Cobalt(II)-Catalyzed Bisfunctionalization of Alkenes with Diarylphosphine Oxide and Peroxide

Article abstract of DOI:10.1002/adsc.201900873

The low-cost cobalt(II) catalyst has been used for the first time to achieve P(O)-radical-mediated bisfunctionalization of alkenes with diarylphosphine oxide and peroxides. This simple process is performed under mild conditions to afford a wide variety of phosphonation-peroxidation products in a one-pot manner. Computational studies are carried out to provide a theoretical support for the P(O)-radical-involved bisfunctionalization of alkenes. (Figure presented.).

Full text of DOI:10.1002/adsc.201900873

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DOI: 10.1002/adsc.201900873
Cobalt(II)-Catalyzed Bisfunctionalization of Alkenes with
Diarylphosphine Oxide and Peroxide
Jian Shen,a Bo Xiao,a Yang Hou,a Xue Wang,a Gui-Zhi Li,a Jin-Chun Chen,a
Wei-Li Wang,b Jian-Bo Cheng,a Bin Yang,a,* and Shang-Dong Yangc
a
College of Chemistry and Chemical Engineering, Yantai University, Yantai 264005, People’s Republic of China
E-mail: yangbin_hy@ytu.edu.cn
School of Chemistry and Material Science, Ludong University, Yantai, 264025, People’s Republic of China
State Key Laboratory of Applied Organic Chemistry, Lanzhou University, Lanzhou 730000, People’s Republic China
b
c
Manuscript received: July 15, 2019; Revised manuscript received: September 2, 2019;
Version of record online: ■■■, ■■■■
Supporting information for this article is available on the WWW under https://doi.org/10.1002/adsc.201900873
Abstract: The low-cost cobalt(II) catalyst has been used for the first time to achieve P(O)-radical-mediated
bisfunctionalization of alkenes with diarylphosphine oxide and peroxides. This simple process is performed
under mild conditions to afford a wide variety of phosphonation-peroxidation products in a one-pot manner.
Computational studies are carried out to provide a theoretical support for the P(O)-radical-involved
bisfunctionalization of alkenes.
Keywords: cobalt-catalyzed; phosphonation; difunctionalization; peroxidation; radicals
Introduction
Organophosphorus compounds have attracted signifi-
cant attention from chemists due to their remarkable
biological,[1] chemical[2] and physical[3] properties. This
range of properties makes them applicable to diverse
fields, ranging from pharmaceutical chemistry to the
material sciences.[4] Consequently, considerable effort
has been directed towards exploring practical and
efficient methods for the formation of CÀ P bonds. In
Scheme 1. P(O)-radical-mediated difunctionalizations.
the past decade, P-radical initiated bisfunctionalization
of alkenes has emerged as one of the most powerful
strategies to install a P(O) moiety along with another
functional group in a single step.[5] Among these, the synthetic chemistry.[11] Since Li’s group pioneered a
metal mediated transformations dominate this field new method of Fe-catalyzed acylation-peroxidation in
(Scheme 1, Path a), with Mn,[6] Ag[7] and Cu[8] being 2011,[12] the bisfunctionalization of alkenes has evolved
the most commonly used metals. Recently, our group as an attractive strategy for the synthesis of
has also developed a Ce(IV)-initiated bisfunctionaliza- peroxides.[13,14] Last year, the same group developed a
tion of alkenes.[9] Despite the high efficiency of these Cu-catalyzed phosphorylation-peroxidation reaction of
systems in most transformations, the problems associ- alkenes.[8g] However, in this work, the P(O)(Ar)2
ated with the limited metal scope and the use of excess radical could not be generated. As diaryl phosphorus is
metal salts hinder the development of this area. the basic framework of most P-ligands, the simulta-
Therefore, exploiting more efficient reaction systems is neous generation of diarylphosphoryl and peroxide
highly desirable and presents a challenge.
moieties in the same molecule may provide easy access
At the same time, peroxide-containing skeletons are to P-ligands. Considering this, as well as our continued
found in a wide variety of natural products and interest in the development of new strategies and
pharmaceutical compounds.[10] Furthermore, peroxides reaction systems for CÀ P bond formation,[9,15] herein,
are often key intermediates and building blocks in we introduce the first example of a Co(II)-catalyzed
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Table 1. Selected reaction condition optimizations. [a]
alkene phosphonation-peroxidation transformation
(Scheme 1, Path b). To the best of our knowledge, Co
(II)-catalyzed P(O)-radical-mediated bisfunctionaliza-
tion has not been reported, and hence this presents an
alternative approach in organophosphorus chemistry.
Entry
catalyst
(10 mol%)
1a/2a
Solvent
Yield
(%)[b]
Results and Discussion
We began our investigation with styrene (1a) and
diphenylphosphine oxide (2a) as model substrates in
the presence of 10 mol% Co(OAc)2 ·4H2O and
1
2
3
4
Co(OAc)2 ·4H2O
Co(OAc)2 ·4H2O
Co(OAc)2 ·4H2O
Co(OAc)2 ·4H2O
Co(OAc)2 ·4H2O
Co(OAc)2 ·4H2O
Co(OAc)2 ·4H2O
Co(OAc)2 ·4H2O
Co(OAc)2 ·4H2O
Co(OAc)2 ·4H2O
AgOAc
1.0:2.0
2.0:1.0
1.5:1.0
3.0:1.0
3.5:1.0
3.0:1.0
3.0:1.0
3.0:1.0
3.0:1.0
3.0:1.0
3.0:1.0
3.0:1.0
3.0:1.0
3.0:1.0
3.0:1.0
3.0:1.0
3.0:1.0
3.0:1.0
3.0:1.0
3.0:1.0
3.0:1.0
3.0:1.0
3.0:1.0
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
DCM
59
68
62
81
78
64
70
40
°
4.0 equiv. of TBHP in MeCN (2.0 mL) at 60 C under
5
a nitrogen atmosphere (Table 1, entry 1). To our
delight, the phosphonation-peroxidation product (3a)
was obtained in 59% yield. Encouraged by this result,
various parameters were screened to optimize the
reaction conditions. Firstly, when we reversed the ratio
of 1a to 2a, the yield was improved to 68% (Table 1,
entry 2). Pleasingly, by increasing the amount of 1a,
the yield increased to 81%. There were no subsequent
improvements upon increasing the equivalents of 1a
further (Table 1, entries 3–5). In the screening of
experimental conditions, a bisperoxide by-product was
detected. The formation of this by-product consumed
the amount of styrene, which lead to the use of
excessive styrene. Following this, the effect of altering
reaction temperature was examined. Changes from the
standard conditions resulted in a lower yield (Table 1,
entries 6–7). Solvent screening showed that MeCN is
the optimum solvent for the reaction (Table 1, en-
6[c]
7[d]
8
9
THF
13
10
11
12
13
14
15
16[f]
17[g]
18[h]
19[i]
20[j]
21[k]
22
23[l]
DMSO
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
trace
17
Cu(OAc)2
Mn(OAc)2 ·4H2O
CoCl2 ·6H2O
n.d.[e]
24
35
36
63
80
37
78
20
29
Co(acac)2
Co(OAc)2 ·4H2O
Co(OAc)2 ·4H2O
Co(OAc)2 ·4H2O
Co(OAc)2 ·4H2O
Co(OAc)2 ·4H2O
Co(OAc)2 ·4H2O
–
n.d.
n.d.
Co(OAc)2 ·4H2O
tries 8–10). Next, different catalysts were tested. [a] Reaction conditions: 1a (0.6 mmol), 2a (0.2 mmol), catalyst
However, none performed as well as Co(OAc)2 ·4H2O
(Table 1, entries 11–15). Altering the amount of TBHP
resulted in a lower yield (Table 1, entries 16–17).
Moreover, when the catalyst loading was reduced to
(10 mol%), TBHP (70% in water, 4 eq.), solvent (2.0 mL),
°
N2, stirred at 60 C for 11 h.
[b] Isolated yield.
[c]
°
Performed at 50 C.
[d]
°
Performed at 70 C.
5 mol%, the yield dropped sharply (Table 1, entry 18).
[e] n. d.=not detected.
When the catalyst loading was increased (Table 1,
[f] TBHP 3 eq.
entry 19), the yield did not increase beyond the
previous best results (Table 1, entry 4).It should be
noted that when TBHP (5.0–6.0 mol/L in decane) was
employed, only a small amount of 3a was obtained
(entry 20). Likewise, when the reaction was performed
in air, desired product 3a was obtained in just 29%
yield (Table 1, entry 21). Finally, control experiments
indicated that the phosphonation-peroxidation reaction
[g] TBHP 5 eq.
[h] cat 5 mol%.
[i] cat 15 mol%.
[j] TBHP (5.0–6.0 mol/L in decane) was used.
[k] Performed in air.
[l] Without TBHP.
did not occur in the absence of either Co(II)catalyst or styrenes were investigated (1b–1u). Both electron-rich
TBHP (entries 22–23). More detailed reaction condi- (1b–1h) and electron-poor (1i–1m) substituents on
tions screenings are listed in the SI. After the screen- the para-position of aryl ring were well tolerated, and
ing, the optimal reaction conditions were established as the corresponding products 3b–3m, containing alkyl
listed in Table 1, entry 4: 3.0 equiv. of 1a and (3a–3e), alkoxy (3f), ester (3g), aryl (3h), halogens
1.0 equiv. of 2a with 10 mol% of Co(OAc)2 ·4H2O and (3i–3k), cyano (3l) and trifluoromethyl (3m) groups,
4.0 equiv. of TBHP (70% in water) in the presence of were afforded in moderate to good yields. Additionally,
°
2.0 mL of MeCN at 60 C under a nitrogen atmos- both ortho- and meta- substituted styrenes are well-
phere.
tolerated in this reaction (3n–3s). The results indicate
With the optimized reaction conditions in hand, the that steric hindrance has an obvious influence on the
generality of this new protocol was explored and the yield. Despite this, multi-substituted styrenes still
results are listed in Table 2. A variety of substituted participated in the reaction smoothly, to afford prod-
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[b]
Table 2. Substrate scope. [a]
,
cumyl hydroperoxide, the phosphonation-peroxidation
process was still achieved (3cc). It is noteworthy that
alternative P(O)À H reagents, such as other diary-
lphosphine oxides and ethyl phenylphosphinate, were
amenable to this reaction, with products 3dd–3hh in
moderate to good yields. Nevertheless, this process
was not applicable to phosphites, the expected
phosphorylation-peroxidation product 3ii was not
detected under standard conditions. It is suggested that
our Co(II)/TBHP initiating system could not generate
the P(O)(OR)2 radical, and this supposition is sup-
ported by the theoretical bond dissociation energies
(BDE) of the PÀ H bonds and the stability of P-
radicals.[16] Moreover, when we use dimethylphosphine
oxide as the P-source, no products were detected. This
may be due to the instability of dialkylphosphine oxide
radical. It should be noted that alkylalkenes were
unsuitable for use in this reaction, and hydrophosphi-
nation-products were detected instead of the desired
phosphonation-peroxidation products. Other alkenes,
which are conjugated with heteroatom, including
phenyl(vinyl)sulfane, 4-vinylpyridine, α,β-unsaturated
carbonyl compounds (methyl acrylate and methyl
methacrylate) have also been investigated, however, no
phosphonation-peroxidation product was detected. We
also investigated a few alkynes, including ethynylben-
zene and some substituted ethynylbenzene, an insepa-
rable mixture was obtained. No phosphonation-perox-
idation products were detected from the NMR of the
crude products mixture. Finally, to showcase the
potential of this method in modification of natural
products, the derivative of estrone (1jj) was chosen as
a substrate, with 3jj was obtained in a moderate yield.
To demonstrate the utility of this reaction in organic
synthesis, several transformations of the peroxide
group on the substrates were performed (Scheme 2).
When 20 mol% DBU was used as a catalytic base, β-
ketophosphonate 4a was formed smoothly in an
excellent yield through a Kornblum-DeLaMare rear-
rangement (Scheme 2, eq 1). Moreover, in the presence
of palladium on carbon in methanol under a H2
[a] Unless specifically noted otherwise, reaction conditions: 1
(0.6 mmol), 2 (0.2 mmol), Co(OAc)2 ·4H2O (10 mol%),
TBHP (70% in water, 0.8 mmol), MeCN (2.0 mL), N2,
°
stirred at 60 C for 11 h.
[b] Isolated yield.
[c] Diastereomeric ratio determined by 31P NMR.
[d] Cumyl hydroperoxide (contains ca. 20% aromatic hydro-
carbon, 0.8 mmol).
[e] n. d.=not detected.
ucts (3t–3u) in good yields. When extended aromatic
systems were employed as substrates, the correspond-
ing products were obtained (3v–3w), although the
yield of 1-vinylnaphthalene is much lower than that of
2-vinylnaphthalene, potentially due to the effect of
steric hindrance. To our delight, the reaction of α-
substituted styrenes proceeded well, to give 3x and 3y
in 78% and 70% yield, respectively. Cyclic alkenes
were also tolerated in this reaction, with products
obtained in excellent diastereomeric ratio (3z–3aa). In
contrast, the use of β-methylstyrene resulted in a low
yield of 3bb, perhaps as a result of increased steric
hindrance. In addition, when TBHP was replaced by
Scheme 2. Transformations of the peroxide group.
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Scheme 3. Control experiments.
Scheme 4. Computational studies.
atmosphere, the peroxide group was transformed to a styrene. These results could also provide theoretical
hydroxyl group, yielding β-hydroxyphosphonate 5a in support for other P(O)-radical-involved bisfunctionali-
85% yield (Scheme 2, eq 2). Furthermore, the α,β- zations of alkenes.[5]
epoxy phosphorus unit is widely found in natural
Based on the above experimental results and
products and commonly used as a precursor for the previous reports,[5,14] we have devised a plausible
synthesis of various functionalized phosphorus com- mechanistic pathway, and this is as illustrated in
pounds, including chiral phosphorus ligands.[17] Pleas- Scheme 5. The generation of tert-butyloxy and tert-
ingly, the epoxide products 6x or 6y could be readily butylperoxy radicals is likely to be facilitated by a Co
obtained by treating 3x or 3y with 2 equivalents of (II)/Co(III) cycle. Subsequently, phosphorus radical C
LHMDS in THF (Scheme 2, eq 3).
is then generated from diphenylphosphine oxide (2a)
In order to shed light on the reaction mechanism, by hydrogen atom abstraction by the tert-butyloxy
several control experiments were conducted radical. Following this, C undergoes addition to the
(Scheme 3). As shown, the phosphonation-peroxida- double bond, leading to a carbon-radical D. Finally,
tion reaction was completely suppressed by the according to the persistent radical effect (PRE),[18] the
addition of 2.0 equivalents of 2,2,6,6-tetramethyl-1- transient carbon-radical D undergoes a radical-radical
piperdinyloxy (TEMPO) (Scheme 3, eq 4). When cross-coupling with a persistent tert-butylperoxy radi-
another radical inhibitor, 2,6-di-tert-butyl-p-cresol cal to afford the product (3a).
(BHT), was present in the reaction mixture, only a
small amount 3a was isolated (Scheme 3, eq 5).
Furthermore, when 1, 1-diphenylethylene (1y) was
Conclusion
employed as a substrate, we observed the generation of In summary, we have developed the first example of
alkenyl diphenylphosphine oxide 7 in addition to the cobalt(II)-catalyzed bisfunctionalization of styrenes
desired product 3y (Scheme 3, eq 6). The above results with aryl phosphorus reagents and peroxides. The
indicate a radical pathway is likely to be operative in reaction proceeds efficiently under mild conditions to
this reaction. In addition, when the reaction was carried
out in the absence of 2a, product 8 was detected
(Scheme 3, eq 7). It suggested that a peroxyl radical
was generated in the presence of Co(II) from TBHP
and could attack the double bond of styrene.
To provide an explanation for the presence of Ph2
*
(O)P radical adduct and the chemoselectivity of this
reaction, computational studies were carried out
(Scheme 4). The results indicate that the attack of Ph2
*
(O)P to styrene has the lowest energy barrier
(9.71 kcal/mol), and the formed radical adduct A is
*
exothermic by 12.44 kcal/mol. Therefore, Ph2(O)P is
more likely to undergo electrophilic addition with
Scheme 5. Plausible mechanistic pathway.
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CDCl3): δ 27.26. HRMS calc. for C24H28O3P (M+H)+:
395.1771, found 395.1771.
provide a convenient approach to various phosphona-
tion-peroxidation compounds in a one-pot manner. A P
(O)-radical-mediated pathway is proposed following
the computational and preliminary mechanistic studies.
Further investigations into the mechanism and the
potential applications of this methodology are ongoing
in our laboratory.
(2-(tert-butylperoxy)-2-(p-tolyl)ethyl)
diphenylphosphine
oxide (3b): The crude product was purified by column
chromatography on silica gel (petroleum ether/ethyl acetate=
2:1 as an eluent) to afford the product 3b (69% yield, 56.3 mg)
as white solid, m. p.=145–146 C. 1H NMR (500 MHz,
°
CDCl3): δ 7.85–7.82 (m, 2H), 7.56–7.45 (m, 5H), 7.39–7.36 (m,
1H), 7.31–7.26 (m, 2H), 7.19–7.18 (m, 2H), 7.02–7.01 (m, 2H),
5.40 (dd, J1 =6.9 Hz, J2 =13.9 Hz, 1H), 3.18–3.12 (m, 1H),
2.68–2.61 (m, 1H), 2.27 (s, 3H), 1.02 (s, 9H). 13C NMR
(125 MHz, CDCl3): δ 137.7, 137.0 (d, JC-P =6.5 Hz), 133.9 (d,
Experimental Section
General methods: 1H and 13C NMR spectra were recorded on a
500 M Bruker AVANCE NEO spectrometer in CDCl3 with
TMS as internal standard. 31P NMR and 19F NMR spectra were
recorded on the same instrument. High resolution mass
spectroscopic (HRMS) and mass spectra were measured using
Thermo Scientific DS II mass spectrometer and Bruker micro
TOF-Q mass spectrometer. Melting points were measured on a
WRS-1C digital melting point apparatus and are uncorrected.
The starting materials were purchased from Aldrich, Acros
Organics, J&K Chemicals or TCI and used without further
purification. Solvents were dried and purified according to the
procedure from “Purification of Laboratory Chemicals book”.
Column chromatography was carried out on silica gel (particle
size 200–400 mesh ASTM). All the computational calculations
are carried out with the GAUSSIAN 09 program.[19] The
optimized geometries and harmonic frequencies of the stable
structures and transition states are calculated using the M06-2X
method[20] with 6-31+G (d,p) basis set. To consider the solvent
effects, the polarizable continuum method (PCM) model[21] with
CH3CN as the solvent is employed.
J
C-P =19.1 Hz), 133.1 (d, JC-P =19.3 Hz), 131.5 (d, JC-P =
2.6 Hz), 131.1 (d, JC-P =2.5 Hz), 130.8 (d, JC-P =9.2 Hz), 130.4
(d, JC-P =9.3 Hz), 128.9, 128.4 (d, JC-P =11.8 Hz), 128.2 (d, JC-P
=11.8 Hz), 127.0, 80.5, 80.1, 35.8 (d, JC-P =69.1 Hz), 26.2,
21.1. 31P NMR (203 MHz, CDCl3): δ 27.50. HRMS calc. for
C25H30O3P (M+H)+: 409.1927, found 409.1934.
(2-(tert-butylperoxy)-2-(4-isopropylphenyl)ethyl) diphenyl-
phosphine oxide (3c): The crude product was purified by
column chromatography on silica gel (petroleum ether/ethyl
acetate=2:1 as an eluent) to afford the product 3c (64% yield,
55.8 mg) as white solid, m. p.=142–144 C. 1H NMR
°
(500 MHz, CDCl3): δ 7.84–7.79 (m, 2H), 7.53–7.45 (m, 5H),
7.35–7.33 (m, 1H), 7.29–7.25 (m, 2H), 7.21–7.19 (m, 2H),
7.05–7.03 (m, 2H), 5.42 (dd, J1 =6.9 Hz, J2 =13.8 Hz, 1H),
3.22–3.15 (m, 1H), 2.84–2.79 (m, 1H), 2.70–2.64 (m, 1H), 1.19
(d, J=6.9 Hz, 6H), 1.05 (s, 9H). 13C NMR (125 MHz, CDCl3):
δ 148.6, 137.0 (d, JC-P =6.2 Hz), 133.9 (d, JC-P =29.2 Hz), 133.1
(d, JC-P =29.1 Hz), 131.6 (d, JC-P =2.6 Hz), 131.2 (d, JC-P
=
2.6 Hz), 130.8 (d, JC-P =9.3 Hz), 130.4 (d, JC-P =9.7 Hz), 128.5
(d, JC-P =11.7 Hz), 128.2 (d, JC-P =11.8 Hz), 127.1, 126.2, 80.6,
80.3, 35.7 (d, JC-P =69.3 Hz), 33.8, 26.2, 23.9, 23.8. 31P NMR
(203 MHz, CDCl3): δ 27.68. HRMS calc. for C27H34O3P (M+
H)+: 437.2240, found 437.2230.
Typical Procedure for the Synthesis of Compounds 3: To a
Schlenk tube were added 2a (0.2 mmol), Cobalt (II) acetate
tetrahydrate (10 mol%) and charged with nitrogen for three
times. Then, TBHP (70% in water, 4.0 eq.), anhydrous MeCN
(2.0 mL) and styrene 1a (0.6 mmol) were added via syringe.
°
The mixture was allowed to stir at 60 C in an oil bath
(2-(4-(tert-butyl)phenyl)-2-(tert-butylperoxy)ethyl) diphenyl-
phosphine oxide (3d): The crude product was purified by
column chromatography on silica gel (petroleum ether/ethyl
acetate=2:1 as an eluent) to afford the product 3d (65% yield,
overnight. At the completion of the reaction, the reaction
mixture was cooled to room temperature, and the solvent was
removed by rotary. The resulting residue was purified by
column chromatography on silica gel (petroleum ether/ethyl
acetate=2:1) to afford the product (2-(tert-butylperoxy)-2-
phenylethyl)diphenylphosphine oxide 3a.
58.5 mg) as white solid, m. p.=161–163 C. 1H NMR
°
(500 MHz, CDCl3): δ 7.83–7.79 (m, 2H), 7.53–7.44 (m, 5H),
7.35–7.32 (m, 1H), 7.27–7.24 (m, 2H), 7.22–7.18 (m, 4H), 5.44
(dd, J1 =6.9 Hz, J2 =13.7 Hz, 1H), 3.22–3.16 (m, 1H), 2.71–
2.64 (m, 1H), 1.26 (s, 9H), 1.06 (s, 9H). 13C NMR (125 MHz,
Characterization of the Products
CDCl3): δ 150.7, 136.6 (d, JC-P =6.1 Hz), 134.0 (d, JC-P
38.6 Hz), 133.2 (d, JC-P =38.4 Hz), 131.5 (d, JC-P =2.5 Hz),
131.1 (d, JC-P =2.6 Hz), 130.7 (d, JC-P =9.2 Hz), 130.4 (d, JC-P
=
(2-(tert-butylperoxy)-2-phenylethyl)
diphenylphosphine
oxide (3a): The crude product was purified by column
chromatography on silica gel (petroleum ether/ethyl acetate=
2:1 as an eluent) to afford the product 3a (81% yield, 63.8 mg)
=
9.4 Hz), 128.4 (d, JC-P =11.8 Hz), 128.2 (d, JC-P =11.7 Hz),
126.7, 125.1, 80.6, 80.2, 35.6 (d, JC-P =69.0 Hz), 34.4, 31.2,
26.2. 31P NMR (203 MHz, CDCl3): δ 27.42. HRMS calc. for
C28H36O3P (M+H)+: 451.2397, found 451.2401.
as white solid, m. p.=139–141 C. 1H NMR (500 MHz,
°
CDCl3): δ 7.86–7.82 (m, 2H), 7.57–7.53 (m, 2H), 7.52–7.45 (m,
3H), 7.39–7.36 (m, 1H), 7.32–7.26 (m, 4H), 7.24–7.17 (m, 3H),
5.45 (dd, J1 =7.3 Hz, J2 =13.7 Hz, 1H), 3.16–3.09 (m, 1H),
2.68–2.61 (m, 1H), 1.01 (s, 9H). 13C NMR (125 MHz, CDCl3):
δ 140.2 (d, JC-P =6.9 Hz), 134.0 (d, JC-P =21.0 Hz), 133.2 (d,
(2-(tert-butylperoxy)-2-(4-(chloromethyl)phenyl)ethyl)
di-
phenylphosphine oxide (3e): The crude product was purified
by column chromatography on silica gel (petroleum ether/ethyl
acetate=2:1 as an eluent) to afford the product 3e (71% yield,
J
C-P =21.4 Hz), 131.5 (d, JC-P =2.6 Hz), 131.2 (d, JC-P =2.6 Hz),
130.8 (d, JC-P =9.2 Hz), 130.3 (d, JC-P =9.3 Hz), 128.4 (d, JC-P
62.7 mg) as white solid, m. p.=151–152 C. 1H NMR
°
=
(500 MHz, CDCl3): δ 7.85–7.81 (m, 2H), 7.54–7.46 (m, 5H),
7.39–7.36 (m, 1H), 7.31–7.27 (m, 4H), 7.23–7.22 (m, 2H), 5.45
(dd, J1 =6.9 Hz, J2 =14.0 Hz, 1H), 4.51 (s, 2H), 3.14–3.08(m,
11.9 Hz), 128.3 (d, JC-P =11.7 Hz), 128.2, 128.0, 127.0, 80.5,
80.1, 35.9 (d, JC-P =69.0 Hz), 26.2. 31P NMR (203 MHz,
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1H), 2.66–2.59 (m, 1H), 1.03 (s, 9H). 13C NMR (125 MHz,
CDCl3): δ 140.4 (d, JC-P =6.4 Hz), 137.0, 133.7 (d, JC-P
10.5 Hz), 132.9 (d, JC-P =10.3 Hz), 131.6 (d, JC-P =2.6 Hz),
2:1 as an eluent) to afford the product 3i (63% yield, 51.9 mg)
=
as white solid, m. p.=146–147 C. 1H NMR (500 MHz,
°
CDCl3): δ 7.84–7.80 (m, 2H), 7.55–7.45 (m, 5H), 7.41–7.38 (m,
1H), 7.32–7.25 (m, 4H), 6.90–6.86 (m, 2H), 5.42 (dd, J1 =
6.9 Hz, J2 =14.0 Hz, 1H), 3.17–3.11 (m, 1H), 2.66–2.59 (m,
1H), 1.03 (s, 9H). 13C NMR (125 MHz, CDCl3): δ 162.4 (d, JC-F
=244.7 Hz), 135.7 (dd, J1 =3.3 Hz, J2 =6.2 Hz), 133.7 (d, JC-P
=7.2 Hz), 132.9 (d, JC-P =7.0 Hz), 131.6 (d, JC-P =2.6 Hz),
131.4 (d, JC-P =2.6 Hz), 130.7 (d, JC-P =9.6 Hz), 130.3 (d, JC-P
9.3 Hz), 128.5, 128.4 (d, JC-P =1.6 Hz), 128.3 (d, JC-P
=
=
11.6 Hz), 127.3, 80.7, 79.8, 45.9, 35.8 (d, JC-P =69.1 Hz), 26.2.
31P NMR (203 MHz, CDCl3): δ 27.19. HRMS calc. for
C25H29ClO3P (M+H)+: 443.1537, found 443.1542.
131.3 (d, JC-P =2.6 Hz), 130.7 (d, JC-P =9.5 Hz), 130.3 (d, JC-P
=
(2-(tert-butylperoxy)-2-(4-methoxyphenyl)ethyl) diphenyl-
phosphine oxide (3f): The crude product was purified by
column chromatography on silica gel (petroleum ether/ethyl
acetate=2:1 as an eluent) to afford the product 3f (62% yield,
9.2 Hz), 128.9 (d, JC-P =8.2 Hz), 128.5 (d, JC-P =11.9 Hz), 128.3
(d, JC-P =11.7 Hz), 115.0 (d, JC-F =21.6 Hz), 80.6, 79.6, 35.7 (d,
J
C-P =69.2 Hz), 26.2. 19F NMR (470 MHz, CDCl3): δ À 114.17.
31P NMR (203 MHz, CDCl3): δ 27.17. HRMS calc. for
52.6 mg) as white solid, m. p.=139–140 C. 1H NMR
°
C24H27FO3P (M+H)+: 413.1676, found 413.1682.
(500 MHz, CDCl3): δ 7.84–7.80 (m, 2H), 7.55–7.45 (m, 5H),
7.38–7.36 (m, 1H), 7.31–7.27 (m, 2H), 7.19–7.18 (m, 2H), 7.20
(d, J=8.6 Hz, 2H), 6.72 (d, J=8.6 Hz, 2H), 5.38 (dd, J1 =
6.9 Hz, J2 =13.8 Hz, 1H), 3.74 (s, 3H), 3.23–3.17 (m, 1H),
2.69–2.63 (m, 1H), 1.04 (s, 9H). 13C NMR (125 MHz, CDCl3):
(2-(tert-butylperoxy)-2-(4-chlorophenyl)ethyl) diphenylphos-
phine oxide (3j): The crude product was purified by column
chromatography on silica gel (petroleum ether/ethyl acetate=
2:1 as an eluent) to afford the product 3j (62% yield, 53.1 mg)
°
δ 159.3, 133.8, 133.0, 131.7 (d, JC-P =6.0 Hz), 131.6 (d, JC-P
=
as white solid, m. p.=148–150 C. 1H NMR (500 MHz,
2.6 Hz), 131.1 (d, JC-P =2.6 Hz), 130.8 (d, JC-P =9.5 Hz), 130.4
(d, JC-P =9.3 Hz), 128.5, 128.4, 128.2 (d, JC-P =11.8 Hz), 113.5,
80.5, 79.9, 55.1, 35.5 (d, JC-P =69.3 Hz), 26.2. 31P NMR
(203 MHz, CDCl3): δ 27.69. HRMS calc. for C25H30O4P (M+
H)+: 425.1876, found 425.1869.
CDCl3): δ 7.84–7.80 (m, 2H), 7.55–7.46 (m, 5H), 7.43–7.40 (m,
1H), 7.33–7.30 (m, 2H), 7.24–7.22 (m, 2H), 7.17–7.15 (m, 2H),
5.42 (dd, J1 =7.0 Hz, J2 =14.0 Hz, 1H), 3.14–3.07 (m, 1H),
2.63–2.57 (m, 1H), 1.03 (s, 9H). 13C NMR (125 MHz, CDCl3):
δ 138.6 (d, JC-P =6.3 Hz), 133.8, 133.7 (d, JC-P =8.7 Hz), 132.9
(d, JC-P =8.1 Hz), 131.7 (d, JC-P =2.5 Hz), 131.3 (d, JC-P
=
4-(1-(tert-butylperoxy)-2-(diphenylphosphoryl)ethyl) phenyl
acetate (3g): The crude product was purified by column
chromatography on silica gel (petroleum ether/ethyl acetate=
2:1 as an eluent) to afford the product 3g (67% yield, 60.6 mg)
2.5 Hz), 130.8 (d, JC-P =9.3 Hz), 130.4 (d, JC-P =9.4 Hz), 128.5
(d, JC-P =11.9 Hz), 128.5, 128.4, 128.3, 80.7, 79.6, 35.8 (d, JC-P
=69.1 Hz), 26.2. 31P NMR (203 MHz, CDCl3): δ 27.06. HRMS
calc. for C24H27ClO3P (M+H)+: 429.1381, found 429.1387.
as white solid, m. p.=167–168 C. 1H NMR (500 MHz,
°
CDCl3): δ 7.86–7.82 (m, 2H), 7.57–7.46 (m, 5H), 7.41–7.31 (m,
5H), 6.95 (d, J=8.6 Hz, 2H), 5.46 (dd, J1 =7.2 Hz, J2 =
13.8 Hz, 1H), 3.13–3.07 (m, 1H), 2.66–2.59 (m, 1H), 2.27 (s,
3H), 1.01 (s, 9H). 13C NMR (125 MHz, CDCl3): δ 169.2, 150.2,
137.8 (d, JC-P =7.1 Hz), 133.7 (d, JC-P =10.9 Hz), 132.9 (d, JC-P
=11.5 Hz), 131.6 (d, JC-P =2.6 Hz), 131.3 (d, JC-P =2.6 Hz),
(2-(4-bromophenyl)-2-(tert-butylperoxy)ethyl) diphenylphos-
phine oxide (3k): The crude product was purified by column
chromatography on silica gel (petroleum ether/ethyl acetate=
2:1 as an eluent) to afford the product 3k (53% yield, 50.0 mg)
as white solid, m. p.=157–158 C. 1H NMR (500 MHz,
°
CDCl3): δ 7.84–7.80 (m, 2H), 7.54–7.46 (m, 5H), 7.43–7.40 (m,
1H), 7.33–7.27 (m, 4H), 7.18–7.16 (m, 2H), 5.40 (dd, J1 =
7.0 Hz, J2 =14.0 Hz, 1H), 3.13–3.06 (m, 1H), 2.62–2.56 (m,
1H), 1.02 (s, 9H). 13C NMR (125 MHz, CDCl3): δ 139.1 (d, JC-P
=6.3 Hz), 133.6 (d, JC-P =13.3 Hz), 132.8 (d, JC-P =12.7 Hz),
131.7 (d, JC-P =2.7 Hz), 131.3, 131.2, 130.7 (d, JC-P =9.2 Hz),
130.3 (d, JC-P =9.3 Hz), 128.8, 128.5 (d, JC-P =11.8 Hz), 128.4
(d, JC-P =11.8 Hz), 122.0, 80.7, 79.6, 35.8 (d, JC-P =69.3 Hz),
26.2. 31P NMR (203 MHz, CDCl3): δ 27.05. HRMS calc. for
C24H27BrO3P (M+H)+: 473.0876, found 473.0884.
130.7 (d, JC-P =9.3 Hz), 130.3 (d, JC-P =9.6 Hz), 128.4 (d, JC-P
=
7.7 Hz), 128.3 (d, JC-P =7.5 Hz), 128.0, 121.2, 80.6, 79.5, 35.9
(d, JC-P =69.1 Hz), 26.1, 21.0. 31P NMR (203 MHz, CDCl3): δ
27.26. HRMS calc. for C26H30O5P (M+H)+: 453.1825, found
453.1832.
(2-([1,1’-biphenyl]-4-yl)-2-(tert-butylperoxy)ethyl) diphenyl-
phosphine oxide (3h): The crude product was purified by
column chromatography on silica gel (petroleum ether/ethyl
acetate=2:1 as an eluent) to afford the product 3h (62% yield,
58.3 mg) as white solid, m. p.=180–182 C. 1H NMR
4-(1-(tert-butylperoxy)-2-(diphenylphosphoryl)ethyl) benzo-
nitrile (3l): The crude product was purified by column
chromatography on silica gel (petroleum ether/ethyl acetate=
2:1 as an eluent) to afford the product 3l (66% yield, 55.3 mg)
°
(500 MHz, CDCl3): δ 7.86–7.82 (m, 2H), 7.55–7.45 (m, 7H),
7.43–7.40 (m, 4H), 7.37–7.32 (m, 4H), 7.28–7.24 (m, 2H), 5.50
(dd, J1 =6.9 Hz, J2 =13.9 Hz, 1H), 3.23–3.16 (m, 1H), 2.73–
2.66 (m, 1H), 1.07 (s, 9H). 13C NMR (125 MHz, CDCl3): δ
140.9, 140.8, 138.9 (d, JC-P =6.2 Hz), 133.8 (d, JC-P =24.0 Hz),
133.0 (d, JC-P =23.6 Hz), 131.6 (d, JC-P =2.6 Hz), 131.1 (d, JC-P
=2.6 Hz), 130.7 (d, JC-P =9.5 Hz), 130.4 (d, JC-P =9.4 Hz),
128.6, 128.5 (d, JC-P =11.8 Hz), 128.2 (d, JC-P =11.8 Hz), 127.5,
127.2, 127.0, 126.9, 80.7, 80.1, 35.8 (d, JC-P =68.9 Hz), 26.2.
31P NMR (203 MHz, CDCl3): δ 27.19. HRMS calc. for
C30H32O3P (M+H)+: 471.2084, found 471.2093.
as white solid, m. p.=156–157 C. 1H NMR (500 MHz,
°
CDCl3): δ 7.85–7.81 (m, 2H), 7.56–7.48 (m, 7H), 7.45–7.41 (m,
3H), 7.35–7.31 (m, 2H), 5.49 (dd, J1 =7.1 Hz, J2 =14.2 Hz,
1H), 3.07–3.01 (m, 1H), 2.61–2.55 (m, 1H), 1.01 (s, 9H). 13C
NMR (125 MHz, CDCl3): δ 145.8 (d, JC-P =6.4 Hz), 133.3 (d,
J
C-P =8.4 Hz), 132.5 (d, JC-P =9.1 Hz), 131.9, 131.8 (d, JC-P
=
2.6 Hz), 131.5 (d, JC-P =2.6 Hz), 130.6 (d, JC-P =9.5 Hz), 130.2
(d, JC-P =9.3 Hz), 128.5 (d, JC-P =11.9 Hz), 128.4 (d, JC-P
11.8 Hz), 127.6, 118.6, 111.6, 80.9, 79.3, 35.7 (d, JC-P
=
=
(2-(tert-butylperoxy)-2-(4-fluorophenyl)ethyl) diphenylphos-
phine oxide (3i): The crude product was purified by column
chromatography on silica gel (petroleum ether/ethyl acetate=
68.9 Hz), 26.0. 31P NMR (203 MHz, CDCl3): δ 26.75. HRMS
calc. for C25H27NO3P (M+H)+: 420.1723, found 420.1714.
Adv. Synth. Catal. 2019, 361, 1–13
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(2-(tert-butylperoxy)-2-(4-(trifluoromethyl)phenyl) ethyl) di-
phenylphosphine oxide (3m): The crude product was purified
by column chromatography on silica gel (petroleum ether/ethyl
acetate=2:1 as an eluent) to afford the product 3m (70% yield,
(d, JC-P =9.3 Hz), 129.1, 128.4, 128.3, 127.4, 122.2, 80.8, 79.0
(d, JC-P =2.6 Hz), 35.1 (d, JC-P =68.4 Hz), 26.1. 31P NMR
(203 MHz, CDCl3): δ 26.13. HRMS calc. for C24H27BrO3P (M
+H)+: 473.0876, found 473.0885.
64.7 mg) as white solid, m. p.=144–146 C. 1H NMR
°
(2-(tert-butylperoxy)-2-(m-tolyl)ethyl)
diphenylphosphine
(500 MHz, CDCl3): δ 7.84–7.80 (m, 2H), 7.53–7.36 (m, 10H),
7.30–7.27 (m, 2H), 5.51 (dd, J1 =7.0 Hz, J2 =14.0 Hz, 1H),
3.12–3.06 (m, 1H), 2.64–2.57 (m, 1H), 1.04 (s, 9H). 13C NMR
oxide (3q): The crude product was purified by column
chromatography on silica gel (petroleum ether/ethyl acetate=
2:1 as an eluent) to afford the product 3q (67% yield, 54.7 mg)
(125 MHz, CDCl3): δ 144.3 (d, JC-P =5.3 Hz), 133.6 (d, JC-P
33.9 Hz), 132.8 (d, JC-P =33.4 Hz), 131.8 (d, JC-P =2.6 Hz),
131.5 (d, JC-P =2.6 Hz), 130.8 (d, JC-P =9.3 Hz), 130.4 (d, JC-P
=
as white solid, m. p.=134–136 C. 1H NMR (500 MHz,
°
CDCl3): δ 7.85–7.81 (m, 2H), 7.56–7.45 (m, 5H), 7.38–7.35 (m,
1H), 7.31–7.26 (m, 2H), 7.12–7.11 (m, 2H), 7.06 (s, 1H), 6.98
(d, J=5.8 Hz, 1H), 5.41 (dd, J1 =7.0 Hz, J2 =13.9 Hz, 1H),
3.17–3.11 (m, 1H), 2.68–2.61 (m, 1H), 2.24 (s, 3H), 1.03 (s,
9H). 13C NMR (125 MHz, CDCl3): δ 139.9 (d, JC-P =6.4 Hz),
137.7, 133.9 (d, JC-P =3.9 Hz), 133.1 (d, JC-P =3.5 Hz), 131.5
=
9.6 Hz), 130.1 (d, JC-F =32.2 Hz), 128.6 (d, JC-P =11.9 Hz),
128.5, 128.4, 127.4, 125.2 (q, JC-F =3.5 Hz), 80.9, 79.7, 35.9 (d,
J
C-P =69.1 Hz), 26.2. 19F NMR (470 MHz, CDCl3):
δ
À 62.64.31P NMR (203 MHz, CDCl3): δ 26.86. HRMS calc. for
C25H27F3O3P (M+H)+: 463.1644, found 463.1630.
(d, JC-P =2.6 Hz), 131.2 (d, JC-P =2.6 Hz), 130.8 (d, JC-P
9.6 Hz), 130.3 (d, JC-P =9.3 Hz), 128.8, 128.4 (d, JC-P
=
=
(2-(tert-butylperoxy)-2-(o-tolyl)ethyl)
diphenylphosphine
oxide (3n): The crude product was purified by column
chromatography on silica gel (petroleum ether/ethyl acetate=
2:1 as an eluent) to afford the product 3n (72% yield, 58.8 mg)
11.9 Hz), 128.2, 128.1 (d, JC-P =4.6 Hz), 127.7, 124.1, 80.6,
80.3, 35.8 (d, JC-P =69.0 Hz), 26.2, 21.2. 31P NMR (203 MHz,
CDCl3): δ 27.58. HRMS calc. for C25H30O3P (M+H)+:
409.1927, found 409.1917.
as white solid, m. p.=117–118 C. 1H NMR (500 MHz,
°
CDCl3): δ 7.86–7.82 (m, 2H), 7.55–7.45 (m, 5H), 7.37–7.26 (m,
4H), 7.08–6.99 (m, 3H), 5.73 (dd, J1 =7.0 Hz, J2 =14.0 Hz,
1H), 3.19–3.13 (m, 1H), 2.69–2.62 (m, 1H), 2.35 (s, 3H), 1.03
(s, 9H). 13C NMR (125 MHz, CDCl3): δ 138.1 (d, JC-P =6.3 Hz),
135.7, 133.9 (d, JC-P =24.8 Hz), 133.2 (d, JC-P =24.2 Hz), 131.5
(2-(tert-butylperoxy)-2-(3-chlorophenyl)ethyl) diphenylphos-
phine oxide (3r): The crude product was purified by column
chromatography on silica gel (petroleum ether/ethyl acetate=
2:1 as an eluent) to afford the product 3r (65% yield, 55.6 mg)
as white solid, m. p.=127–128 C. 1H NMR (500 MHz,
°
(d, JC-P =2.6 Hz), 131.2 (d, JC-P =2.6 Hz), 130.7 (d, JC-P
9.5 Hz), 130.3, 130.2 (d, JC-P =9.4 Hz), 128.4 (d, JC-P
=
=
CDCl3): δ 7.85–7.81 (m, 2H), 7.57–7.46 (m, 5H), 7.41–7.37 (m,
1H), 7.34–7.30 (m, 2H), 7.27 (s, 1H), 7.21–7.19 (m, 1H), 7.15–
7.13 (m, 2H), 5.42 (dd, J1 =7.2 Hz, J2 =13.9 Hz, 1H), 3.10–
3.03 (m, 1H), 2.62–2.56 (m, 1H), 1.02 (s, 9H). 13C NMR
(125 MHz, CDCl3): δ 142.3 (d, JC-P =6.7 Hz), 134.0, 133.6 (d,
11.8 Hz), 128.2 (d, JC-P =11.7 Hz), 127.8, 126.7, 125.8, 80.4,
76.5, 35.2 (d, JC-P =69.2 Hz), 26.2, 19.2. 31P NMR (203 MHz,
CDCl3): δ 27.31. HRMS calc. for C25H30O3P (M+H)+:
409.1927, found 409.1933.
J
C-P =11.9 Hz), 132.8 (d, JC-P =11.2 Hz), 131.7 (d, JC-P =
(2-(tert-butylperoxy)-2-(2-chlorophenyl)ethyl) diphenylphos-
phine oxide (3o): The crude product was purified by column
chromatography on silica gel (petroleum ether/ethyl acetate=
2:1 as an eluent) to afford the product 3o (62% yield, 53.1 mg)
2.6 Hz), 131.4 (d, JC-P =2.6 Hz), 130.7 (d, JC-P =9.4 Hz), 130.3
(d, JC-P =9.5 Hz), 129.5, 128.5 (d, JC-P =11.9 Hz), 128.3 (d, JC-P
=11.7 Hz), 128.1, 127.0, 125.2, 80.7, 79.5, 35.8 (d, JC-P
=
68.8 Hz), 26.1. 31P NMR (203 MHz, CDCl3): δ 26.99. HRMS
as white solid, m. p.=114–116 C. 1H NMR (500 MHz,
calc. for C24H27ClO3P (M+H)+: 429.1381, found 429.1384.
°
CDCl3): δ 7.87–7.83 (m, 2H), 7.70–7.66 (m, 2H), 7.53–7.41 (m,
5H), 7.39–7.35 (m, 2H), 7.27–7.21 (m, 3H), 5.88–5.83 (m, 1H),
2.93–2.87 (m, 1H), 2.79–2.72 (m, 1H), 1.02 (s, 9H). 13C NMR
(2-(3-bromophenyl)-2-(tert-butylperoxy)ethyl) diphenylphos-
phine oxide (3s): The crude product was purified by column
chromatography on silica gel (petroleum ether/ethyl acetate=
2:1 as an eluent) to afford the product 3s (61% yield, 57.6 mg)
(125 MHz, CDCl3): δ 138.3 (d, JC-P =9.1 Hz), 133.9 (d, JC-P
15.5 Hz), 133.1 (d, JC-P =16.2 Hz), 132.4, 131.5 (d, JC-P
=
=
as white solid, m. p.=128–129 C. 1H NMR (500 MHz,
°
2.6 Hz), 131.4 (d, JC-P =2.6 Hz), 130.8 (d, JC-P =9.5 Hz), 130.5
(d, JC-P =9.5 Hz), 129.5, 128.8, 128.4 (d, JC-P =2.7 Hz), 128.3
(d, JC-P =2.7 Hz), 128.3, 126.8, 80.8, 76.9 (d, JC-P =2.0 Hz),
34.9 (d, JC-P =68.6 Hz), 26.1. 31P NMR (203 MHz, CDCl3): δ
26.84. HRMS calc. for C24H27ClO3P (M+H)+: 429.1381, found
429.1387.
CDCl3): δ 7.85–7.80 (m, 2H), 7.57–7.46 (m, 5H), 7.42–7.37 (m,
2H), 7.34–7.24 (m, 4H), 7.07 (t, J=7.8 Hz, 1H), 5.41 (dd, J1 =
7.1 Hz, J2 =13.9 Hz, 1H), 3.10–3.03 (m, 1H), 2.62–2.55 (m,
1H), 1.02 (s, 9H). 13C NMR (125 MHz, CDCl3): δ 142.6 (d, JC-P
=6.8 Hz), 133.6 (d, JC-P =19.3 Hz), 132.8 (d, JC-P =18.5 Hz),
131.7 (d, JC-P =2.6 Hz), 131.4 (d, JC-P =2.6 Hz), 131.0, 130.7
(d, JC-P =9.3 Hz), 130.3 (d, JC-P =9.7 Hz), 129.9, 129.8, 128.5
(d, JC-P =11.8 Hz), 128.3 (d, JC-P =11.8 Hz), 125.7, 122.3, 80.7,
79.4, 35.8 (d, JC-P =68.8 Hz), 26.1. 31P NMR (203 MHz,
CDCl3): δ 26.98. HRMS calc. for C24H27BrO3P (M+H)+:
473.0876, found 473.0885.
(2-(2-bromophenyl)-2-(tert-butylperoxy)ethyl) diphenylphos-
phine oxide (3p): The crude product was purified by column
chromatography on silica gel (petroleum ether/ethyl acetate=
2:1 as an eluent) to afford the product 3p (56% yield, 52.9 mg)
as white solid, m. p.=131–133 C. 1H NMR (500 MHz,
°
CDCl3): δ 7.88–7.83 (m, 2H), 7.72–7.68 (m, 2H), 7.54–7.42 (m,
6H), 7.39–7.36 (m, 2H), 7.29–7.26 (m, 1H), 7.10–7.06 (m, 1H),
5.84–5.79 (m, 1H), 2.87–2.72 (m, 2H), 1.02 (s, 9H). 13C NMR
(2-(tert-butylperoxy)-2-(2,5-dimethylphenyl)ethyl) diphenyl-
phosphine oxide (3t): The crude product was purified by
column chromatography on silica gel (petroleum ether/ethyl
acetate=2:1 as an eluent) to afford the product 3t (73% yield,
(125 MHz, CDCl3): δ 140.0 (d, JC-P =9.3 Hz), 133.9 (d, JC-P
23.9 Hz), 133.1 (d, JC-P =24.6 Hz), 132.7, 131.5 (d, JC-P
=
=
61.6 mg) as white solid, m. p.=141–143 C. 1H NMR
°
2.7 Hz), 131.4 (d, JC-P =2.6 Hz), 130.8 (d, JC-P =9.4 Hz), 130.5
(500 MHz, CDCl3): δ 7.85–7.81 (m, 2H), 7.52–7.44 (m, 5H),
Adv. Synth. Catal. 2019, 361, 1–13
7
© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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7.35–7.32 (m, 1H), 7.28–7.24 (m, 2H), 7.05 (s, 1H), 6.90–6.84
(m, 2H), 5.70 (dd, J1 =6.9 Hz, J2 =13.8 Hz, 1H), 3.23–3.17 (m,
1H), 2.70–2.63 (m, 1H), 2.32 (s, 3H), 2.18 (s, 3H), 1.06 (s, 9H).
13C NMR (125 MHz, CDCl3): δ 137.3 (d, JC-P =5.8 Hz), 135.0,
134.0 (d, JC-P =48.1 Hz), 133.2 (d, JC-P =47.7 Hz), 132.7, 131.5
69.1 Hz), 26.2. 31P NMR (203 MHz, CDCl3): δ 27.47. HRMS
calc. for C28H30O3P (M+H)+: 445.1927, found 445.1921.
(2-(tert-butylperoxy)-2-phenylpropyl)
diphenylphosphine
oxide (3x): The crude product was purified by column
chromatography on silica gel (petroleum ether/ethyl acetate=
2:1 as an eluent) to afford the product 3x (78% yield, 63.6 mg)
(d, JC-P =2.6 Hz), 131.1 (d, JC-P =2.6 Hz), 130.7 (d, JC-P
9.2 Hz), 130.2, 130.1, 128.6, 128.4 (d, JC-P =11.8 Hz), 128.1 (d,
=
as white solid, m. p.=150–152 C. 1H NMR (500 MHz,
°
J
C-P =11.8 Hz), 127.5, 80.4, 76.7, 35.1 (d, JC-P =69.3 Hz), 26.2,
CDCl3): δ 7.82–7.78 (m, 2H), 7.46–7.29 (m, 8H), 7.23–7.20 (m,
2H), 7.16–7.08 (m, 3H), 3.08–3.03 (m, 1H), 2.80–2.75 (m, 1H),
2.05 (s, 3H), 1.04 (s, 9H). 13C NMR (125 MHz, CDCl3): δ
144.2 (d, JC-P =5.6 Hz), 134.7 (d, JC-P =100.1 Hz), 133.8 (d,
20.9, 18.8. 31P NMR (203 MHz, CDCl3): δ 27.36. HRMS calc.
for C26H32O3P (M+H)+: 423.2084, found 423.2088.
(2-(tert-butylperoxy)-2-(3,4-dimethylphenyl)ethyl) diphenyl-
phosphine oxide (3u): The crude product was purified by
column chromatography on silica gel (petroleum ether/ethyl
acetate=2:1 as an eluent) to afford the product 3u (75% yield,
J
C-P =99.4 Hz), 131.3 (d, JC-P =2.6 Hz), 130.8 (d, JC-P =2.7 Hz),
130.5 (d, JC-P =9.1 Hz), 130.2 (d, JC-P =9.2 Hz), 128.4 (d, JC-P
=
11.8 Hz), 128.1 (d, JC-P =11.6 Hz), 127.8, 127.1, 125.8, 125.2,
82.9 (d, JC-P =1.9 Hz)„ 79.2, 41.7 (d, JC-P =68.1 Hz), 26.4, 23.6.
31P NMR (203 MHz, CDCl3): δ 25.79. HRMS calc. for
C25H30O3P (M+H)+: 409.1927, found 409.1918.
63.3 mg) as white solid, m. p.=109–110 C. 1H NMR
°
(500 MHz, CDCl3): δ 7.84–7.80 (m, 2H), 7.53–7.44 (m, 5H),
7.37–7.34 (m, 1H), 7.28–7.25 (m, 2H), 7.05–6.96 (m, 3H), 5.38
(dd, J1 =6.9 Hz, J2 =13.8 Hz, 1H), 3.21–3.14 (m, 1H), 2.68–
2.62 (m, 1H), 2.15 (s, 3H), 2.13 (s, 3H), 1.05 (s, 9H). 13C NMR
(125 MHz, CDCl3): δ 137.1 (d, JC-P =6.1 Hz), 136.4, 136.1,
133.8 (d, JC-P =15.1 Hz), 133.0 (d, JC-P =14.9 Hz), 131.5 (d,
(2-(tert-butylperoxy)-2,2-diphenylethyl) diphenylphosphine
oxide (3y): The crude product was purified by column
chromatography on silica gel (petroleum ether/ethyl acetate=
2:1 as an eluent) to afford the product 3y (70% yield, 65.8 mg)
J
C-P =2.6 Hz), 131.0 (d, JC-P =2.6 Hz), 130.7 (d, JC-P =9.4 Hz),
as white solid, m. p.=164–165 C. 1H NMR (500 MHz,
°
130.3 (d, JC-P =9.6 Hz), 129.4, 128.4 (d, JC-P =11.7 Hz), 128.3,
CDCl3): δ 7.63–7.60 (m, 4H), 7.39–7.29 (m, 10H), 7.17–7.13
128.1 (d, JC-P =11.8 Hz), 124.5, 80.6, 80.3, 35.8 (d, JC-P
=
(m, 6H), 3.64 (d, J=11.7 Hz, 2H), 0.96 (s, 9H). 13C NMR
69.3 Hz), 26.2, 19.6, 19.4. 31P NMR (203 MHz, CDCl3): δ
27.77. HRMS calc. for C26H32O3P (M+H)+: 423.2084, found
423.2074.
(125 MHz, CDCl3): δ 142.9 (d, JC-P =4.7 Hz), 134.7 (d, JC-P
99.9 Hz), 130.8 (d, JC-P =2.5 Hz), 130.6 (d, JC-P =9.0 Hz),
128.2, 128.0 (d, JC-P =11.7 Hz), 127.2, 127.1, 86.1 (d, JC-P
3.5 Hz), 79.7, 39.4 (d,
C-P =70.4 Hz), 26.4. 31P NMR
=
=
(2-(tert-butylperoxy)-2-(naphthalen-2-yl)ethyl)
diphenyl-
J
phosphine oxide (3v): The crude product was purified by
column chromatography on silica gel (petroleum ether/ethyl
acetate=2:1 as an eluent) to afford the product 3v (70% yield,
(203 MHz, CDCl3): δ 24.68. HRMS calc. for C30H32O3P (M+
H)+: 471.2084, found 471.2075.
(1-(tert-butylperoxy)-2,3-dihydro-1H-inden-2-yl) diphenyl-
phosphine oxide (3z): The crude product was purified by
column chromatography on silica gel (petroleum ether/ethyl
acetate=2:1 as an eluent) to afford the product 3z (45% yield,
62.2 mg) as white solid, m. p.=172–173 C. 1H NMR
°
(500 MHz, CDCl3): δ 7.86–7.82 (m, 2H), 7.74–7.68 (m, 4H),
7.51–7.44 (m, 6H), 7.43–7.40 (m, 2H), 7.21–7.18 (m, 1H),
7.16–7.12 (m, 2H), 5.62 (dd, J1 =7.0 Hz, J2 =14.0 Hz, 1H),
3.23–3.17 (m, 1H), 2.74–2.68 (m, 1H), 1.04 (s, 9H). 13C NMR
1
36.5 mg) as colorless oil. H NMR (500 MHz, CDCl3): δ 7.90–
7.84 (m, 4H), 7.52–7.41 (m, 7H), 7.26–7.23 (m, 1H), 7.19–7.14
(m, 2H), 5.77 (dd, J1 =2.3 Hz, J2 =12.1 Hz, 1H), 3.64–3.60 (m,
1H), 3.42–3.34 (m, 1H), 3.28–3.20 (m, 1H), 1.06 (s, 9H). 13C
NMR (125 MHz, CDCl3): δ 143.1 (d, JC-P =3.3 Hz), 138.9 (d,
(125 MHz, CDCl3): δ 137.5 (d, JC-P =6.7 Hz), 133.7 (d, JC-P
=
35.5 Hz), 133.1, 132.9, 132.8 (d, JC-P =34.8 Hz), 131.6 (d, JC-P
=2.6 Hz), 131.0 (d, JC-P =2.6 Hz), 130.8 (d, JC-P =9.3 Hz),
130.2 (d, JC-P =9.3 Hz), 128.5 (d, JC-P =11.8 Hz), 128.2, 128.1,
128.0, 127.9, 127.4, 126.5, 125.8 (d, JC-P =3.3 Hz), 124.4, 80.6,
80.3, 35.9 (d, JC-P =69.0 Hz), 26.2. 31P NMR (203 MHz,
CDCl3): δ 27.52. HRMS calc. for C28H30O3P (M+H)+:
445.1927, found 445.1933.
J
C-P =3.6 Hz), 133.2, 132.3 (d, JC-P =11.6 Hz), 131.7 (d, JC-P =
2.5 Hz), 131.6 (d, JC-P =2.7 Hz), 131.5 (d, JC-P =9.1 Hz), 131.5,
130.9 (d, JC-P =9.0 Hz), 129.4, 128.7 (d, JC-P =11.4 Hz), 128.3
(d, JC-P =11.5 Hz), 126.6 (d, JC-P =49.7 Hz), 124.6, 87.3 (d, JC-P
=2.8 Hz), 80.5, 40.9 (d, JC-P =70.8 Hz), 31.5, 26.2. 31P NMR
(203 MHz, CDCl3): δ 33.73. HRMS calc. for C25H28O3P (M+
H)+: 407.1771, found 407.1764.
(2-(tert-butylperoxy)-2-(naphthalen-1-yl)ethyl)
diphenyl-
phosphine oxide (3w): The crude product was purified by
column chromatography on silica gel (petroleum ether/ethyl
acetate=2:1 as an eluent) to afford the product 3w (23% yield,
(1-(tert-butylperoxy)-1,2,3,4-tetrahydronaphthalen-2-yl) di-
phenylphosphine oxide (3aa): The crude product was purified
by column chromatography on silica gel (petroleum ether/ethyl
acetate=2:1 as an eluent) to afford the product 3aa (31% yield,
20.4 mg) as white solid, m. p.=134–136 C. 1H NMR
°
(500 MHz, CDCl3): δ 7.87–7.82 (m, 2H), 7.75–7.69 (m, 4H),
7.52–7.42 (m, 8H), 7.23–7.19 (m, 1H), 7.17–7.13 (m, 2H), 5.62
(dd, J1 =7.0 Hz, J2 =13.9 Hz, 1H), 3.23–3.17 (m, 1H), 2.74–
2.68 (m, 1H), 1.04 (s, 9H). 13C NMR (125 MHz, CDCl3): δ
137.5 (d, JC-P =6.5 Hz), 133.8 (d, JC-P =35.0 Hz), 133.2, 133.0
(d, JC-P =35.0 Hz), 132.9, 131.6 (d, JC-P =2.6 Hz), 131.1 (d, JC-P
=2.6 Hz), 130.8 (d, JC-P =9.2 Hz), 130.3 (d, JC-P =9.3 Hz),
128.5 (d, JC-P =11.8 Hz), 128.2, 128.1, 128.0, 127.9, 127.5,
1
26.0 mg) as colorless oil. H NMR (500 MHz, CDCl3): δ 7.92–
7.83 (m, 4H), 7.52–7.40 (m, 6H), 7.27–7.25 (m, 1H), 7.21–7.18
(m, 1H), 7.14–7.11 (m, 1H), 7.07 (d, J=7.6 Hz, 1H), 5.22 (d,
J=7.9 Hz, 1H), 3.67–3.63 (m, 1H), 3.17–3.11 (m, 1H), 2.72–
2.67 (m, 1H), 2.34–2.21 (m, 1H), 2.04–1.94 (m, 1H), 1.19 (s,
9H). 13C NMR (125 MHz, CDCl3): δ 139.0, 132.9 (d, JC-P
=
39.2 Hz), 132.1 (d, JC-P =38.1 Hz), 131.5, 131.4, 131.3, 130.9,
130.8, 130.7, 128.7, 128.6, 128.5, 128.3 (d, JC-P =11.2 Hz),
125.8, 80.7, 78.3 (d, JC-P =5.5 Hz), 34.9 (d, JC-P =69.4 Hz),
126.6, 125.9 (d, JC-P =3.6 Hz), 124.4, 80.,7, 80.4, 36.0 (d, JC-P
=
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26.8 (d, JC-P =3.9 Hz), 26.5, 18.7 (d, JC-P =2.2 Hz). 31P NMR
(203 MHz, CDCl3): δ 32.26. HRMS calc. for C26H30O3P (M+
H)+: 421.1927, found 421.1920.
3.09–3.03 (m, 1H), 2.62–2.55 (m, 1H), 1.04 (s, 9H). 13C NMR
(125 MHz, CDCl3): δ 162.1 (d, JC-P =2.6 Hz), 161.8 (d, JC-P
2.8 Hz), 140.3 (d, JC-P =6.6 Hz), 132.7 (d, JC-P =10.8 Hz), 132.2
(d, JC-P =10.8 Hz), 128.1, 127.9, 127.0, 125.4 (d, JC-P
20.6 Hz), 124.5 (d, JC-P =20.8 Hz), 113.9 (d, JC-P =12.9 Hz),
=
=
(1-(tert-butylperoxy)-1-phenylpropan-2-yl)
diphenylphos-
phine oxide (3bb): The crude product was purified by column
chromatography on silica gel (petroleum ether/ethyl acetate=
2:1 as an eluent) to afford the product 3bb (28% yield,
22.8 mg) as white solid. d.r.=5.5:1. 1H NMR (500 MHz,
CDCl3): δ 7.85–7.80 (m, 2H), 7.73–7.69 (m, 2H), 7.48–7.40 (m,
4H), 7.38–7.33 (m, 2H), 7.27–7.25 (m, 2H), 7.23–7.18 (m, 2H),
7.16–7.13 (m, 1H), 5.37 (dd, J1 =4.5 Hz, J2 =8.8 Hz, 1H),
2.76–2.69 (m, 1H), 1.21 (dd, J1 =7.4 Hz, J2 =16.3 Hz, 3H),
113.8 (d, JC-P =12.8 Hz), 80.5, 80.3, 55.3, 55.2, 36.2 (d, JC-P
=
69.7 Hz), 26.2. 31P NMR (203 MHz, CDCl3): δ 27.66. HRMS
calc. for C26H32O5P (M+H)+: 455.1982, found 455.1971.
bis(4-(tert-butyl)phenyl)(2-(tert-butylperoxy)-2-phenylethyl)
phosphine oxide (3ff): The crude product was purified by
column chromatography on silica gel (petroleum ether/ethyl
acetate=2:1 as an eluent) to afford the product 3ff (72% yield,
1.14 (s, 9H). 13C NMR (125 MHz, CDCl3): δ 140.4 (d, JC-P
8.8 Hz), 132.6(d, JC-P =95.8 Hz), 131.4 (d, JC-P =2.6 Hz), 131.2
(d, JC-P =8.4 Hz), 130.9 (d, JC-P =8.9 Hz), 128.5 (d, JC-P
=
72.8 mg) as white solid, m. p.=177–178 C. 1H NMR
°
(500 MHz, CDCl3): δ 7.80–7.76 (m, 2H), 7.50–7.46 (m, 4H),
7.31–7.26 (m, 4H), 7.21–7.14 (m, 3H), 5.45 (dd, J1 =7.2 Hz,
J2 =13.8 Hz, 1H), 3.10–3.04 (m, 1H), 2.64–2.57 (m, 1H), 1.31
(s, 9H), 1.26 (s, 9H), 0.99 (s, 9H). 13C NMR (125 MHz,
CDCl3): δ 154.8 (d, JC-P =2.7 Hz), 154.4 (d, JC-P =2.6 Hz),
140.4 (d, JC-P =6.6 Hz), 130.7 (d, JC-P =9.4 Hz), 130.6, 130.2
(d, JC-P =9.6 Hz), 129.9 (d, JC-P =16.3 Hz), 128.1, 127.8, 127.0,
125.4 (d, JC-P =11.9 Hz), 125.2 (d, JC-P =11.9 Hz), 80.5, 80.2,
36.3 (d, JC-P =69.2 Hz), 34.9, 34.7, 31.0, 30.9, 26.1. 31P NMR
(203 MHz, CDCl3): δ 27.11. HRMS calc. for C32H44O3P (M+
H)+: 507.3023, found 507.3017.
=
11.4 Hz), 128.3 (d, JC-P =11.2 Hz), 128.1, 127.8, 127.4, 126.9,
125.6, 82.0, 80.5, 40.6 (d, JC-P =68.9 Hz), 26.5, 8.1. 31P NMR
(203 MHz, CDCl3): δ 32.72. HRMS calc. for C25H30O3P (M+
H)+: 409.1927, found 409.1929.
diphenyl(2-phenyl-2-((2-phenylpropan-2-yl)peroxy) ethyl)
phosphine oxide (3cc): The crude product was purified by
column chromatography on silica gel (petroleum ether/ethyl
acetate=2:1 as an eluent) to afford the product 3cc (45% yield,
1
41.0 mg) as colorless oil. H NMR (500 MHz, CDCl3): δ 7.73–
7.69 (m, 2H), 7.53–7.45 (m, 3H), 7.40–7.35 (m, 3H), 7.30–7.19
(m, 12H), 5.47 (dd, J1 =7.0 Hz, J2 =14.2 Hz, 1H), 3.05–2.99
(m, 1H), 2.63–2.56 (m, 1H), 1.39 (s, 3H), 1.34 (s, 3H). 13C
NMR (125 MHz, CDCl3): δ 145.2, 140.1 (d, JC-P =6.6 Hz),
133.8 (d, JC-P =35.7 Hz), 133.0 (d, JC-P =36.3 Hz), 131.5 (d,
(2-(tert-butylperoxy)-2-phenylethyl)bis(3,5-dimethylphenyl)
phosphine oxide (3gg): The crude product was purified by
column chromatography on silica gel (petroleum ether/ethyl
acetate=2:1 as an eluent) to afford the product 3gg (75% yield,
1
67.5 mg) as colorless oil. H NMR (500 MHz, CDCl3): δ 7.41
J
C-P =2.7 Hz), 131.3 (d, JC-P =2.7 Hz), 130.8 (d, JC-P =9.6 Hz),
(d, J=12.0 Hz, 2H), 7.31–7.29 (m, 2H), 7.23–7.17 (m, 3H),
7.13 (m, d, J=12.4 Hz, 2H), 6.98 (s, 1H), 5.40 (dd, J1 =6.8 Hz,
J2 =14.1 Hz, 1H), 3.11–3.05 (m, 1H), 2.65–2.58 (m, 1H), 2.34
(s, 6H), 2.23 (s, 6H), 1.05 (s, 9H). 13C NMR (125 MHz,
CDCl3): δ 140.3 (d, JC-P =6.1 Hz), 138.0 (d, JC-P =12.2 Hz),
137.9, 137.8, 133.6 (d, JC-P =6.1 Hz), 133.2 (d, JC-P =2.8 Hz),
130.4 (d, JC-P =9.5 Hz), 128.4 (d, JC-P =24.5 Hz), 128.3, 128.1,
128.0, 127.8, 127.0, 126.8, 125.5, 83.2, 80.0, 35.8 (d, JC-P
=
69.2 Hz), 27.0, 25.9. 31P NMR (203 MHz, CDCl3): δ 27.53.
HRMS calc. for C29H30O3P (M+H)+: 457.1927, found
457.1921.
132.9 (d, JC-P =2.6 Hz), 132.8 (d, JC-P =5.6 Hz), 128.3 (d, JC-P
9.2 Hz), 128.0, 127.9, 127.0, 80.5, 80.3, 35.8 (d, JC-P
=
=
(2-(tert-butylperoxy)-2-phenylethyl)di-p-tolylphosphine
oxide (3dd): The crude product was purified by column
chromatography on silica gel (petroleum ether/ethyl acetate=
2:1 as an eluent) to afford the product 3dd (50% yield,
68.6 Hz), 26.1, 21.2, 21.1. 31P NMR (203 MHz, CDCl3): δ
27.98. HRMS calc. for C28H36O3P (M+H)+: 451.2397, found
451.2388.
42.2 mg) as white solid, m. p.=154–156 C. 1H NMR
°
(500 MHz, CDCl3): δ 7.73–7.69 (m, 2H), 7.45–7.41 (m, 2H),
7.31–7.26 (m, 4H), 7.24–7.19 (m, 3H), 7.11–7.09 (m, 2H), 5.41
(dd, J1 =7.3 Hz, J2 =13.8 Hz, 1H), 3.10–3.04 (m, 1H), 2.64–
2.57 (m, 1H), 2.38 (s, 3H), 2.31 (s, 3H), 1.03 (s, 9H). 13C NMR
ethyl
(2-(tert-butylperoxy)-2-phenylethyl)
(3,5-dimeth-
ylphenyl)phosphinate (3gg): The crude product was purified
by column chromatography on silica gel (petroleum ether/ethyl
acetate=2:1 as an eluent) to afford the product 3gg (53% yield,
38.4 mg) as colorless oil. d.r.=1:1. 1H NMR (500 MHz,
CDCl3): δ 7.78–7.74 (m, 2H), 7.58–7.51 (m, 3H), 7.47–7.41 (m,
3H), 7.36–7.28 (m, 7H), 7.22–7.16 (m, 5H), 5.28 (dd, J1 =
7.2 Hz, J2 =14.4 Hz, 1H), 5.23 (dd, J1 =7.6 Hz, J2 =13.8 Hz,
1H), 4.03–3.95 (m, 1H), 3.93–3.87 (m, 1H), 3.85–3.77 (m, 1H),
3.75–3.69 (m, 1H), 2.89–2.82 (m, 1H), 2.77–2.70 (m, 1H),
2.44–2.32 (m, 2H), 1.24 (t, J=7.1 Hz, 3H), 1.19 (s, 9H), 1.12
(t, J=7.1 Hz, 3H), 1.03 (s, 9H). 13C NMR (125 MHz, CDCl3):
δ 140.1 (d, JC-P =7.7 Hz), 139.2 (d, JC-P =5.9 Hz), 132.1 (d, JC-P
=2.7 Hz), 131.8 (d, JC-P =2.8 Hz), 131.5 (d, JC-P =10.0 Hz),
131.4 (d, JC-P =10.0 Hz), 131.3, 130.6 (d, JC-P =70.0 Hz), 128.4
(d, JC-P =12.5 Hz), 128.3, 128.2, 128.2, 128.1, 128.1, 128.0,
(125 MHz, CDCl3): δ 141.9 (d, JC-P =2.7 Hz), 141.6 (d, JC-P
2.7 Hz), 140.4 (d, JC-P =7.0 Hz), 130.9 (d, JC-P =9.8 Hz), 130.8
(d, JC-P =27.4 Hz), 130.4 (d, JC-P =9.8 Hz), 130.0 (d, JC-P
=
=
27.7 Hz), 129.1 (d, JC-P =13.5 Hz), 129.0, 128.1, 127.8, 127.0,
80.5, 80.3, 36.1 (d, JC-P =69.0 Hz), 26.2, 21.5, 21.4. 31P NMR
(203 MHz, CDCl3): δ 27.74. HRMS calc. for C26H32O3P (M+
H)+: 423.2084, found 423.2076.
(2-(tert-butylperoxy)-2-phenylethyl)bis(4-methoxyphenyl)
phosphine oxide (3ee): The crude product was purified by
column chromatography on silica gel (petroleum ether/ethyl
acetate=2:1 as an eluent) to afford the product 3ee (63% yield,
57.2 mg) as white solid, m. p.=152–154 C. 1H NMR
°
127.3 (d, JC-P =11.9 Hz), 80.6 (d, JC-P =1.7 Hz), 80.4 (d, JC-P
1.6 Hz), 60.5 (d, JC-P =5.9 Hz), 60.3 (d, JC-P =6.3 Hz), 35.8 (d,
C-P =2.3 Hz), 35.0 (d, JC-P =1.5 Hz), 26.3, 26.2, 16.3 (d, JC-P
=
(500 MHz, CDCl3): δ 7.75–7.71 (m, 2H), 7.47–7.43 (m, 2H),
7.30–7.18 (m, 5H), 6.98–6.96 (m, 2H), 6.81–6.79 (m, 2H), 5.39
(dd, J1 =7.0 Hz, J2 =14.1 Hz, 1H), 3.83 (s, 3H), 3.77 (s, 3H),
J
=
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6.8 Hz), 16.2 (d, JC-P =6.6 Hz). 31P NMR (203 MHz, CDCl3): δ
39.77, 39.55. HRMS calc. for C20H28O4P (M+H)+: 363.1720,
found 363.1725.
46.8 mg) as colorless oil. H NMR (500 MHz, CDCl3): δ 7.86–
7.77 (m, 4H), 7.60–7.49 (m, 6H), 7.38–7.26 (m, 5H), 3.33 (d,
J=33.4 Hz, 1H), 1.97 (s, 3H). 13C NMR (125 MHz, CDCl3): δ
141.4, 132.4 (d, JC-P =2.6 Hz), 132.3 (d, JC-P =2.7 Hz), 131.9
(d, JC-P =40.1 Hz), 131.5 (d, JC-P =9.5 Hz), 131.3, 130.9 (d, JC-P
=9.3 Hz), 128.9 (d, JC-P =11.8 Hz), 128.7 (d, JC-P =11.9 Hz),
3-(1-(tert-butylperoxy)-2-(diphenylphosphoryl)ethyl)-13-
methyl-7,8,9,11,12,13,15,16-octahydro-6H-cyclopenta[a]phe-
nanthren-17(14H)-one (3jj): The crude product was purified
by column chromatography on silica gel (petroleum ether/ethyl
acetate=2:1 as an eluent) to afford the product 3jj (40% yield,
45.6 mg) as colorless oil. d.r.=1:1. 1H NMR (500 MHz,
CDCl3): δ 7.83–7.79 (m, 2H), 7.52–7.45 (m, 5H), 7.36–7.33 (m,
1H), 7.29–7.25 (m, 2H), 7.13–7.09 (m, 2H), 6.95 (s, 1H), 5.39
(d, J1 =6.5 Hz, J2 =13.1 Hz, 1H), 3.23–3.16 (m, 1H), 2.78–2.75
(m, 2H), 2.70–2.62 (m, 1H), 2.53–2.48 (m, 1H), 2.38–2.35 (m,
1H), 2.21–2.11 (m, 2H), 2.09–2.03 (m, 1H), 1.98–1.94 (m, 2H),
1.64–1.60 (m, 1H), 1.54–1.42 (m, 3H), 1.38–1.26 (m, 2H), 1.08
(m, 9H), 0.91 (d, J=3.0 Hz, 3H). 13C NMR (125 MHz, CDCl3):
δ 220.9, 139.5 (d, JC-P =1.7 Hz), 136.9 (dd, J1 =5.5 Hz, J2 =
13.3 Hz), 136.1 (d, JC-P =1.7 Hz), 133.9 (dd, J1 =3.6 Hz, J2 =
128.5, 127.9, 124.9, 63.7 (d, JC-P =1.8 Hz), 62.5 (d, JC-P
=
95.6 Hz), 18.3. 31P NMR (203 MHz, CDCl3): δ 22.73. HRMS
calc. for C21H20O2P (M+H)+: 335.1195, found 335.1199.
(3,3-diphenyloxiran-2-yl)diphenylphosphine oxide (6y): The
crude product was purified by column chromatography on silica
gel (petroleum ether/ethyl acetate=2:1 as an eluent) to afford
1
the product 6y (68% yield, 53.9 mg) as colorless oil. H NMR
(500 MHz, CDCl3): δ 8.08–8.03 (m, 2H), 7.72–7.63 (m, 3H),
7.56–7.49 (m, 4H), 7.46–7.39 (m, 6H), 7.29–7.17 (m, 5H), 4.17
(d, J=25.6 Hz, 1H). 13C NMR (125 MHz, CDCl3): δ 139.9,
134.2, 133.4 (d, JC-P =101.5 Hz), 132.0 (d, JC-P =2.6 Hz), 131.7
(d, JC-P =9.1 Hz), 131.0 (d, JC-P =2.8 Hz), 130.5 (d, JC-P
=
27.6 Hz), 133.1 (dd, J1 =3.5 Hz, J2 =27.3 Hz), 131.6 (d, JC-P
=
9.1 Hz), 129.0, 128.7 (d, JC-P =11.6 Hz), 128.4, 128.2, 127.8,
127.7, 127.6, 127.5, 126.3, 67.3 (d, JC-P =1.5 Hz), 63.1 (d, JC-P
=98.7 Hz). 31P NMR (203 MHz, CDCl3): δ 23.38. HRMS calc.
for C26H22O2P (M+H)+: 397.1352, found 397.1358.
2.5 Hz), 130.9 (d, JC-P =2.4 Hz), 130.7 (d, JC-P =9.6 Hz), 130.4
(dd, J1 =2.2 Hz, J2 =9.9 Hz), 128.5 (d, JC-P =11.8 Hz), 128.1
(d, JC-P =11.9 Hz), 127.8 (d, JC-P =21.9 Hz), 125.3, 124.5 (d,
J
C-P =13.5 Hz), 80.7, 80.3 (d, JC-P =14.3 Hz), 50.4 (d, JC-P
=
1.5 Hz), 47.9, 44.4 (d, JC-P =2.5 Hz), 37.9 (d, JC-P =3.6 Hz),
Acknowledgements
35.8, 35.7 (dd, J1 =8.5 Hz, J2 =69.2 Hz), 31.5, 29.2 (d, JC-P
=
6.1 Hz), 26.4, 26.2, 25.5 (d, JC-P =1.5 Hz), 21.5, 13.8. 31P NMR
(203 MHz, CDCl3): δ 27.69, 27.63. HRMS calc. for C36H44O4P
(M+H)+: 571.2972, found 571.2966.
We thank the Natural Science Foundation of Shandong Province
(no. ZR2017LB007 and ZR2017BEM016), A Project of Shan-
dong Province Higher Educational Science and Technology
Program (no. J18KA074) and A Project of Shandong Province
Joint Postgraduate-Education Training Base Construction (no.
07140) for financial support.
2-(diphenylphosphoryl)-1-phenylethanone (4a): The crude
product was purified by column chromatography on silica gel
(petroleum ether/ethyl acetate=2:1 as an eluent) to afford the
product 4a (92% yield, 58.9 mg) as white solid, m. p.=138–
140 C. 1H NMR (500 MHz, CDCl3): δ 7.98–7.96 (m, 2H),
°
References
7.82–7.78 (m, 4H), 7.53–7.49 (m, 3H), 7.46–7.38 (m, 6H), 4.16
(d, J=15.4 Hz, 2H), 2.80–2.73 (m, 1H), 2.61–2.56 (m, 1H). 13
C
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°
p.=139–141 C. H NMR (500 MHz, CDCl3): δ 7.81–7.77 (m,
2H), 7.71–7.67 (m, 2H), 7.58–7.49 (m, 4H), 7.45–7.42 (m, 2H),
7.34–7.20 (m, 5H), 5.18–5.14 (m, 1H), 5.08 (s, 1H), 2.80–2.73
(m, 1H), 2.61–2.56 (m, 1H). 13C NMR (125 MHz, CDCl3): δ
143.8 (d, JC-P =13.4 Hz), 133.0 (d, JC-P =99.6 Hz), 132.1 (d,
J
C-P =2.7 Hz), 132.0 (d, JC-P =2.7 Hz), 131.2, 130.9 (d, JC-P =
9.3 Hz), 130.3 (d, JC-P =9.9 Hz), 128.8 (d, JC-P =11.8 Hz), 128.7
(d, JC-P =11.9 Hz), 128.4, 127.5, 125.4, 69.1 (d, JC-P =4.3 Hz),
39.1 (d, JC-P =68.0 Hz). 31P NMR (203 MHz, CDCl3): δ 33.75.
HRMS calc. for C20H20O2P (M+H)+: 323.1195, found
323.1197.
(3-methyl-3-phenyloxiran-2-yl)diphenylphosphine
oxide
(6x): The crude product was purified by column chromatog-
raphy on silica gel (petroleum ether/ethyl acetate=2:1 as an
eluent) to afford the product 6x (Isomer 1) (70% yield,
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Cobalt(II)-Catalyzed Bisfunctionalization of Alkenes with Di-
arylphosphine Oxide and Peroxide
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J. Shen, B. Xiao, Y. Hou, X. Wang, G.-Z. Li, J.-C. Chen, W.-
L. Wang, J.-B. Cheng, B. Yang*, S.-D. Yang