H), 7.45ꢀ7.51 (m, 4H), 4.15 (d, J = 15.0 Hz, 2H); 13C NMR
(100 MHz, CDCl3): δ 191.8 (d, J = 5.8 Hz), 139.8, 132.4 (d, J = 2.7 Hz), 132.3, 131.0 (d, J = 9.8 Hz),
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129.8, 128.8 (d, J = 12.4 Hz), 117.9, 116.7, 44.0 (d, J = 55.0 Hz); P NMR (162 MHz, CDCl3): δ
26.5. HRMS (ESIꢀTOF) m/z: (M+H)+ Calcd for C21H17NO2P 346.0997, found 346.1002.
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2ꢀ(Diphenylphosphoryl)ꢀ1ꢀ(4ꢀnitrophenyl)ethanone (3j’). Yellow solid; m.p. 163ꢀ164 C,7 30%
yield (109.0 mg). 1H NMR (400 MHz, CDCl3): δ 8.26 (d, J = 8.9 Hz, 2H), 8.20 (d, J = 8.9 Hz, 2H),
7.76ꢀ7.83 (m, 4H), 7.54ꢀ7.59 (m, 2H), 7.46ꢀ7.53 (m, 4H), 4.17 (d, J = 15.1 Hz); 13C NMR (100 MHz,
CDCl3): δ 191.6 (d, J = 5.8 Hz), 150.5, 141.2, 132.5 (d, J = 2.9 Hz), 131.9, 131.0 (d, J = 9.8 Hz),
130.4, 128.8 (d, J = 12.4 Hz), 123.7, 44.3 (d, J = 54.8 Hz).
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1ꢀ(Diphenylphosphoryl)ꢀ2ꢀphenylpropanꢀ2ꢀyl acetate (3k). White solid; m.p. 137ꢀ138 C, 67%
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yield (253.4 mg). H NMR (400 MHz, CDCl3): δ 7.77ꢀ7.86 (m, 2H), 7.61ꢀ7.70 (m, 2H), 7.33ꢀ7.53
(m, 7H), 7.12ꢀ7.30 (m, 4H), 3.33ꢀ3.43 (m, 1H), 2.90ꢀ3.02 (m, 1H), 2.17 (s, 3H), 1.56 (s, 3H); 13C
NMR (100 MHz, CDCl3): δ 169.1, 144.8 (d, J = 7.5 Hz), 134.2 (d, J = 48.5 Hz), 133.2 (d, J = 49.3
Hz), 131.1 (d, J = 5.8 Hz), 130.7 (d, J = 9.2 Hz), 130.1 (d, J = 8.9 Hz), 128.3, 128.2 (d, J = 5.1 Hz),
128.1, 127.0, 123.8, 81.8 (d, J = 4.0 Hz), 37.5 (d, J = 68.3 Hz), 26.5, 21.3; 31P NMR (162 MHz,
CDCl3): δ 25.4. HRMS (ESIꢀTOF) m/z: (M+Na)+ Calcd for C23H23NaO3P 401.1283, found 401.1286.
Mixture of 2ꢀ(diphenylphosphoryl)ꢀ1ꢀphenylpropyl acetate (3l) and (1ꢀhydroxyꢀ1ꢀphenylpropanꢀ
2ꢀyl) diphenylphosphine oxide (3l’).White solid; 40% (3l) and 40% (3l’) yield (285.8 mg),
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respectively, 3l : 3l’ = 1 : 1, analyzed by 1H NMR spectrum. H NMR (600 MHz, CDCl3): δ 7.81ꢀ
7.86 (m, 2H), 7.71ꢀ7.80 (m, 4H), 7.42ꢀ7.54 (m, 6H), 7.26ꢀ7.37 (m, 6H), 7.15ꢀ7.24 (m, 7H), 7.04ꢀ7.13
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(m, 5H), 6.24 (d, J = 21.0 Hz, 1H), 4.60 (d, J = 30.0 Hz, 1H), 2.95ꢀ3.01 (m, 1H), 2.74ꢀ2.80 (m, 1H),
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1.95 (s, 3H), 1.20 (dd, J = 7.2, 15.6 Hz, 1H), 1.05 (dd, J = 7.2, 16.8 Hz, 3H); C NMR (150 MHz,
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CDCl3): δ 169.3, 139.4 (d, J = 12.2 Hz), 139.2 (d, J = 3.9 Hz), 135.0 (d, J = 95.3 Hz), 132.2 (d, J =
8.3 Hz), 131.7 (d, J = 2.4 Hz), 131.6 (d, J = 2.4 Hz), 131.2 (d, J = 8.6 Hz), 131.0 (d, J = 8.7 Hz),
130.8, 130.6 (d, J = 8.9 Hz), 128.7 (d, J = 11.3 Hz), 128.6 (d, J = 11.3 Hz), 128.4, 128.1 (d, J = 11.0
Hz), 127.9, 127.7, 127.5 (d, J = 11.3 Hz), 126.7, 125.7, 71.9 (d, J = 1.7 Hz), 53.5 (d, J = 2.9 Hz),
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39.9 (d, J = 68.7 Hz), 37.1 (d, J = 72.9 Hz), 20.8, 16.7, 7.7; P NMR (162 MHz, CDCl3): δ 33.1,
37.5. HRMS (ESIꢀTOF) of 3l m/z: (M+H)+ Calcd for C23H24O3P 379.1463, found 379.1482; HRMS
(ESIꢀTOF) of 3l’ m/z: (M+Na)+ Calcd for C21H21O2PNa 359.1177, found 359.1150.
(2ꢀBromoꢀ2ꢀphenylvinyl)diphenylphosphine oxide (3m). Colorless liquid, 30% yield (114.6 mg).
1H NMR (400 MHz, CDCl3): δ 7.77ꢀ7.88 (m, 4H), 7.62ꢀ7.67 (m, 2H), 7.45ꢀ7.55 (m, 7H), 7.35ꢀ7.40
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(m, 2H), 7.14 (d, J = 16.0 Hz, 1H); C NMR (75 MHz, CDCl3): δ 144.1, 139.3 (d, J = 11.9 Hz),
131.9, 131.2 (d, J = 9.5 Hz), 130.7, 128.8, 128.7, 128.5, 127.8; 31P NMR (162 MHz, CDCl3): δ 21.1.
HRMS (ESIꢀTOF) m/z: (M+H)+ Calcd for C20H17BrOP 383.0200, found 383.0207.
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2ꢀ(Diphenylphosphoryl)ꢀ1ꢀphenylethanone (3m’). White solid; m.p. 160ꢀ161 C,8 50% yield
(160.0 mg). 1H NMR (400 MHz, CDCl3): δ 7.96ꢀ8.02 (m, 2H), 7.77ꢀ7.85 (m, 4H), 7.50ꢀ7.55 (m, 3H),
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7.39ꢀ7.49 (m, 6H), 4.14 (d, J = 15.6 Hz, 2H); C NMR (75 MHz, CDCl3): δ 192.8 (d, J = 5.2 Hz),
136.9, 133.6, 132.6, 132.2, 131.1 (d, J = 9.8 Hz), 129.2, 128.7, 128.5, 43.2 (d, J = 57.8 Hz). HRMS
(ESIꢀTOF) m/z: (M+H)+ Calcd for C20H18O2P 321.1044, found 321.1047.
(E)ꢀDiphenyl(styryl)phosphine oxide (3n). White solid; m.p. 169ꢀ170 oC,9 65% yield (197.6 mg).
1H NMR (400 MHz, CDCl3): δ 7.78 (dd, J = 7.4, 11.9 Hz, 4H), 7.45ꢀ7.60 (m, 9H), 7.35ꢀ7.42 (m,
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3H), 6.87 (dd, J = 17.4, 22.3 Hz, 1H); C NMR (100 MHz, CDCl3): δ 147.6 (d, J = 3.6 Hz), 135.2
(d, J = 17.9 Hz), 133.0 (d, J = 105.2 Hz), 131.9 (d, J = 2.7 Hz), 131.4 (d, J = 10.0 Hz), 130.1, 128.9,
128.7 (d, J = 12.1 Hz), 127.8, 119.2 (d, J = 103.9 Hz).
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(2ꢀHydroxyꢀ2,2ꢀdiphenylethyl)diphenylphosphine oxide (3o). White solid; m.p. 183ꢀ184 C,10
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71% yield (282.7 mg). H NMR (400 MHz, CDCl3): δ 7.47ꢀ7.53 (m, 4H), 7.40ꢀ7.45 (m, 2H), 7.30ꢀ
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7.38 (m, 8H), 7.02ꢀ7.13 (m, 6H), 4.50 (s, 1 H), 3.40 (d, J = 9.6 Hz, 2H); 13C NMR (100 MHz,
CDCl3): δ 146.1 (d, J = 7.3 Hz), 133.4, 132.4, 131.6 (d, J = 2.6 Hz), 130.4 (d, J = 9.6 Hz), 128.5 (d,
J = 7.9 Hz), 127.9, 126.9, 125.9, 77.7 (d, J = 4.8 Hz), 41.2 (d, J = 69.0 Hz); 31P NMR (162 MHz,
CDCl3): δ 33.4.
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2ꢀ(Diphenylphosphoryl)ꢀ1,2ꢀdiphenylethyl acetate (3p). White solid; m.p. 248ꢀ249 oC, 50% yield
(220.0 mg). 1H NMR (400 MHz, CDCl3): 7.71ꢀ7.83 (m, 2H), 7.55ꢀ7.65 (m, 1H), 7.40ꢀ7.53 (m, 5H),
7.10ꢀ7.25 (m, 7H), 6.97ꢀ7.07 (m, 5H), 6.52ꢀ6.62 (m, 1H), 3.80ꢀ3.90 (m, 1H), 1.97 (s, 3H); 13C NMR
(100 MHz, CDCl3): δ 169.3, 138.7 (d, J = 7.0 Hz), 131.4 (d, J = 2.8 Hz), 131.2 (d, J = 6.0 Hz), 131.1,
131.0, 130.9, 130.8, 128.5 (d, J = 12.0 Hz), 128.2 (d, J = 1.6 Hz), 128.04, 128.0, 127.9, 127.8, 127.3
(d, J = 1.8 Hz), 127.1, 126.8, 73.4, 53.4 (d, J = 66.0 Hz), 20.9; 31P NMR (162 MHz, CDCl3): δ 29.0.
HRMS (ESIꢀTOF) m/z: (M+H)+ Calcd for C28H26O3P 441.1620, found 441.1631.
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Diphenyl (3ꢀphenylpropyl)phosphine oxide (3q). White solid; m.p. 116ꢀ117 C,11 87% yield
(278.5 mg). 1H NMR (400 MHz, CDCl3): δ 7.63ꢀ7.73 (m, 4H), 7.40ꢀ7.56 (m, 7H), 7.06ꢀ7.28 (m, 4H),
2.68ꢀ2.78 (m, 2H), 2.18ꢀ2.40 (m, 2H), 1.90ꢀ2.00 (m, 2H); 13C NMR (75 MHz, CDCl3): δ 140.6,
132.8 (d, J = 97.4 Hz), 131.7, 130.7 (d, J = 11.7 Hz), 128.7, 128.5 (d, J = 2.9 Hz), 128.4, 126.1, 36.6
(d, J = 14.7 Hz), 28.9 (d, J = 71.5 Hz), 23.0. HRMS (ESIꢀTOF) m/z: (M+H)+ Calcd for C21H22OP
321.1408, found 321.1415.
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Diphenyl(4ꢀphenylbutyl)phosphine oxide (3r). White solid; m.p. 150ꢀ151 C,12 92% yield (307.4
mg). 1H NMR (400 MHz, CDCl3): δ 7.66ꢀ7.75 (m, 4H), 7.38ꢀ7.55 (m, 6H), 7.08ꢀ7.25 (m, 5H), 2.52ꢀ
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2.62 (m, 2H), 2.20ꢀ2.31 (m, 2H), 1.63ꢀ1.75 (m, 4H); C NMR (75 MHz, CDCl3): δ 141.9, 133.0 (d,
J = 96.9 Hz), 131.7, 130.8 (d, J = 8.8 Hz), 128.7, 128.5, 128.3, 125.8, 36.4, 32.7 (d, J = 14.2 Hz),
29.6 (d, J = 71.3 Hz), 21.2. HRMS (ESIꢀTOF) m/z: (M+H)+ Calcd for C22H24OP 335.1565, found
335.1575.
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Diphenyl(3ꢀ(pꢀtolyloxy)propyl)phosphine oxide (3s). White solid; m.p. 113ꢀ114 C,12 83% yield
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(290.6 mg). H NMR (400 MHz, CDCl3): δ 7.70ꢀ7.80 (m, 4H), 7.43ꢀ7.54 (m, 6H), 7.04 (d, J = 8.0
Hz, 2H), 6.73 (d, J = 8.0 Hz, 2H), 3.93ꢀ4.00 (m, 2H), 2.42ꢀ2.52 (m, 2H), 2.27 (s, 3H), 2.05ꢀ2.15 (m,
2H); 13C NMR (75 MHz, CDCl3): δ 156.5, 132.8 (d, J = 97.6 Hz), 131.8, 130.8 (d, J = 9.1 Hz),
129.9, 129.8, 128.7 (d, J = 11.3 Hz), 114.3, 67.6 (d, J = 14.2 Hz), 26.5 (d, J = 72.4 Hz), 21.8 (d, J =
2.0 Hz), 20.5. HRMS (ESIꢀTOF) m/z: (M+H)+ Calcd for C22H24O2P 351.1514, found 351.1513.
Octyldiphenylphosphine oxide (3t). White solid m.p. 57ꢀ58 oC;12 60% yield (188.5 mg). 1H NMR
(400 MHz, CDCl3): δ 7.68ꢀ7.80 (m, 4H), 7.42ꢀ7.53 (m, 6H), 2.10ꢀ2.32 (m, 2H), 1.53ꢀ1.65 (m, 2H),
1.32ꢀ1.42 (m, 2H), 1.18ꢀ1.30 (m, 8H), 0.80ꢀ0.88 (m, 3H); 13C NMR (75 MHz, CDCl3): δ 133.3 (d, J
= 97.4 Hz), 131.6, 130.6 (d, J = 8.1 Hz), 128.5 (d, J = 11.3 Hz), 31.6, 30.8 (d, J = 14.2 Hz), 29.5 (d,
J = 71.8 Hz), 28.9, 22.4, 21.2 (d, J = 2.6 Hz), 21.1, 14.0.
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Preparation of 2ꢀ(dialkoxyphosphoryl)ꢀ1ꢀarylethyl acetate 5. Typical procedure for the
preparation of 2ꢀ(dimethoxyphosphoryl)ꢀ1ꢀphenylethyl acetate (5a).To a solution of acetic acid (10
mL), styrene (1.0 mmol) and dimethyl phosphite (1.5 mmol) was added Mn(OAc)3 (2.0 mmol) in 30
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min at 70 C, about 60 min later the reaction was completed. The mixture was cooled to room
temperature and the solvent was removed under vacuum. To the residue was added water (20 mL)
and extracted with ethyl acetate (10 mL x 3). The combined organic fractions were dried over
anhydrous Na2SO4 and concentrated under vacuum to yield the crude product, which was purified by
column chromatography (silica gel, petroleum ether/EtOAc/CH2Cl2 (8:1:1)) to give pure 2ꢀ
(dimethoxyphosphoryl)ꢀ1ꢀphenylethyl acetate (5a).
2ꢀ(Dimethoxyphosphoryl)ꢀ1ꢀphenylethyl acetate (5a). Colorless liquid; 68% yield (195.9 mg).
1H NMR (400 MHz, CDCl3): δ 7.27ꢀ7.42 (m, 5H), 6.02ꢀ6.11 (m, 1H), 3.63 (d, J = 10.8 Hz, 6H),
2.42ꢀ2.55 (m, 1H), 2.21ꢀ2.32 (m, 1H), 2.05 (s, 3H); 13C NMR (75 MHz, CDCl3): δ 169.5, 139.7 (d, J
= 10.5 Hz), 128.5, 128.4, 126.4, 70.5, 52.4 (d, J = 6.5 Hz), 52.2 (d, J = 6.5 Hz), 32.3 (d, J = 139.7
Hz), 21.0; 31P NMR (162 MHz, CDCl3): δ 28.1. HRMS (ESIꢀTOF) m/z: (M+Na)+ Calcd for
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2ꢀ(Diethoxyphosphoryl)ꢀ1ꢀphenylethyl acetate (5a’). Colorless liquid; 63% yield (189.1 mg). 1H
NMR (400 MHz, CDCl3): δ 7.27ꢀ7.42 (m, 5H), 6.05ꢀ6.15 (m, 1H), 3.94ꢀ4.10 (m, 4H), 2.45ꢀ2.58 (m,
1H), 2.22ꢀ2.35 (m, 1H), 2.07 (s, 3H), 1.21ꢀ1.30 (m, 6H); 13C NMR (100 MHz, CDCl3): δ 169.6,
139.9 (d, J = 10.3 Hz), 128.6, 128.4, 126.6, 70.8 (d, J = 1.5 Hz), 61.8 (d, J = 6.4 Hz), 61.6 (d, J = 6.4
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Hz), 33.3 (d, J = 139.5 Hz), 21.1, 16.3 (d, J = 4.8 Hz), 16.2 (d, J = 4.8 Hz); P NMR (162 MHz,
CDCl3): δ 28.3. HRMS (ESIꢀTOF) m/z: (MꢀOAc)+ Calcd for C12H18O3P 241.0994, found 241.0997.
2ꢀ(Dimethoxyphosphoryl)ꢀ1ꢀ(pꢀtolyl)ethyl acetate (5b). Colorless liquid; 65% yield (183.0 mg).
1H NMR (400 MHz, CDCl3): δ 7.26 (d, J = 8.0 Hz, 2H), 7.16 (d, J = 8.0 Hz, 2H), 6.05 (td, J = 5.7,
8.7 Hz, 1H), 3.66 (d, J = 1.6 Hz, 3H), 3.64 (d, J = 1.6 Hz, 3H), 2.46ꢀ2.57 (m, 1H), 2.33 (s, 3H), 2.20ꢀ
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2.30 (m, 1H), 2.06 (s, 3H); C NMR (100 MHz, CDCl3): δ 169.6, 138.3, 136.8 (d, J = 10.7 Hz),
129.3, 126.5, 70.5 (d, J = 1.7 Hz), 52.5 (d, J = 6.5 Hz), 52.3 (d, J = 6.5 Hz), 32.4 (d, J = 139.3 Hz),
21.1 (d, J = 3.3 Hz); 31P NMR (162 MHz, CDCl3): δ 28.3. HRMS (ESIꢀTOF) m/z: (M+Na)+ Calcd
for C13H19NaO5P 309.0868, found 309.0877.
2ꢀ(Dimethoxyphosphoryl)ꢀ1ꢀ(4ꢀmethoxyphenyl)ethyl acetate (5c). Colorless liquid; 66% yield
(119.4 mg). 1H NMR (600 MHz, CDCl3): δ 7.28 (d, J = 8.4 Hz, 2H), 6.85 (d, J = 8.4 Hz, 2H), 5.98ꢀ
6.04 (m, 1H), 3.76 (s, 3H), 3.63 (d, J = 6.0 Hz, 3H), 3.61 (d, J = 6.0 Hz, 3H), 2.46ꢀ2.54 (m, 1H),
2.22ꢀ2.30 (m, 1H), 2.02 (s, 3H); 13C NMR (150 MHz, CDCl3): δ 169.6, 159.6, 131.0 (d, J = 10.2 Hz),
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128.0, 113.9, 70.3, 52.4 (d, J = 6.5 Hz), 52.2 (d, J = 6.5 Hz), 32.3 (d, J = 139.2 Hz), 21.1; P NMR
(162 MHz, CDCl3): δ 28.3. HRMS (ESIꢀTOF) m/z: (MꢀOAc)+ Calcd for C11H16O4P 243.0786, found
243.0810.
2ꢀ(Dimethoxyphosphoryl)ꢀ1ꢀ(4ꢀfluorophenyl)ethyl acetate (5d). Colorless liquid; 59% yield
(171.1 mg). 1H NMR (400 MHz, CDCl3): δ 7.29ꢀ7.38 (m, 2H), 6.96ꢀ7.06 (m, 2H), 5.98ꢀ6.08 (m, 1H),
3.64 (d, J = 4.8 Hz, 3H), 3.62 (d, J = 4.8 Hz, 3H), 2.48 (ddd, J = 8.0, 15.5, 17.6 Hz, 1H), 2.25 (ddd, J
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= 6.1, 15.4, 18.9 Hz, 1H), 2.04 (s, 3H); C NMR (100 MHz, CDCl3): δ 169.6, 162.6 (d, J = 245.8
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Hz), 135.6 (dd, J = 3.3, 10.0 Hz), 128.5 (d, J = 8.3 Hz ), 115.6, 115.4, 70.0, 52.5 (d, J = 6.4 Hz), 52.3
(d, J = 6.4 Hz), 32.4 (d, J = 139.7 Hz), 21.1; 31P NMR (162 MHz, CDCl3): δ 27.8. HRMS (ESIꢀTOF)
m/z: (M+Na)+ Calcd for C12H16FNaO5P 313.0617, found 313.0633.
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2ꢀ(Dimethoxyphosphoryl)ꢀ1ꢀ(4ꢀchlorophenyl)ethyl acetate (5e). Colorless liquid; 62% yield
(189.7 mg). 1H NMR (400 MHz, CDCl3): δ 7.28 (d, J = 8.4 Hz, 2H), 6.85 (d, J = 8.4 Hz, 2H), 5.99ꢀ
6.08 (m, 1H), 3.67 (d, J = 6.0 Hz, 3H), 3.65 (d, J = 6.0 Hz, 3H), 2.43ꢀ2.51 (m, 1H), 2.20ꢀ2.32 (m,
1H), 2.07 (s, 3H); 13C NMR (100 MHz, CDCl3): δ 169.5, 138.2 (d, J = 10.2 Hz), 134.3, 130.0 (d, J =
139.3 Hz), 128.4 (d, J = 85.2 Hz), 70.0, 52.5 (d, J = 7.4 Hz), 52.4 (d, J = 7.4 Hz), 33.1 (d, J = 14.0
Hz), 21.1; 31P NMR (162 MHz, CDCl3): δ 27.7. HRMS (ESIꢀTOF) m/z: (M+H)+ Calcd for
C12H17ClO5P 307.0502, found 307.0512.
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2ꢀ(Dimethoxyphosphoryl)ꢀ1ꢀ(4ꢀbromophenyl)ethyl acetate (5g). Colorless liquid; 51% yield
(180.0 mg). 1H NMR (400 MHz, CDCl3): δ 7.51 (d, J = 8.4 Hz, 2H), 7.29 (d, J = 8.4 Hz, 2H), 6.00ꢀ
6.08 (m, 1H), 3.71 (d, J = 2.6 Hz, 3H), 3.68 (d, J = 2.6 Hz, 3H), 2.46ꢀ2.58 (m, 1H), 2.23ꢀ2.34 (m,
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1H), 2.09 (s, 3H); C NMR (100 MHz, CDCl3): δ 169.6, 138.7 (d, J = 10.3 Hz), 131.8 (d, J = 6.3
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Hz), 128.3, 122.5, 70.1, 52.6 (d, J = 6.4 Hz), 52.4 (d, J = 6.4 Hz), 32.3 (d, J = 140.0 Hz), 21.1; P
NMR (162 MHz, CDCl3): δ 27.7. HRMS (ESIꢀTOF) m/z: (M+Na)+ Calcd for C12H16BrNaO5P
372.9816, found 372.9827.
Mixture of 2ꢀ(dimethoxyphosphoryl)ꢀ1ꢀ(3ꢀ(trifluoromethyl)phenyl)ethyl acetate (5h) and
dimethyl (2ꢀoxoꢀ2ꢀ(3ꢀ(trifluoromethyl)phenyl)ethyl)phosphonate (5h’). Colorless liquid; 37% (5h)
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and 37% (5h’) yield (245.5 mg), respectively, 5h : 5h’ = 1 : 1, analyzed by 1H NMR spectrum. H
NMR (400 MHz, CDCl3): δ 8.16ꢀ8.28 (m, 1H), 7.84 (d, J = 7.5 Hz, 1H), 7.32ꢀ7.70 (m, 6H), 7.40 (dd,
J = 8.0, 18.4 Hz, 1H), 6.05ꢀ6.15 (m, 1H), 3.75ꢀ3.80 (m, 2H), 3.31ꢀ3.68 (m, 6H), 2.44ꢀ2.56 (m, 1H),
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2.22ꢀ2.33 (m, 1H), 2.08 (d, J = 2.5 Hz, 3H); C NMR (100 MHz, CDCl3): δ 190.5 (d, J = 6.7 Hz),
169.5, 140.8 (d, J = 10.2 Hz), 136.7 (d, J = 2.1 Hz), 132.2, 131.0 (d, J = 32.4 Hz), 130.1 (d, J = 14.6
Hz), 129.4, 129.2, 125.8 (d, J = 3.8 Hz), 125.7 (d, J = 3.8 Hz), 125.3 (d, J = 3.7 Hz), 123.3 (d, J =
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3.7 Hz), 122.5, 70.0, 52.5 (d, J = 6.5 Hz), 52.4 (d, J = 6.5 Hz), 38.4, 37.8 (d, J = 130.0 Hz), 37.1,
32.4 (d, J = 140.0 Hz), 21.0; 31P NMR (162 MHz, CDCl3): δ 21.9, 27.4. HRMS (ESIꢀTOF) of 5h m/z:
(MꢀOAc)+ Calcd for C10H13F3O3P 281.0554, found 281.0561; HRMS (ESIꢀTOF) of 5h’ m/z:
(M+H)+ Calcd for C11H13F3O4P 297.0504, found 297.0511.
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Mixture of 2ꢀ(dimethoxyphosphoryl)ꢀ1ꢀ(4ꢀcyanophenyl)ethyl acetate (5i) and dimethyl (2ꢀ(4ꢀ
cyanophenyl)ꢀ2ꢀoxoethyl)phosphonate (5i’). Colorless liquid; 30% (5i) and 30% (5i’) yield (165.0
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mg), respectively, 5i : 5i’ = 1 : 1, analyzed by H NMR spectrum. H NMR (400 MHz, CDCl3): δ
8.11 (d, J = 8.3 Hz, 2H), 7.79 (d, J = 8.3 Hz, 2H), 7.66 (d, J = 8.2 Hz, 2H), 7.49 (d, J = 8.2 Hz, 2H),
6.02ꢀ6.11 (m, 1H), 3.79 (d, J = 11.3 Hz, 6H), 3.67 (d, J = 1.6 Hz, 3H), 3.65 (d, J = 1.6 Hz, 3H), 3.63
(d, J = 57.0 Hz, 2H), 2.42ꢀ2.53 (m, 1H), 2.20ꢀ2.32 (m, 1H), 2.09 (s, 3H); 13C NMR (100MHz,
CDCl3): δ 190.6 (d, J = 6.6 Hz), 169.4, 144.8 (d, J = 10.0 Hz), 139.2, 132.5 (d, J = 5.2 Hz), 130.9,
129.4, 128.9 (d, J = 10.0 Hz), 127.3, 118.1 (d, J = 63.2 Hz), 117.0, 112.4, 70.0, 53.3 (d, J = 6.6 Hz),
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52.6 (d, J = 6.5 Hz), 52.5 (d, J = 6.5 Hz), 38.0 (d, J = 129.4 Hz), 32.3 (d, J = 140.4 Hz), 20.9; P
NMR (162 MHz, CDCl3): δ 21.5, 27.1. HRMS (ESIꢀTOF) of 5i m/z: (M+Na)+ Calcd for
C13H16NO5PNa 320.0664, found 320.0681; HRMS (ESIꢀTOF) of 5i’ m/z: (M+Na)+ Calcd for
C11H12NO4PNa 276.0402, found 276.0409.
Dimethyl (2ꢀ(4ꢀnitrophenyl)ꢀ2ꢀoxoethyl)phosphonate (5j’). Yellow oil; 45% yield (122.8 mg).
1H NMR (400 MHz, CDCl3): δ 8.33 (d, J = 8.8 Hz, 2H), 8.18 (d, J = 8.8 Hz, 2H), 3.80 (d, J = 11.3
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Hz, 6H), 3.68 (d, J = 57.0 Hz, 2H); C NMR (100 MHz, CDCl3): δ 190.4 (d, J = 6.6 Hz), 150.6,
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140.6, 130.1, 123.9, 53.4 (d, J = 6.6 Hz), 38.2 (d, J = 129.3 Hz); P NMR (162 MHz, CDCl3): δ
21.3. HRMS (ESIꢀTOF) m/z: (M+Na)+ Calcd for C10H12NNaO6P 296.0300, found 296.0318.
1ꢀ(Dimethoxyphosphoryl)ꢀ2ꢀphenylpropanꢀ2ꢀyl acetate (5k). Colorless liquid; 67% yield (191.7
mg). 1H NMR (400 MHz, CDCl3): δ 7.32ꢀ7.39 (m, 4H), 7.23ꢀ7.30 (m, 1H), 3.76 (s, 3H), 3.61 (d, J =
11.2 Hz, 3H), 3.54 (d, J = 11.2 Hz, 3H), 2.90ꢀ3.00 (m, 1H), 2.64ꢀ2.75 (m, 1H), 2.02 (s, 3H), 1.96 (s,
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3H); C NMR (75 MHz, CDCl3): δ 169.8, 144.7 (d, J = 9.2 Hz), 128.4, 127.3, 124.2, 80.2 (d, J =
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2.7 Hz), 52.3 (d, J = 6.5 Hz), 52.1 (d, J = 6.5 Hz), 35.4 (d, J = 64.4 Hz), 27.8, 22.2; P NMR (162
MHz, CDCl3): δ 28.1. HRMS (ESIꢀTOF) m/z: (M+Na)+ Calcd for C13H19NaO5P 309.0868, found
309.0878.
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Mixture of 2ꢀ(dimethoxyphosphoryl)ꢀ1ꢀphenylpropyl acetate (5l) and dimethyl (1ꢀhydroxyꢀ1–
phenylpropanꢀ2ꢀyl)phosphonate (5l’). Colorless liquid; 50% (5l) and 25% (5l’) yield (204 mg),
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respectively, 5l : 5l’ = 2 : 1, analyzed by 1H NMR spectrum. H NMR (400 MHz, CDCl3): δ 7.31ꢀ
7.39 (m, 9 H), 7.26ꢀ7.30 (m, 6H), 6.21 (dd, J = 4.5, 8.3 Hz, 2H), 5.91 (t, J = 9.0 Hz, 1H), 3.76 (d, J =
3.0 Hz, 3H), 3.74 (d, J = 3.0 Hz, 3H), 3.67 (d, J = 10.7 Hz, 12H), 2.53 (ddd, J = 7.4, 9.2, 17.9 Hz,
1H), 2.29ꢀ2.40 (m, 2H), 2.13 (s, 6H), 2.07 (s, 3H), 1.21 (dd, J = 7.3, 17.8, 6H), 0.99 (dd, J = 7.4,
17.6 Hz, 3H); 13C NMR (100 MHz, CDCl3): δ 169.5 (d, J = 9.4 Hz), 138.8 (d, J = 11.4 Hz), 138.0 (d,
J = 11.8 Hz), 128.4 (d, J = 2.7 Hz), 128.3, 127.9, 127.4, 126.2, 74.9 (d, J = 2.8 Hz), 73.1, 52.7 (d, J =
7.0 Hz), 52.6 (d, J = 7.0 Hz), 52.5 (d, J = 6.7 Hz), 52.4 (d, J = 6.7 Hz), 37.4 (d, J = 140.0 Hz), 36.2
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(d, J = 140.0 Hz), 21.0 (d, J = 18.3 Hz), 11.2 (d, J = 5.5 Hz), 8.5 (d, J = 3.7 Hz); P NMR (162
MHz, CDCl3): δ 32.0, 32.1. HRMS (ESIꢀTOF) of 5l m/z: (MꢀOAc)+ Calcd for C11H16O3P 227.0837,
found 227.0833; HRMS (ESIꢀTOF) of 5l’ m/z: (M+Na)+ Calcd for C11H17O4P Na 267.0762, found
267.0763.
Dimethyl (2ꢀbromoꢀ2ꢀphenylvinyl)phosphonate (5m). Colorless liquid; 21% yield (60.9 mg). 1H
NMR (400 MHz, CDCl3): δ 7.60ꢀ7.65 (m, 2H), 7.37ꢀ7.44 (m, 3H), 6.65 (d, J = 9.7 Hz, 1H), 3.85 (d,
J = 11.4 Hz, 6H); 13C NMR (100 MHz, CDCl3): δ 142.3, 138.9 (d, J = 17.7 Hz), 130.7, 128.6, 127.8,
117.0 (d, J = 196.0 Hz), 52.8 (d, J = 5.9 Hz); 31P NMR (162 MHz, CDCl3): δ 16.0. HRMS (ESIꢀTOF)
m/z: (M+Na)+ Calcd for C10H12BrNaO3P 312.9605, found 312.9606.
Dimethyl (2ꢀoxoꢀ2ꢀphenylethyl)phosphonate (5m’). 13 Colorless liquid; 50% yield (114.0 mg).
1H NMR (400 MHz, CDCl3): δ 7.97ꢀ8.02 (m, 2H), 7.56ꢀ7.62 (m, 1H), 7.45ꢀ7.52 (m, 2H), 3.77 (d, J
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= 11.2 Hz, 6H), 3.64 (d, J = 22.8 Hz, 2H); C NMR (75 MHz, CDCl3): δ 191.7 (d, J = 6.5 Hz),
136.3 (d, J = 2.5 Hz), 133.8, 128.9, 128.7, 53.2 (d, J = 6.5 Hz), 37.4 (d, J = 131.0 Hz). HRMS (ESIꢀ
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(E)ꢀDimethyl styrylphosphonate (5n).14 Colorless liquid; 61% yield (129.3 mg). H NMR (400
MHz, CDCl3): δ 7.54ꢀ7.62 (m, 1H), 7.49ꢀ7.53 (m, 2H), 7.38ꢀ7.43 (m, 3H), 6.24 (dd, J = 17.6, 17.8
Hz, 1H), 3.79 (d, J = 11.1 Hz, 6H); 13C NMR (100 MHz, CDCl3): δ 149.7 (d, J = 6.7 Hz), 134.6 (d, J
= 23.3 Hz), 130.4, 128.9, 127.8, 112.3 (d, J = 191.3 Hz), 52.5 (d, J = 5.6 Hz).
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Dimethyl (2,2ꢀdiphenylvinyl)phosphonate (5o’).15 Colorless liquid; 78% yield (224.7 mg). H
NMR (400 MHz, CDCl3): δ 7.27ꢀ7.42 (m, 10H), 6.18 (d, J = 15.6 Hz, 1H), 3.49 (d, J = 11.2 Hz, 6H);
13C NMR (75 MHz, CDCl3): δ 160.8 (d, J = 6.4 Hz), 141.1 (d, J = 23.8 Hz), 138.7 (d, J = 7.6 Hz),
129.5, 128.7, 128.2 (d, J = 15.2 Hz) , 127.9, 127.0, 125.7, 113.5 (d, J = 193.3 Hz), 52.3 (d, J = 6.5
Hz), 52.1 (d, J = 6.0 Hz). HRMS (ESIꢀTOF) m/z: (M+H)+ Calcd for C16H18O3P 289.0994, found
289.1003.
Mixture of 2ꢀ(dimethoxyphosphoryl)ꢀ1,2ꢀdiphenylethyl acetate (5p) and dimethyl (2ꢀoxoꢀ1,2ꢀ
diphenylethyl) phosphonate (5p’).Colorless liquid; 48% (5p) and 12% (5p’) yield (200.0 mg),
respectively, 5p : 5p’ = 4 : 1, analyzed by 1H NMR spectrum. 1H NMR (400 MHz, CDCl3): δ 7.38 ꢀ
7.43 (m, 2H), 7.26ꢀ7.35 (m, 8 H), 6.52 (dd, J = 6.2, 7.5 Hz, 1H), 3.85 (dd, J = 0.5, 11.3 Hz, 1H), 3.56
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(dd, J = 7.6, 23.1 Hz, 1H), 3.43 (d, J = 10.9 Hz, 3H), 3.31 (d, J = 10.6 Hz, 3H), 1.91 (s, 3H); C
NMR (100 MHz, CDCl3): δ 191.6 (d, J = 4.0 Hz), 169.4, 138.5 (d, J = 6.5 Hz), 134.3 (d, J = 8.8 Hz),
133.3, 133.0, 132.9 (d, J = 2.9 Hz), 132.8 (d, J = 5.5 Hz), 130.2 (d, J = 6.9 Hz), 128.3 (d, J = 1.8 Hz),
128.2, 128.1, 127.6 (d, J = 2.5 Hz), 127.2, 74.0 (d, J = 3.9 Hz), 53.4 (d, J = 6.9 Hz), 53.0 (d, J = 5.9
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Hz), 52.4 (d, J = 7.3 Hz), 51.9, 50.5, 20.8; P NMR (162 MHz, CDCl3): δ 25.9, 26.0. HRMS (ESIꢀ
TOF) of 5p m/z: (M+Na)+ Calcd for C18H21O5PNa 371.1025, found 371.1035.
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Dimethyl (4ꢀphenylbutyl)phosphonate (5r). Colorless liquid; 75% yield (181.6 mg). H NMR
(400 MHz, CDCl3): δ 7.27ꢀ7.32 (m, 2H), 7.15ꢀ7.23 (m, 3H), 3.74 (d, J = 10.8 Hz, 6H), 2.64 (t, J =
7.6 Hz, 2H), 1.64ꢀ1.84 (m, 6H); 13C NMR (100 MHz, CDCl3): δ 141.8, 128.4, 128.3, 125.8, 52.4 (d,
J = 6.6 Hz), 35.4 (d, J = 1.0 Hz), 32.2 (d, J = 16.0 Hz), 24.4 (d, J = 140.0 Hz), 21.9 (d, J = 5.2 Hz);
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31P NMR (162 MHz, CDCl3): δ 34.9. HRMS (ESIꢀTOF) m/z: (M+H)+ Calcd for C12H20O3P
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243.1150, found 243.1164.
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ASSOCIATED CONTENT
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Supporting Information
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1H, C and P NMR spectra for compounds 3 and 5, and mechanism discussion. This material is
available free of charge via the Internet at http://pubs.acs.org.
AUTHOR INFORMATION
Corresponding Author
*Eꢀmail: jpzou@suda.edu.cn.
Notes
The authors declare no competing financial interest.
ACKNOWLEDGEMENTS
JPZ thanks the grant support by National Natural Science Foundation of China (No. 20772088,
21172163) and the Priority Academic Program Development of Jiangsu Higher Education
Institutions for financial support.
REFERENCES
(1) For selected reviews see: (a) Kolb, H. C.; VanNieuwenhze, M. S.; Sharpless, K. B. Chem. Rev. 1994, 94,
2483. (b) Bataille, C. J. R.; Donohoe, T. J. Chem. Soc. Rev. 2011, 40, 114.
(2) (a) Maryanoff, B. E.; Reitz, A. B. Chem. Rev. 1989, 89, 863. (b) Yan, B.; Spilling, C. D. J. Org. Chem.
2008, 73, 5385. (c) Perumal, S. K.; Adediran, S. A.; Pratt, R. F. Bioorg. Med. Chem. 2008, 16, 6987. (d)
Cotton, F. A.; Schunn, R. A. J. Am. Chem. Soc. 1963, 85, 2394. (e) Ryglowski, A.; Kafarski, P.
Tetrahedron 1996, 52, 10685. (f) Kitamura, M.; Tokunaga, M.; Noyori, R. J. Am. Chem. Soc. 1995, 117,
2931. (g) Woodyer, R. D.; Li, G.; Zhao, H.; van der Donk, W. A. Chem. Commun. 2007, 359. (h) Cui, P.;
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Tomsig, J. L.; McCalmont, W. F.; Lee, S.; Becker, C. J.; Lynch, K. R.; Macdonald, T. L. Bioorg. Med.
Chem. Lett. 2007, 17, 1634. (i) Munos, J. W.; Moon, S. J.; Mansoorabadi, S. O.; Chang, W.; Hong, L.;
Yan, F.; Liu, A.; Liu, H. W. Biochemistry 2008, 47, 8726.
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(3) Selected recent Pꢀcentered radical reviews: (a) Hideki, Y. Beilstein J. Org. Chem. 2013, 9, 1269. (b) Van
der Jeught, S.; Stevens, C. V. Chem. Rev. 2009, 109, 2672. (c) Coudray, L.; Montchamp, J. L. Eur. J. Org.
Chem. 2008, 3601. (d) Arbuzova, S. N.; Gusarova, N. K.; Trofimov, B. A. Arkivoc 2006, 12. (e) Laca, D.;
Fensterbank, L.; Lacote, E.; Malacria, M. Chem. Soc. Rev. 2005, 34, 858. (f) Marque, S.; Tordo, P.
Topics in Curr. Chem. 2005, 250, 43. (g) Delacroix, O.; Gaumont, A. C. Curr. Org. Chem. 2005, 9, 1851.
Selected recent Pꢀcentered radical papers: (h) Ma, W.; Ackermann, L. Synthesis 2014, 46, 2297. (i)
Zhang, F.; Wang, L.; Zhang C.; Zhao, Y. Chem. Commun. 2014, 50, 2046. (j) Zhang, B.; Daniliuc, C. G.;
Studer, A. Org. Lett. 2014, 16, 250. (k) Mi, X.; Wang, C.; Huang, M.; Zhang, J.; Wu, Y.; Wu, Y. Org.
Lett. 2014, 16, 3356. (l) Chu, X.ꢀQ.; Zi, Y.; Meng, H.; Xu X.ꢀP.; Ji, S.ꢀJ. Chem. Commun. 2014, 50, 7642.
(m) Chen, X.ꢀL.; Li, X.; Qu, L.ꢀB.; Tang, Y.ꢀC.; Mai, W.ꢀP.; Wei, D.ꢀH.; Bi, W.ꢀZ.; Duan, L.ꢀK.; Sun, K.;
Chen, J.ꢀY.; Ke, D.ꢀD.; Zhao, Y.ꢀF. J. Org. Chem. 2014, 79, 8407. (n) Li, Y.; Qiu, G.; Ding, Q.; Wu, J.
Tetrahedron 2014, 70, 4652. (o) Yoo, W.ꢀJ.; Kobayashi, S. Green Chemistry 2014, 16, 2438. (p) Kong,
W.; Merino, E.; Nevado, C. Angew. Chem. Int. Ed. 2014, 53, 5078. (q) Chen, S.ꢀY.; Zeng, R.ꢀS.; Zou, J.ꢀ
P.; Asekun, O. T. J. Org. Chem. 2014, 79, 1449. (r) Chen, Y.ꢀR.; Duan, W.ꢀL. J. Am. Chem. Soc. 2013,
135, 16754. (s) Biresaw, G.; Bantchev, G. B. J. Am. Oil Chem. Soc. 2013, 90, 891. (t) HernandezꢀGuerra,
D.; Rodriguez, M. S.; Suarez, E. Org. Lett. 2013, 15, 250.
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50
51
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53
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55
56
57
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(4) (a) Wei, W.; Ji, J.ꢀX. Angew. Chem. Int. Ed. 2011, 50, 9097. (b) Zhang, C.ꢀW.; Li, Z.ꢀD.; Zhu, L.; Yu, L.ꢀ
M.; Wang, Z.ꢀT.; Li, C.ꢀZ. J. Am. Chem. Soc. 2013, 135, 14082.
(5) Selected recent Mn(OAc)3ꢀmediated reaction reviews: (a) Mondal, M.; Bora, U. RSC Adv. 2013, 3,
18716. (b) Yan, G.; Yang, M.; Wu, X. Org. Biomol. Chem. 2013, 11, 7999. (c) Pan, X.ꢀQ.; Zou, J.ꢀP.;
Zhang, W. Mol. Divers. 2009, 13, 421. (d) Snider, B. B. Tetrahedron, 2009, 65, 10738. (e) Demir A. S.;
Emrullahoglu, M. Curr. Org. Syn. 2007, 4, 321. (f) Linker, T. J. Organomet. Chem. 2002, 661, 159. (g)
Parsons, A. F. C. R. Acad. Sci. Paris, Chimie / Chemistry, 2001, 4, 391. (h) Snider, B. B. Chem. Rev.
1996, 96, 339. Selected recent Mn(OAc)3ꢀmediated reaction papers: (i) Li, Y.; Qiu, G.; Ding, Q.; Wu, J.
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3
4
5
6
7
8
Tetrahedron 2014, 70, 4652. (j) Alagoez, O.; Yilmaz, M.; Pekel, A. T.; Graiff, C.; Maggi, R., RSC Adv.
2014, 4, 14644. (k) Li, D.ꢀP.; Pan, X.ꢀQ.; An, L.ꢀT.; Zou, J.ꢀP.; Zhang, W. J. Org. Chem. 2014, 79, 1850.
(l) He, S.; Yang, W.; Zhu, L.; Du, G.; Lee, C.ꢀS. Org. Lett. 2014, 16, 496. (m) Cao, X.ꢀH.; Pan, X.ꢀQ.;
Zhou, P.ꢀJ.; Zou, J.ꢀP.; Asekun, O. T. Chem. Commun. 2014, 50, 3359. (n) Bouhlel, A.; Curti, C.; Tabele,
C.; Vanelle, P. Molecules 2013, 18, 4293. (o) Chuang, C.ꢀP.; Tsai, A.ꢀI.; Tsai, M.ꢀY. Tetrahedron 2013,
69, 3293. (p) Sun, W.ꢀB.; Ji, Y.ꢀF.; Pan, X.ꢀQ.; Zhou, S.ꢀF.; Zou, J.ꢀP.; Zhang, W.; Asekun, O. T.
Synthesis 2013, 45, 1529.
9
10
11
12
13
14
15
16
(6) Pan, X.ꢀQ.; Wang, L.; Zou, J.ꢀP.; Zhang, Wei. Chem. Commun. 2011, 47, 7875.
(7) Steenis, V.; Hein, J.; Gen, V. D. Eur. J. Org. Chem. 2001, 5, 897.
(8) GonzálezꢀNogal, A. M.; Cuadrado, P.; Sarmentero, M. A. Eur. J. Org. Chem. 2009, 850.
(9) Kawaguchi, S.; Nomoto, A.; Sonoda, M.; Ogawa, A. Tetrahedron Lett. 2009, 506, 624.
(10) Christiane, S. R. Synthesis 1988, 1, 64.
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
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43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
(11) Vedejs, E. J. Org. Chem. 1981, 46, 5253.
(12) Takaki, K.; Takeda, M.; Koshoji, G.; Shishido, T.; Takehira, K. Tetrahedron Lett. 2001, 42, 6357.
(13) Maloney, K. M.; Chung, J. Y. L. J. Org. Chem., 2009, 74, 7574.
(14) Koh, Y. J.; Oh, D. Y. Syn. Commun. 1995, 25, 2587.
(15) Kawashima, T. Tetrahedron Lett. 1983, 24, 739.
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