Visible photocatalysis of novel oxime phosphonates: Synthesis of β-aminophosphonates

Article abstract of DOI:10.1039/c9cc06075h

A novel type of oxime phosphonate was synthesized and used in the intermolecular cascade radical addition reaction of alkenes to access β-aminophosphonates via visible-light-driven N-centered iminyl radical-mediated and redox-neutral selective C-P single-bond cleavage in an active phosphorus radical route. The procedure is characterized by its ability to achieve the construction of Csp³-P and Csp³-N bonds without the requirement for oxidants and bases.

Full text of DOI:10.1039/c9cc06075h

View Article Online
View Journal
ChemComm
Chemical Communications
Accepted Manuscript
This article can be cited before page numbers have been issued, to do this please use: S. Yang, Y. Li, C.
Wang, S. Gao and F. Qi, Chem. Commun., 2019, DOI: 10.1039/C9CC06075H.
Volume 54
This is an Accepted Manuscript, which has been through the
Number
January 2018
Pages 1-112
1
4
Royal Society of Chemistry peer review process and has been
accepted for publication.
ChemComm
Chemical Communications
rsc.li/chemcomm
Accepted Manuscripts are published online shortly after acceptance,
before technical editing, formatting and proof reading. Using this free
service, authors can make their results available to the community, in
citable form, before we publish the edited article. We will replace this
Accepted Manuscript with the edited and formatted Advance Article as
soon as it is available.
You can find more information about Accepted Manuscripts in the
Information for Authors.
Please note that technical editing may introduce minor changes to the
text and/or graphics, which may alter content. The journal’s standard
Terms & Conditions and the Ethical guidelines still apply. In no event
shall the Royal Society of Chemistry be held responsible for any errors
or omissions in this Accepted Manuscript or any consequences arising
from the use of any information it contains.
ISSN 1359-7345
COMMUNICATION
S. J. Connon, M. O. Senge et al.
Conformational control of nonplanar free base porphyrins:
towards bifunctional catalysts of tunable basicity
rsc.li/chemcomm

Please do not adjust margins
Page 1 of 5
ChemComm
View Article Online
DOI: 10.1039/C9CC06075H
Journal Name
COMMUNICATION
New Oxime Phosphonates Participated Visible Photocatalysis:
Synthesis of -Aminophosphonates
Yong-Hong Li,a† Chun-Hai Wang,a† Su-Qian Gao,a Feng-Ming Qi,a Shang-Dong Yang*a,b
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
www.rsc.org/
A new type of oxime phosphonates was firstly synthesized and been used as substrates and added to alkene leading to form
used in the intermolecular cascade radical addition reaction of carbon nucleophilic intermediate (a, Scheme 1). In this
alkenes to access -aminophosphonates via visible-light-driven N- transformation, the formation of the phosphorus radical still
centered iminyl radical-mediated and redox-neutral selective C–P requires the assistance of an external bases or oxidants, which
single-bond cleavage in an active phosphorus radical route. The does not satisfy the requirement of the environmental
procedure is characterized by its ability to achieve the friendliness or cleanliness of reactions.
construction of Csp3–P and Csp3–N bonds without the requirement
for oxidants and bases.
It is known that Ir(III)-complex-prompted photoredox
reactions involved in an oxidative quenching cycle,[4] which has
rarely been applied to the phosphorus radical reactions for the
H-phosphonates unsuitable for this photooxidation process.
Thus, searching for a new oxidizing phosphorus radical reagent
that produced not only a phosphorus radical, but also oxidized
Difunctionalization of alkenes[1] using phosphorus-centered
radicals has become a powerful strategy for the preparation of
various -functionalized phosphonates.[2] Advantages of this
strategy include high efficiency and step economy. However,
existing some deficiencies for the preparation of phosphorus
radicals still remain to be settled; e.g., it is often necessary to
add stoichiometric amounts of oxidants, bases, or various
additives to the reaction system, which result in the
generation of copious stoichiometric waste. Furthermore, the
addition of equivalent oxidants not only impairs the scope of
substrate and evokes the issue of chemoselectivity, it also
generates obnoxious byproducts. In efforts to establish cleaner
and more environmentally friendly reactions, new strategies
and reagents for the phosphorus-centered radical
difunctionalization of alkene without the requirement for
external oxidants, bases, or various additives, are desirable.
Very recently, the use of visible light photoredox catalysis[3] to
generate phosphorus radical has been reported because this
tactics offers more sustainable chemical processes. The
reaction conditions are mild, thereby allowing for the potential
ability to involve multiple catalytic pathways. However, in the
vast majority of transition-metal-catalyzed or visible-light-
driven phosphorus radical reactions, H-phosphonates have
Ir(III)* to Ir(IV), subsequently forming
a
carbocation
intermediate, then trapped by a nucleophile to achieve alkene
difunctionalization is desirable and challenge. Based on these
insights, we investigated and synthesized new phosphine
sources of oxime-containing phosphonates.[5] The latter were
a) Phosphorylation of alkene via reductive quenching cycle (Reported)
E
O
O
O
PR2R3
R1
E+
PR2R3
PR2R3
Transition Metal or
Base, oxidant
H
R
+
R
R
R1
R1
nucleophilic intermediate
b) Phosphorylation of alkene via oxidative quenching cycle (This work)
O
BzO
Bz
N
N
O
H3C
O
CH3CN
III)
Ir(
R2
P(OR3)2
R2
P(OR3)2
R
+
R
Ar
R
R2
ArCN
P(OR3)2
O
New multifunctional
oxime phosphonates
electrophilic intermediate
O
O
Bz
H3C
N
N
Bz
N
Bz
R1
P(O)(OEt)2
P(O)(OEt)2
H3C
P(O)(OEt)2
O
Me
(-)--phellandrene-aminophosphonates
macrocyclic lactamide
-aminophosphonates
a. State Key Laboratory of Applied Organic Chemistry, Lanzhou University, Lanzhou
730000, P. R. China.
New phosphorus radical reagent
Multiple bonds breakage and recombination
Oxidant and base free



b. Key Lab of Functional Molecular Engineering of Guangdong Province, South China
University of Technology, Guangzhou 510640, P. R. China.
† These authors contributed equally to this work.
Scheme 1. Strategy for visible photocatalysis to construct -
Electronic Supplementary Information (ESI) available: [details of any
supplementary information available should be included here]. See
DOI: 10.1039/x0xx00000x
aminophosphonates
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 1
Please do not adjust margins

Please do not adjust margins
ChemComm
Page 2 of 5
COMMUNICATION
Journal Name
used for the intermolecular radical addition cascade reaction cleavage and recombination process. Inspired bVyiewthAirsticlreeOsnulilnte,
DOI: 10.1039/C9CC06075H
of alkenes to access -functionalized phosphonates via visible- We further optimized reaction conditions and results revealed
light-driven N-centered iminyl radical-mediated multiple bond that the loading of the photocatalyst fac-Ir(ppy)3 could be
cleavage and recombination process (b, Scheme 1). Use of this reduced to 0.5 mol % with no change in the yield. Control
new phosphorus radical reagent not only avoids the experiments revealed that the fac-Ir(ppy)3 and visible light
requirement for the addition of external oxidants and bases, irradiation are essential for the reaction.
but also used in conjunction with photocatalysis to achieve
more sustainable and environmentally friendly processes.
-Aminophosphonates are isosteres of -amino acid
derivatives,[8] which are reported to possess various biological
Oximes and their derivatives have relatively high activities and potential medicinal properties,including
oxidability. So, that it is relatively easy to prepare the highly antibacterial,[9] enzyme inhibitors,[10] catalytic antibio tics,[11]
reactive imine radical species by cleavage of the N–O bond anti-HIV,[12] and anti-inflammatory[13] activities. In the next, we
under heating or illumination.[6] The iminyl radical is rapidly synthesized different phosphoryl oxime ethers and
converted to form other more stable radicals through the investigated their activities in this transformation (Table 2).
release of an oxygen anion and intramolecular When the protecting group on the oxygen atom is the methyl
rearrangement.[7] Phosphoryl oxime ethers not only provide (2b) or 4-nitrobenzoyl (2h), the reaction did not proceed.
the phosphorus radical, but also as the oxidant to actualize However, when using different acyls such as -Ac, -Piv, -Bz, and
Ir(III)* to Ir(IV) in the reaction simultaneously. Thus, we 4-arylbenzoyl (instead of methyl group) as protecting groups,
synthesized
the
diethyl the reactions proceeded smoothly (2c–2g). Reactions of
[(benzoyloxy)imino](phenyl)methylphosphonate (2a), which oximes with some other aryl groups (2i–2l) also proceed, albeit
was storability and stability toward moisture and oxygen,[5] with lower yields.
and attempted to carry out the difunctionalization of alkenes
through the visible-light-promoted oxidative quenching tactics Table 2. Screening of phosphine sourcesa,b
under oxidant- and base-free conditions (Table 1). Various of
photocatalysts were firstly screened with acetonitrile as
O
PG
OPG
H3C
N
5 W
N
CH3
+
CH3
0.5 mol % Ir(ppy)3
CH3CN
solvent, the new difunctionalization of alkene really occured
and the -aminophosphonate of 3a was obtained in 77% yield
by using fac-Ir(ppy)3 as catalyst. In this transformation,
acetonitrile not only acted as solvent, but also as substrate
participated in the reaction of involving the multiple bond
+
ArCN
CH3
P(O)(OEt)2
P(O)(OEt)2
1a
2b-2l
2ab-2al
O
N
OMe
OAc
OPiv
N
N
N
O
P(O)(OEt)2
P(O)(OEt)2
P(O)(OEt)2
P(O)(OEt)2
Table 1. Screening of Reaction Conditionsa
2b
, n.d.
2c
, 67%
2d
, 64%
2e
, 30%
O
OBz
Bz
OCH3
Cl
NO2
N
H3C
N
5 W
CH3
CH3
photosensitizer
P(O)(OEt)2
O
O
N
O
N
+
PhCN
resultb
OBz
+
CH3CN
N
P(O)(OEt)2
O
O
O
N
3a
1a
2a
P(O)(OEt)2
entry
photocatalyst (mol %)
P(O)(OEt)2
P(O)(OEt)2
P(O)(OEt)2
Me
IrIII(dmppy)2(dtbbpy)PF6 (1)
IrIII(dmppy)2(bpy)PF6 (1)
IrIII(dF(CF3)mppy)2(dtbbpy)PF6 (1)
1
2
3
N.R.
N.R.
N.R.
2f
2g
, 68%
2h
, n.d.
2i
, 62%
, 45%
IrIII(dF(CF3)mppy)2(d(CF3)bpy)PF6 (1)
fac-Ir(ppy)3 (1)
OBz
OBz
OBz
4
N.R.
N
N
N
5
6
77%
77%
P(O)(OEt)2
P(O)(OEt)2
P(O)(OEt)2
fac-Ir(ppy)3 (0.5)
7
8c
9
N.R.
N.R.
MeO
Cl
F3C
fac-Ir(ppy)3 (0.5)
2j, 57%
2k, 53%
2l, 22%
Ru(bpy)3Cl26H2O (1)
Eosin Y (5)
N.R.
aReaction conditions:
a
solution of 1a (1.5 equiv),
2
(1.0 equiv),
10
11
N.R.
N.R.
Rhodamine B (5)
photocatalyst (1.0 mol %) in CH3CN (0.25 M) was irradiated by 5W Blue LED
lamp at rt for 8 h under Ar. bIsolated yield.
-
-
]
CF3 [PF6
CF3
]
-
[PF6
[PF6]
F
F
N
N
N
N
N
N
N
N
N
N
Ir+
Ir+
F
F
Ir
Ir+
N
With the optimal conditions in hand, a wide range of
aromatic olefins were submitted to the photoredox catalysis
protocol. First, we investigated the influence of the terminal
group of styrene. As shown in Table 3, -alkyl-substituted
styrenes gave the corresponding products 3 in moderate to
good yields (3a–3h). When the cpropyl group was introduced
to the styrene, good yield and high diastereomeric ratio (dr)
were obtained (3d, 70%, dr > 20:1). Next, we investigated a
N
N
N
N
CF3
CF3
IrIII(dmppy)2(dtbbpy)[PF6
]
-
-
-
IrIII(dmppy)2(bpy)[PF6
]
IrIII(dF(CF3)mppy)2(d(CF3)bpy) )[PF6
]
fac-Ir(ppy)3
2+
CF3
2Cl- 6H2
O
-
]
[PF6
F
2Na+
COO
N
N
Ru
N
COOH
N
N
N
N
N
F
F
Ir+
Br
Br
N
Et
Et2
N
O
N
N
Cl-
O
O
O
Et
F
Br
Br
CF3
IrIII(dF(CF3)mppy)2(dtbbpy) )[PF6
-
]
Ru(bpy)3Cl2.6H2
O
Rhodamine B
EOSIN Y
aReaction conditions:
a solution of 1a (1.5 equiv), 2a (1.0 equiv), variety of substituted -methyl styrene substrates (3i–3u, 3w,
photocatalyst (1.0 mol %) in CH3CN (0.25 M) was irradiated by 5W Blue LED 3x). We were delighted that the reactions proceeded in
lamp at rt for 8 h under Ar. bIsolated yield. cN.R.= No Reaction.
moderate to good yields (29–82%) when electron-withdrawing
2 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Please do not adjust margins
Page 3 of 5
ChemComm
Journal Name
COMMUNICATION
and electron-donating groups were introduced into the para When using 8-phenyloct-7-enenitrile as the substrate in
View Article Online
DOI: 10.1039/C9CC06075H
position of alkene. Furthermore, a wide range of meta- and dioxane, the terminal nitrile could also be used as the
ortho-substituted -methyl styrenes were also tolerated in this nucleophile to afford the macrocyclic lactamide 3ae in 57%
transformation. Good yields were obtained (56–72%), moderate yield with dr
= 5:1. Notably, cyclopenta[a]
particularly for 3q and 3x, both good yields and high dr were phenanthrene (a steroid) and esterified lovastatin (a drug)
obtained (72%, dr > 20:1; 73%, dr > 20:1). When the could also be modified by this radical phosphorylation; -
naphthalene ring was used instead of benzene, a low yield was benzoxyphosphonates of 3af and 3ag were obtained in 47%
obtained (3v, 47%). When a methoxy group was used on the and 51% yields, respectively. These reactions all exhibited
phosphorus instead of an oxyethyl group, good yield and dr excellent regioselectivity and stereoselectivity, which highlight
value were obtained (78%, dr = 9:1). To our further delight, the synthetic value of our photoredox catalysis protocol.
indene could also be used as substrate to afford the
corresponding -aminophosphonates 3z in moderate yield and
O
N
Bz
P(O)(OEt)2
Me
with a high dr (57%, dr > 20:1). If we selected the aliphatic
alkene of 1-heptane (3az) to carry out this difunctionalization,
reaction didn’t work for the formation of cation intermediate
is difficult.
P(O)(OMe)2
Me
3ae, 57%, dr = 5:1
Me
O
Bz
(-)--phellandrene
(+)-limonene
CH3CN
N
O
P(O)(OEt)2
CN
5
CH3CN
H3C
H3
C
N
Dioxane
Me
Bz
3aa, 51%, dr = 5:1
Me
3ab, 55%
H
N
OBz
O
N
P(O)(OEt)2
CH3
()--pinene
HN
(+)--pinene
S
P(O)R2

Table 3. The investigation of scope of substratesa,b
Me
O
CH3CN, H2O (2 equiv.)
CH3CN, H2O (2 equiv.)
AcO
CH3
P(O)(OEt)2
3ac, 51%
0.5 mol % fac-Ir(ppy)3
O
3ad, 60%
5 W
O
O
O
OBz
H
N
5 W
Bz
AcO
O
O
H3C
Ar
N
H
H
H
0.5 mol % fac-Ir(ppy)3
CH3CN
R1
O
R1
P(O)(OR3)2
O
+
PhCN
+
Ar
cyclopenta
H
H
[a]phenanthrene
O
esterified-lovastatin
CH3CN
P(O)(OR3)2
OBz
CH3CN
P(O)(OEt)2
1
2
3
R

3af, 47%
O
O
OBz
O
P(O)(OEt)2
Bz
Bz
Bz
3ag, 51%
H3C
N
H3C
N
H3C
N
R1
R2
CH3
CH3
Scheme 2. Different photo-catalyzed phosphorus-radical
P(O)(OEt)2
P(O)(OEt)2
1 = Me, 74%, dr > 20:1
P(O)(OEt)2
R2
involved in difunctionalization of alkenes
R
R
2 = Me, 71%, dr = 4:1
R
R
R
2 = Me, 63%, dr = 16:1
2 = Cl, 67%, dr = 20:1
2 = Br, 72%, dr > 20:1
3a:
3h:
3o:
3p:
3q:
3r:
3b:
3c:
3d:
3e:
3f:
3i:
R
1 = H, 67%
1 = Et, 62%, dr = 12:1
R2 = F, 71%, dr = 5:1
R2 = Cl, 82%, dr = 7:1
3j:
R
R
In order to obatin pivotal informations about the
mechanism, we have done some control experiments which
including radical traping and deuterium-labeled acetonitrile
(details see supporting information). Moreover, to further
testify new type of oxime phosphonates could impelled
photocatalytic cycle of fac-Ir(ppy)3, we have also done the
luminescence quenching and cyclic voltammerty (CV)
experiments under the model reaction condition respectively
(details see supporting information). Considering the results of
our experiments and the reported literature,[14] a plausible
mechanism is proposed for this transformation (Scheme 3).
1 = Cpropyl, 70%, dr > 20:1
R
2 = Br, 72%, dr = 7:1
R2 = OAc, 63%, dr = 16:1
3k:
3l:
R
=
n-Bu, 51%, dr = 12:1
R1 = Isoamyl, 57%, dr = 12:1
R2 = CN, 47%, dr = 2:1
1
R
2 = CF3, 29%, dr = 8:1
3m:
3n:
3g:
R
1 = CH2NHTs, 45%, dr =17:1
R
2 = BPin, 40%, dr = 13:1
O
O
O
Bz
N
Bz
Bz
H3C
H3C
N
F
N
CH3
CH3
CH3
CH3
P(O)(OEt)2
R2
P(O)(OEt)2
P(O)(OEt)2
Br
R
2 = Me, 63%, dr = 5:1
3s:
3v:
3w:
57%, dr = 15:1
47%, dr = 9:1
3t:
R
2 = Br, 56%, dr > 20:1
3u:
R
2 = Ph, 65%, dr > 20:1
O
O
O
O
Bz
H3C
N
Bz
Bz
H3C
H3C
N
Bz
H3C
H3C
N
N
MeO
CH3
CH3
P(O)(OMe)2
78%, dr > 20:1
*
Initially, the excited state Ir(III) photocatalyst, excited by the
P(O)(OEt)2
6
P(O)(OEt)2
P(O)(OEt)2
3az:
N.R.
blue LED irradiation, is capable of reducing the phosphine
source 2a, to generate the highly reactive Ir(IV) complex and
N-centered iminyl radical intermediate A, with the release of a
OMe
3x:
3y:
3z:
73%, dr > 20:1
57%, dr > 20:1
aReaction conditions: a solution of 1 (0.6 mmol), 2 (0.4 mmol), and fac-
Ir(ppy)3 (0.002 mmol, 0.5 mol %) in CH3CN (1.60 mL) was irradiated by a 5
W blue LED lamp at rt for 8 h.bIsolated yield. cN.R. is not reaction.
O
CH3
OBz
R1
P(O)(OEt)2
Ritter
reaction
O
R
Ph
CH3CN
N
Ir(III)
H3C
N
R1
R
To highlight the synthetic value of our photoredox catalysis
protocol, more complex alkenes were used as the substrates
(Scheme 2). To our delight, some natural conjugated dienes,
such as (–)--phellandrene and (+)--limonene reacted
successfully under the optimized conditions: i.e., bifunctional
1,4-aminophosphinoylated chiral products 3aa and 3ab were
obtained in 51% and 55% yields, respectively. When using the
endocyclic groups of (–)--pinene and (+)--pinene, and
adding 2.0 equiv water to the reaction, radical migration led to
ring opening and afforded corresponding secondary
aminophosphonates in moderate yields (3ac, 51%; 3ad, 60%).
Add H2O in the reaction maybe conducived to ring opening.
P(O)(OEt)2
D
C
Oxidative
quenching cycle
O
R
P(O)(OEt)2
R
Bz
Ir(III)*
H3C
N
R1
R1
Ir(IV)
P(O)(OEt)2
3a
BzO-
R1
R
Ph
OBz
intramolecular
rearrangement
O
Me
N
N
O
O
H
H
R
stereoselectivity
H
P
N
R1
H
O
Me
N
EtO
OEt
Ph
Ph
P(O)(OEt)2
2a
P(O)(OEt)2
P(O)(OEt)2
R1
Ph
O
P(O)(OEt)2
R
PhCN
B
A
favor
unfavor
New multifunctional
oxime phosphonates
unstable iminyl
radical intermediate
Scheme 3. Proposed reaction mechanism
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 3
Please do not adjust margins

Please do not adjust margins
ChemComm
Page 4 of 5
COMMUNICATION
Journal Name
2
For selected examples, see: (a) Y.-M. Li, M. Sun, H.-L. Wang,
benzoxyl anion. The iminyl radical A undergoes an β-
fragmentation reaction to afford the phosphorus radical B.[15]
Here, the styrene 1a can act as a radical acceptor to capture
the phosphorus radical by delivering the benzyl radical.
Subsequently, regeneration of the ground state photocatalyst
results from reduction by the benzyl radical to afford benzyl
cation immediately attacked by acetonitrile to the final benzyl
nitrilium cation intermediate C with completing the catalytic
cycle. Finally, the nitrilium cation C is attacked by the benzoxyl
anion, followed by an acyl migration, to afford the -
aminophosphinoylation product 3a through a Ritter-type
reaction.[7]
In conclusion, we have discovered a new application of
phosphorus reagent of oxime phosphonate, which was
successfully used for the intermolecular cascade radical
addition reaction of alkenes to form -aminophosphonates via
visible-light-driven N-centered iminyl radical-mediated and
redox-neutral selective C–P bond cleavage in an active
phosphorus radical route. This strategy tolerates a wide range
of alkenes. It enables the highly selective formation of various
chemical bonds in a single step.
View Article Online
Q.-P. Tian, S.-D. Yang, Angew. Chem., DInOtI.: E10d..1023091/C3,9C5C2,063097752H.
(b) S.-F. Zhou, D.-P. Li, K. Liu, J.-P. Zou, O. T. Asekun, J. Org.
Chem. 2015, 80, 1214. (c) Y. Gao, X. Li, W. Chen, G. Tang, Y.-
F. Zhao, J. Org. Chem. 2015, 80, 11398. (d) W. Kong, E.
Merino, C. Nevado, Angew. Chem., Int. Ed. 2014, 53, 5078.
(e) Y.-Z. Gao, X.-Q. Li, J. Xu, Y.-L. Wu, W.-Z. Chen, G. Tang, Y.-
F. Zhao, Chem. Commun. 2015, 51, 1605. (f) H.-Y. Zhang, L.-L.
Mao, B. Yang, S.-D. Yang, Chem. Commun. 2015, 51, 4101. (g)
J.-A. Li, P.-Z. Zhang, K. Liu, A. Shoberu, J.-P. Zou, W. Zhang,
Org. Lett. 2017, 19, 4704. (h) P.-Z. Zhang, L. Zhang, J.-A. Li, A.
Shoberu, J.-P. Zou, W. Zhang, Org. Lett. 2017, 19, 5537.
For selected examples, see: (a) K. Luo, W.-C. Yang, L. Wu,
Asian, J. Org. Chem. 2017, 6, 350. (b) C.-X. Li, D.-S. Tu, R. Yao,
H. Yan, C.-S. Lu, Org. Lett. 2016, 18, 4928. (c) L.-L. Liao, Y.-Y.
Gui, X.-B. Zhang, G. Shen, H.-D. Liu, W.-J. Zhou, J. Li, D.-G. Yu,
Org. Lett. 2017, 19, 3735. (d) C.-H. Wang, Y.-H. Li, S.-D. Yang,
Org. Lett. 2018, 20, 2382.
3
4
For selected examples, see: (a) M. H. Shaw, J. Twilton, D. W.
C. MacMillan, J. Org. Chem. 2016, 81, 6898. (b) K. L. Skubi, T.
R. Blum, T. P. Yoon, Chem. Rev. 2016, 116, 10035. (c) C. K.
Prier, D. A. Rankic, D. W. C. MacMillan, Chem. Rev. 2013,
113, 5322. (d) J. Xuan, W.-J. Xiao, Angew. Chem., Int. Ed.
2012, 51, 6828. (e) J. M. R. Narayanam, C. R. J. Stephenson,
Chem. Soc. Rev. 2011, 40, 102.
5
6
T.-I. Chudakova, Y.-V. Rassuakanaya, A.-A. Sinitsa, P.-P.
Onyśko, Russ. J. Gen. Chem. 2009, 79, 195.
We are grateful for the NSFC (Nos. 21532001) and
Supported by the Open Fund of the Key Laboratory of
Functional Molecular Engineering of Guangdong Province
(2016kf04) for financial support.
For selected examples, see: (a) H. Jiang, X. An, K. Tong, T.
Zheng, Y. Zhang, S. Yu, Angew. Chem., Int. Ed. 2015, 54,
4055. (b) H.-B. Yang, S. R. Pathipati, N. Selander, ACS Catal.
2017, 7, 8441. (c) E. M. Dauncey, S. P. Morcillo, J. J. Douglas,
N. S. Sheikh, D. Leonori, Angew. Chem., Int. Ed. 2018, 57,
744. (d) X.-Y. Yu, Q.-Q. Zhao, J. Chen, J.-R. Chen, W.-J. Xiao,
Angew. Chem., Int. Ed. 2018, 57, 15505. (e) X.-Y. Yu, J.-R.
Chen, P.-Z. Wang, M.-N. Yang, D. Liang, W.-J. Xiao, Angew.
Chem., Int. Ed. 2018, 57, 738.
(a) J.-J. Ritter, P.-P. Minieri, J. Am. Chem. Soc. 1948, 70, 4045.
(b) A. G. Martínez, R. M. Alvarez, E. T. Vilar, A. G. Fraile, M.
Hanack, L. R. Subramanian, Tetrahedron Lett. 1989, 30, 581.
(c) K. Kiyokawa, T. Watanabe, L. Fra, T. Kojima, S. Minakata,
J. Org. Chem. 2017, 82, 11711. (d) C. Feng, Y. Li, X. Sheng, L.
Pan, Q. Liu, Org. Lett., 2018, 20, 6449.
Conflicts of interest
There are no conflicts to declare.
7
Notes and references
1
For selected examples, see: (a) T. Koike, M. Akita, Acc. Chem.
Res. 2016, 49, 1937. (b) G.-Y. Yin, X. Mu, G.-S. Liu, Acc. Chem.
Res. 2016, 49, 2413. (c) T. Koike, M. Akita, Chem. 2018, 4,
409. (d) X.-W. Lan, N.-X. Wang, Y. Xing, Eur. J. Org. Chem.
2017, 39, 5821. (e) S. R. Chemler, M. T. Bovino, ACS Catal.
2013, 3, 1076. (f) Q. Wei, J.-R. Chen, X.-Q. Hu, X.-C. Yang, B.
Lu, W.-J. Xiao, Org. Lett. 2015, 17, 4464. (g) R. Sakae, K.
Hirano, M. Miura, J. Am. Chem. Soc. 2015, 137, 6460. (h) Q.-
X. Qin, Y.-Y. Han, Y.-Y. Jiao, S.-Y. Yu, Org. Lett. 2017, 19, 2909.
(i) K. Muniz, L. Barreiro, R. M. Romero, C. Martinez, J. Am.
Chem. Soc. 2017, 139, 4354. (j) Y. Cheng, C. Muck-
Lichtenfeld, A. Studer, J. Am. Chem. Soc. 2018, 140, 6221. (k)
J.-J. Yu, Z. Wu, C. Zhu, Angew. Chem., Int. Ed. 2018, 57,
17156. (l) J. Hou, A. Ee, H. Cao, H.-W. Ong, J.-H. Xu, J. Wu,
Angew. Chem., Int. Ed. 2018, 57, 17220. (m) E. D. McCoy, T.
Feo, T. A. Harvey, R. O. Prum, Nat. Commun. 2018, 9, 1. (n) K.
M. Nakafuku, S. C. Fosu, D. A. Nagib, J. Am. Chem. Soc. 2018,
140, 11202. (o) A. Barthelemy, B. Tuccio, E. Magnier, G.
Dagousset, Angew. Chem., Int. Ed. 2018, 57, 13790. (p) S. Jin,
O. V. Larionov, Chem. 2018, 4, 1205. (q) N. Otomura, Y.
Okugawa, K. Hirano, M. Miura, Org. Lett. 2017, 19, 4802. (r)
N. Otomura, Y. Okugawa, K. Hirano, M. Miura, Synthesis
2018, 50, 3402. (s) N. Otomura, K. Hirano, M. Miura, Org.
Lett. 2018, 20, 7965. (t) Y. Yuan, Y. Chen, S. Tang, Z. Huang, A.
Lei, Sci. Adv. 2018, 4, DOI: 10.1126/sciadv.aat5312. (u) L.
Zhang, G. Zhang, P. Wang, Y. Li, A. Lei, Org. Lett. 2018, 20,
7396. (v) Y. Yuan, Y. Cao, Y. Lin, Y. Li, Z. Huang, A. Lei, ACS
Catal., 2018, 8, 10871.
8
9
F. Palacios, C. Alonso, M. de Los Santos J, Chem. Rev. 2005,
105, 899.
J. G. Allen, F. R. Arthenton, M. J. Hall, C. H. Hassall, S. W.
Holmes, R. W. Lambert, L. J. Nisbet, P. S. Ringrose, Nature.
1978, 272, 56.
10 (a) W. W. Smith, P. A. Bartlett, J. Am. Chem. Soc. 1998, 120,
4622. (b) M. C. Allen, W. Fuhrer, B. Tuck, R. Wade, J. M.
Wood, J. Med. Chem. 1989, 32, 1652.
11 R. Hirschmann, A. B. Smith, C. M. Taylor, P. A. Benkovic, S. D.
Taylor, K. M. Yager, P. A. Sprengler, S. J. Benkovic, Science.
1994, 265, 234.
12 E. Alonso, E. Alonso, A. Solis, C. del Pozo, Synlett 2000, 0698.
13 H. Masaaki, K. Makoto, Nature. 1959, 184, 901.
14 For selected examples, see: (a) J. E. Baxter, P. R. S. Davidson,
Makromol, Chem., Rapid Commun. 1987, 8, 311. (b) W. A.
Pryor, J.-T. Gu, D. F. Church, J. Org. Chem. 1985, 50, 185. (c)
D. Weldon, S. Holland, J. C. Scaiano, J. Org. Chem. 1996, 61,
8544. (d) P. S. Engle, S.-L. He, J. T. Banks, K. U. Ingold, J.
Lusztyk, J. Org. Chem. 1997, 62, 1210. (e) T. Courant, G.
Masson, J. Org. Chem. 2016, 81, 6945.
15 A. Boto, R. Freire, R. Hernández, E. Suárez, J. Org. Chem. 1997,
62, 2975.
4 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 5 of 5
ChemComm
View Article Online
DOI: 10.1039/C9CC06075H
A new oxime phosphonate was firstly synthesized and used in the intermolecular radical addition cascade
reaction of alkenes to access -functionalized phosphonates via visible-light-driven N-centered iminyl
radical-mediated multiple bond cleavage and recombination process.