Eosin Y-catalyzed, visible-light-promoted carbophosphinylation of allylic alcohols via a radical neophyl rearrangement

Article abstract of DOI:10.1039/c8ob00231b

A visible-light-promoted phosphinylation of allylic alcohols with concomitant 1,2-aryl migration is described. This transformation proceeds smoothly under metal-free and mild conditions by using an inexpensive organic dye, eosin Y, as the photocatalyst, affording various β-aryl-γ-ketophosphine oxides in moderate to good yields. Mechanistic studies suggested that the 1,2-aryl migration proceeded through a radical (neophyl) rearrangement.

Full text of DOI:10.1039/c8ob00231b

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Takeharu Haino et al.
Solvent-induced emission of organogels based on tris(phenylisoxazolyl)
benzene
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Eosin Y-catalyzed, visible-light-promoted carbophosphinylation of
allylic alcohols via radical neophyl rearrangement
Yao Yin, Wei-Zhi Weng, Jian-Guo Sun and Bo Zhang*
Received 00th January 20xx,
Accepted 00th January 20xx
A visible-light-promoted phosphinylation of allylic alcohols with concomitant 1,2-aryl migration is described. This
transformation proceeds smoothly under metal-free and mild conditions by using inexpensive organic dye, eosin Y, as the
photocatalyst, affording various β-aryl-γ-ketophosphine oxides in moderate to good yields. Mechanistic studies suggested
DOI: 10.1039/x0xx00000x
www.rsc.org/
that
the
1,2-aryl
migration
proceeded
through
a
radical
(neophyl)
rearrangement.
bonds have been established, developing facile and “greener”
methods for C(sp3)-P bond formation is still highly desirable
due to the importance of phosphorus-containing molecules in
various fields as mentioned above.
Introduction
Organophosphorus compounds represent a highly important
and valuable class of compounds, which have been widely
used in organic synthesis, medicinal chemistry, and
agrochemistry.1 Many phosphorus-containing molecules show
prominent biological activities.2 In addition, they have been
extensively utilized as ligands in transition-metal catalysis or as
organocatalyst.3 Accordingly, the development of new and
efficient synthetic methods for C-P bond construction
continues to be an important topic in organic chemistry.
Photoredox catalysis enabled by visible light has been
widely recognized as a sustainable and environmentally benign
synthetic tool in organic synthesis.9 Recently, several elegant
photocatalyzed reactions for the preparation of aromatic
organophosphorus compounds have been reported.10
Moreover,
hydrophosphination11
of
alkenes
and
oxyphosphorylation12 of alkynes by photocatalysis have been
developed for the construction of C(sp3)-P bonds. Despite
these progresses, to the best of our knowledge, visible-light-
induced phosphinylation of allylic alcohols with concomitant
1,2-aryl migration, leading to β-aryl-γ-ketophosphine oxides
that have found important applications in medicinal
chemistry13, has not been explored.14,15 Although methods for
the preparation of β-aryl-γ-ketophosphine oxides via radical
carbophosphinylaiton of allylic alcohols have been described,16
they are still plagued with problems including the need for
expensive transition metal salts, high reaction temperatures,
and/or the use of additives. Inspired by these precedents10-12
and our recent work17 on visible-light-promoted radical
phosphinylation reactions, we envisioned that the above
radical carbophosphinylaiton of allylic alcohols might be
realizable in a simple and green way under photocatalysis.
Over the past several years, great efforts have been devoted
to development of simple and efficient approaches for the
incorporation of phosphorus moieties into organic
molecules.1,4 Among them, the addition of a P-H bond to an
unsaturated C-C double bond is one of the most
straightforward and atom-economical approach for C(sp3)-P
bond formation.5 For example, the conjugate addition of P(O)H
compounds to α,β-unsaturated carbonyls provides an efficient
strategy for the preparation of γ-ketophosphine oxides.6
Moreover, the hydrophosphination reactions of unactivated
alkenes, which proceed through a radical or ionic pathway,
have been developed.7 These hydrophosphination reactions
were achieved in the presence of radical initiators,
stoichiometric oxidants, strong bases, acids, UV- or
microwave-irradiation. In recent years, P-centered, radical-
initiated vicinal difunctionalization reactions of unactivated
alkenes have been studied intensively.8 In these reactions, P-
centered radicals were generated from P(O)H compounds
upon oxidation in the presence of metal salts or oxidants.
Although various methods for the construction of C(sp3)-P
Herein, we present
a
simple visible-light-promoted
phosphinylation-induced 1,2-rearrangement reaction of allylic
alcohols using cheap organic dye, eosin Y, as the photocatalyst
to prepare various β-aryl-γ-ketophosphine oxides under metal-
free and mild conditions.
Results and discussion
We initiated our study by using allylic alcohol 1a and
diphenylphosphine oxide 2a as model substrates in the
presence of 10 mol % fluorescein in DMA at room temperature
under a nitrogen atmosphere. After 24 hours of irradiation
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with 12 W blue LED lights, the desired product 3aa was formed by using 5 mol % eosin Y (Table 1, entry 18). Next, we
in 60% yield (Table 1, entry 1). Motivated by this result, we performed the reaction under air or 1 atm of O2, and 3aa was
further
obtained in 66% and 24% yields, respectively (Table 1, entries
19 and 20). The low yields were due to the formation of
byproducts. It is reported that P(O)H compounds are prone to
autoxidation once they are exposed to oxygen.8f,10e These
byproducts probably were derived from the autoxidation of
the P(O)H compounds. When the reaction was conducted
without photocatalyst, the yield of 3aa was dramatically
decreased to 20% (Table 1, entry 21). Moreover, the reaction
did not work in the absence of light (Table 1, entry 22). These
results imply that both eosin Y and visible light are essential for
the success of the carbophosphinylation of allylic alcohols.
Table 1 Optimization of reaction conditionsa
Table 2 Scope of allylic alcoholsa,b
OH
R1
O
O
Ar
Eosin Y (10 mol %)
Ar
Ar
O
H
P
Ph
+
DMA, rt, N2
12 W blue LEDs
Ar
P
Ph
Ph
Entry
1
Photocatalyst (mol %)
fluorescein (10)
eosin Y (10)
Solvent
DMA
DMA
DMA
DMA
DMA
DMA
DMA
DMA
DMA
DMA
DMA
DMF
Yieldb (%)
60
R1
Ph
1
3
2a
(a) symmetrical
-diaryl allylic alcohols
2
77
Me
Me
3
eosin Y disodium (10)
rose bengal (10)
eosin B (10)
62
Me
4
72
O
O
O
O
O
O
O
P
5
49
Me
O
P
Ph
Ph
P
Ph
6
rhodamine B (10)
rhodamine 6G (10)
Mes-Acr+ (10)
9-fluorenone (10)
Ru(bpy)3Cl2 (1)
fac-Ir(ppy)3 (1)
eosin Y (10)
33
P
Ph
Ph
Ph
Ph
Me
7
10
Ph
8
25
Me
3aa, 77% (60%)c
3ba, 63%
3ca, 71%
3da, 76%
9
43
F
Cl
Br
OMe
10
11
12
13
14
15
16
17
18
19c
20d
21
22e
25
51
O
O
O
O
O
O
O
O
P
70
P
Ph
Cl
P
Ph
P
Ph
Ph
eosin Y (10)
1,4-dioxane
DCE
54
Ph
Ph
Ph
Ph
eosin Y (10)
40
F
Br
MeO
eosin Y (10)
DMSO
CH3CN
MeOH
DMA
DMA
DMA
DMA
DMA
65
3ea, 50%
3fa, 73%
3ga, 50%
3ha, 61%
eosin Y (10)
35
(b) unsymmetrical
-diaryl allylic alcohols
eosin Y (10)
30
eosin Y (5)
51
CF3
N
O
O
O
eosin Y (10)
66
O
P
O
O
eosin Y (10)
24
Ph
P
Ph
P
Ph
Me
Ph
none
20
Ph
Ph
eosin Y (10)
0
Me
3ia, 57%d (2.5:1)e
3ja, 70%d (2.9:1)e
3ka, 68%d (3.3:1)e
a
Reaction conditions: 1a (0.2 mmol), 2a (0.5 mmol), and photocatalyst (10
mol %) in solvent (2.0 mL) were irradiated with 12 W blue LEDs at room
temperature under N2 for 24 h. b Isolated yields. c The reaction was conducted
under air. d The reaction was conducted under O2 (1 atm). e The reaction was
(c) formation of quaternary C center
Ph
P
Ph
O
O
Ph
performed in the dark. Mes-Acr+
perchlorate.
= 9-mesityl-10-methyl-acridinium
OH
Ph
optimized the reaction conditions. Various organic
photocatalysts including eosin Y, eosin Y disodium, rose
bengal, eosin B, rhodamine B, rhodamine 6G, Mes-Acr+, and 9-
fluorenone were examined under the same conditions,
producing 3aa in 10-77% yields (Table 1, entries 2-9). These
results indicated that eosin Y is the most suitable. Besides
organic photocatalysts, metal-based photocatalysts, such as
Ru(bpy)3Cl2 and fac-Ir(ppy)3, were also tested, which delivered
3aa in 25% and 51% yields, respectively (Table 1, entries 10
and 11). A screening of solvent revealed that DMA is the best
solvent for this transformation. Other solvents, such as DMF,
1,4-dioxane, DCE, DMSO, CH3CN, and MeOH resulted in lower
yields (Table 1, entries 12-17). The yield was decreased to 51%
3l
3la, 41%
a Reaction conditions: see entry 2, Table 1. b Isolated yields. c 1.23g of 3aa
prepared. d Yields of 3 and its isomer, only major products are shown. e The
ratio of 3 and its isomer was determined by 1H NMR analysis of the isolated
product.
With optimized reaction conditions in hand, we turned our
attention to investigate the generality of our protocol. As
shown in Table 2, symmetrical α,α-diaryl allylic alcohols
bearing electron-donating groups at the para-position of the
arene ring provided the corresponding β-aryl-γ-ketophosphine
oxides in good yields (3ba and 3ha). Meta- and ortho-
substituted aryl groups also acted as a migrating group,
2 | J. Name., 2012, 00, 1-3
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leading to the desired products 3ca and 3da in 71% and 76% moderate to good yields (see 3ag and 3ah). Interestingly,
yields, respectively. Various halogen substituents on the dialkylphosphine oxides could also reacted with 1a to afford
aromatic ring of α,α-diaryl allylic alcohols were well-tolerated, 3ai in 34% yield. Unfortunately, when diethyl phosphonate 2j
and the corresponding migrated products 3ea
-ga were was employed, only traces of product 3aj were observed.
obtained in moderate to good yields. To probe the selectivity
To gain a deeper understanding of this reaction mechanism,
of the aryl migration, unsymmetrical allylic alcohols carrying some preliminary studies were performed (Scheme 1). First,
two different aryl groups were examined. We found that the this reaction was completely suppressed in the presence of
more electron-deficient aryl group migrated preferentially to 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) as
produce the products 3ia
indicated that the 1,2-aryl migration might proceed through a 2,6-di-tert-butyl-4-methylphenol
a
radical
-
ka in good yields. These results scavenger. This reaction did not work well in the presence of
(BHT)
(Scheme
1a).
radical (neophyl) rearrangement.18 Moreover, we could show Meanwhile, we found that the TEMPO-trapped product
4
that creation of quaternary C centers is possible using this could be identified by high-resolution mass spectrometry.
novel protocol (see 3la). The structure of 3la was confirmed by Moreover, when the reaction was conducted in the presence
X-ray analysis (see the Supporting Information).19 To of 1,1-diphenylethylene as a radical trapper, no product 3aa
demonstrate the practicality of this reaction, we performed was observed, and the trapped compounds 5 and 6 were
the reaction of 1a and 2a on a gram scale under the irradiation obtained in 10% and 6% yields, respectively (Scheme 1b).20
of visible light and isolated 3aa in 60% yield (1.23 g).
These results support the hypothesis that P-centered radical
addition pathway is likely involved in the current reaction.
Since this reaction occurs efficiently without the help of an
obvious sacrificial oxidant, hydrogen gas may be the only
Table 3 Scope of P(O)H compoundsa,b
1
byproduct. However, we did not detected hydrogen gas by H
NMR and gas chromatography, thus suggesting that a cross-
coupling hydrogen evolution pathway is not likely involved in
the current transformation.21
Scheme 1 Mechanistic studies.
a Reaction conditions: see entry 2, Table 1. b Isolated yields. c The dr was
determined by 1H NMR analysis of the crude products.
On the basis of these experimental results, a plausible
reaction mechanism is proposed in Scheme 2. Eosin Y (EY) is
first excited under visible light irradiation to produce its
excited state species EY*, which undergoes a single electron
transfer (SET) with phosphinous acid 2' to form the
We next explored the scope of the reaction towards P(O)H
compounds (Table 3). Diarylphosphine oxides containing
electron-donating and electron-withdrawing substituents at
the para-position of the benzene ring underwent the desired
1,2-aryl migration smoothly to deliver the corresponding
products in moderate to good yield (see 3ab and 3ac). The
substituent positions did not affect the efficiency of this
transformation (see 3ae and 3af). Diarylphosphine oxide with
naphthyl groups resulted in moderate yield due to the
incomplete conversions of substrate 1a (see 3ad). Notably, the
current protocol is not restricted to symmetric phosphine
oxides. Unsymmetric phosphine oxides were also proved to be
corresponding radical cation
centered radical
would be generated.11a,22 Subsequently,
addition of to the double bond of allylic alcohol affords a
carbon-centered radical . A neophyl rearrangement via a
spiro[2,5]octadienyl radical might predominate, which
generates the radical . The proposed pathway is in accord
with our experimental observations (see 3ia-ka). Finally, SET
from to EY* would give the radical cation , which gets
deprotonated to deliver the desired product . As for the
A. Upon deprotonation, the P-
B
B
1
C
D
E
E
F
viable
substrates
for
this
transformation.
Thus,
3
butyl(phenyl)phosphine oxide and ethyl phenylphosphinate
were successfully transformed into the targeted products in
reduced photocatalyst EY radical anion, it may be quenched by
trace amounts of oxygen gas in the solvent to regenerate EY
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1
White solid (62.0 mg, 77%); H NMR (300 MHz, CDCl3) δ 7.89-
7.81 (m, 2H), 7.72-7.66 (m, 2H), 7.63-7.57 (m, 2H), 7.39-7.22
(m, 11H), 7.11-7.00 (m, 3H), 5.35-5.27 (m, 1H), 3.54-3.43 (m,
1H), 2.82-2.71 (m, 1H); 13C NMR (75 MHz, CDCl3) δ 197.6 (d, J =
6.0 Hz), 138.3 (d, J = 7.1 Hz), 135.5, 133.2 (d, J = 40.1 Hz),
132.6, 131.8 (d, J = 40.1 Hz), 131.4 (d, J = 2.8 Hz), 131.1 (d, J =
2.8 Hz), 130.4 (dd, J = 10.7, 9.6 Hz), 128.6 (d, J = 9.4 Hz), 128.2
(d, J =5.6 Hz), 128.1-128.0 (m), 127.0, 46.3 (d, J = 1.7 Hz), 33.6
(d, J = 70.4 Hz); 31P NMR (121.5 MHz, CDCl3) δ 30.28; HRMS
(ESI) calculated for C27H24O2P [M+H]+ m/z 411.1508, found
411.1510.
and provide superoxide radical anion. The superoxide radical
anion reacts with a proton to produce a peroxide radical,
which could abstract a hydrogen atom from phosphinous acid
2
to give the P-centered radical B, with H2O and oxygen
released as well.
Acknowledgements
This work is financially supported by the National Natural
Science Foundation of China (21702230), the Natural Science
Foundation of Jiangsu Province (BK20160743), the Program
for Jiangsu Province Innovative Research Team, and the 111
Project (B16046).
Notes and references
1
For some reviews, see: (a) Organophosphorus Reagents; P. J.
Murphy, Ed.; Oxford Univ. Press: Oxford, UK, 2004; (b) D. T.
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Scheme 2 Proposed reaction mechanism.
Conclusions
2
For selected examples, see: (a) X. S. Li, D. W. Zhang, H. Pang,
In summary, we have presented a simple and mild visible-light-
promoted carbophosphinylation of allylic alcohols via radical
neophyl rearrangement. The novel transformation employs
commercially available and inexpensive organic dye, eosin Y,
as the photocatalyst. Notably, neither transition-metal nor
additive is required in this process. Experiments are very easy
to conduct and furnishes various β-aryl-γ-ketophosphine
oxides in moderate to good yields. Further studies on the
mechanism and the synthetic applications are currently
ongoing.
F. Shen, H. Fu, Y. Y. Jiang and Y. F. Zhao, Org. Lett., 2005,
4919; (b) X. Yu, Q. Ding and J. Wu, J. Comb. Chem., 2010, 12
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3
4
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Experimental
General
carbophosphinylation of allylic alcohols (GP)
Allylic alcohol (0.2 mmol, 1.0 equiv), P(O)H compound
procedure
for
visible-light-promoted
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1
2 (0.5
mmol, 2.5 equiv), and eosin Y (0.02 mmol, 0.1 equiv) were
placed in a dry 10 mL Schlenk tube under a nitrogen
atmosphere. Then DMA (2.0 mL) was added. The reaction
mixture was stirred and irradiated by 12 W blue LEDs (450 nm)
at room temperature for 24 h. After the reaction was
completed monitored by TLC, H2O (10.0 mL) was added, and
the mixture was extracted by EtOAc (3x10.0 mL). The
combined organic layer was dried over anhydrous Na2SO4,
filtered, and concentrated by rotary evaporation. The crude
reaction mixture was purified by flash column chromatography
on silica gel to afford the corresponding product.
7
K. J. Gallagher and R. L. Webster, Chem. Commun., 2014, 50
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Characterisation data for a representative product
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3-(Diphenylphosphoryl)-1,2-diphenylpropan-1-one (3aa)
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Organic & Biomolecular Chemistry
Page 6 of 6
View Article Online
DOI: 10.1039/C8OB00231B
Yao Yin, WeiꢀZhi Weng, JianꢀGuo Sun,
and Bo Zhang*
Eosin
Yꢀcatalyzed,
visibleꢀlightꢀpromoted
A
eosin Yꢀcatalyzed, visibleꢀlightꢀpromoted phosphinylationꢀ
carbophosphinylation of allylic alcohols via radical
neophyl rearrangement
induced 1,2ꢀrearrangement reaction of allylic alcohols to prepare
various βꢀarylꢀγꢀketophosphine oxides is presented.