Disulfide Promoted C?P Bond Cleavage of Phosphoramide: “P” Surrogates to Synthesize Phosphonates and Phosphinates

Article abstract of DOI:10.1002/adsc.202000511

A metal-free C?P bond cleavage reaction is described herein. Phosphoramides, a phosphine source, can react with alcohols to produce phosphonate and phosphinate derivatives in the presence of a disulfide. P?H₂, P-alkyl, and P,P-dialkyl phosphoramides can be used as substrates to obtain the corresponding pentavalent phosphine products. (Figure presented.).

Full text of DOI:10.1002/adsc.202000511

Title: Disulfide promoted C-P bond cleavage of phosphoramide: novel
“P” surrogates to synthesize phosphonates and phosphinates
Authors: Fei Hou, Xing-Peng Du, Anwar l. Alduma, Zhi-Feng Li,
Congde Huo, Xi-Cun Wang, Xiao-Feng Wu, and Zheng-Jun
Quan
This manuscript has been accepted after peer review and appears as an
Accepted Article online prior to editing, proofing, and formal publication
of the final Version of Record (VoR). This work is currently citable by
using the Digital Object Identifier (DOI) given below. The VoR will be
published online in Early View as soon as possible and may be different
to this Accepted Article as a result of editing. Readers should obtain
the VoR from the journal website shown below when it is published
to ensure accuracy of information. The authors are responsible for the
content of this Accepted Article.
To be cited as: Adv. Synth. Catal. 10.1002/adsc.202000511
Link to VoR: https://doi.org/10.1002/adsc.202000511

10.1002/adsc.202000511
Advanced Synthesis & Catalysis
UPDATE
DOI: 10.1002/adsc.201((will be filled in by the editorial staff))
Disulfide promoted C-P bond cleavage of phosphoramide: novel
“P” surrogates to synthesize phosphonates and phosphinates
Fei Hou,[‡a] Xing-Peng Du,[‡a] Anwar I. Alduma, [a] Zhi-Feng Li,*[b] Cong-De Huo,[a] Xi-
Cun Wang,[a] Xiao-Feng Wu,*[c] Zheng-Jun Quan*[a]
a
International Scientific and Technological Cooperation Base of Water Retention Chemical Functional Materials,
College of Chemistry and Chemical Engineering, Northwest Normal University, Lanzhou, Gansu 730070, People’s
Republic of China.
E-mail: quanzhengjun@hotmail.com.
College of Chemical Engineering and Technology, Key Laboratory for New Molecule Design and Function of Gansu
b
Universities, Tianshui Normal University, Tianshui 741001, People's Republic of China.
E-mail: zfli@tsnu.edu.cn.
Department of Chemistry, University of Liverpool, Crown Street, Liverpool L69 7ZD, UK.
c
E-mail: xfwu@liverpool.ac.uk.
Received: ((will be filled in by the editorial staff))
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201######.((Please
delete if not appropriate))
acyl phosphorus C-P bond cleavage using Pd or Ni
catalysts (Scheme 1A, c).[17]
Abstract. A metal-free C-P bond cleavage reaction is
described herein. Phosphoramides, a phosphine source, can
react with alcohols to produce phosphonate and
phosphinate derivatives in the presence of a disulfide. P-H2,
P-alkyl, and P,P-dialkyl phosphoramides can be used as
substrates to obtain the corresponding pentavalent
phosphine products.
Keywords: C-P bond cleavage; Disulfide; Alkyl
phosphonates; Phosphoramides; Phosphinates
Organophosphorus compounds are widely used in
materials,[1]
catalysis,[2]
agriculture,[3]
pharmaceuticals,[4] and modern organic syntheses.[5]
One representative is phosphonate which has
attracted significant attention in recent years.[6] The
current strategy for synthesizing phosphonates mainly
includes the classical Michaelis-Arbuzov reaction and
Atherton-Todd reaction,[7] direct esterification of
phosphoric acid,[8] phosphorylation of alcohols [9] and
C-P coupling reaction.[10] These strategies often
require pre-activated organic halides or pseudo
halides as substrates.[11] The severe effects associated
with the industrial preparation of organophosphorus
compounds are well known.[12] Therefore, it is
important to develop a new and environment-friendly
method to synthesize phosphonates and phosphinates.
In the past few decades, the cleavage of C-P bond
has emerged as an interesting topic of research.[13, 14]
The C-P bond cleavage is mostly realized through
transition metal catalysis (Scheme 1A, a).[15] In
addition, Davidson[16] has demonstrated the
photocatalytic acyl C-P bond cleavage of acyl
phosphine oxide under UV irradiation (Scheme 1A,
b). Recently, Wang and co-workers have reported the
Scheme 1. C-P bond cleavage to synthesize new
organophosphorus compounds.
Phosphinecarboxamide was initially reported by
Goicoechea et al[18] and our group[19] recently. We
reported the reaction of phosphinecarboxamide with
nucleophiles in an addition-elimination reaction, and
the phosphorylation of alcohols the P-H bond.[20] We
also
observed
the
dephosphorization
of
phosphinecarboxamide (removal of PH2) in these
reactions. These phenomena drew our attention, and
we speculated that these side reactions could be a
new route for the synthesis of phosphine organic
compounds (Scheme 1B). C-P bond rupture and
reconstruction has been an emerging topic because it
provides an easy way to prepare value-added
products from low-functionality molecule.[21] In this
1
This article is protected by copyright. All rights reserved.

10.1002/adsc.202000511
Advanced Synthesis & Catalysis
h)
i)
study, we developed an efficient method to cleave the
C-P bond of phosphoramides for synthesizing
phosphates and phosphinates.
Reaction at 40 °C. Reaction at 80 °C. S-(p-tolyl) (4-
methoxyphenyl)carbamothioate was obtained.
Initially, reaction of phosphoramide 1a and 1,2-
diphenyldisulfane was tested in ethanol in the
presence of K2CO3. However, the desired product
was not obtained, and all the starting materials were
fully recovered. Interestingly, phosphoramide 1b
reacted with EtOH gave the target product diethyl
phosphite (4a) in 23% yield under the same reaction
conditions (Scheme 2).
Inspired by the above results, P-alkylated
phosphinecarboxamide (1c) with EtOH (2a) was used
as the model substrates to explore the optimal
reaction conditions in the presence of disulfide 3a for
3 h at room temperature (Table 2). First, we
investigated the effect of disulfide concentration on
the yield of the reaction (entries 1-6, Table 1). No
product was detected in the absence of disulfide
(entry 1). The product yield gradually increased with
increasing amount of the disulfide compound. When
2.5 equivalent of disulfide was added, the product
yield increased to 52% (entries 2-6). Different types
of bases were also examined (entries 7-13). K2CO3
was found to be the most beneficial for this reaction,
and yield of the target product (4b) increased to 83%
(entry 12). Following this, various solvents were
screened (entries 14-18). When ethanol was replaced
by equivalent amount of acetonitrile, 4b was isolated
in 80% yield (entry 14), suggesting that acetonitrile
was also effective in this reaction. Considering the
generity and sustainability, ethanol was chosen as the
optimal solvent for this reaction (entry 12).
Increasing the temperature inhibited the reaction
(entries 19-20). Particularly, it is worth mentioned
that air was an essential component for this reaction.
Under inert atmosphere, the product was obtained in
only 10% yield (entry 21). When 3a was replaced by
thiophenol, 4b was obtained in a very low yield (10%,
entry 22). Moreover, the use of various disulfide such
as 4-methyl disulfide (3b) gave a good yield of 4b
(entry 22). Although thioester 5a or 5b is a byproduct
of this reaction, it is a valuable and useful
intermediate that has been widely used in organic
synthesis.[22, 23]
Scheme 2. Disulfide-promoted alkyl phosphate formation.
Table 1. Optimization of reaction conditions.a
1c:3a
Entry (mmo
l)
Yield (%)c
Base
(equiv)
Solvent
4b
5a
1
2
3
4
5
6
7
8
1:0
1:0.5
1:1
1:1.5
1:2
1:2.5
1:2
1:2
1:2
1:2
1:2
1:2
1:2
1:2
1:2
1:2
1:2
1:2
Cs2CO3 (1) EtOH
Cs2CO3 (1) EtOH
Cs2CO3 (1) EtOH
Cs2CO3 (1) EtOH
Cs2CO3 (1) EtOH
Cs2CO3 (1) EtOH
0
0
14
20
40
50
52
64
76
78
78
80
79
66
DBU (1)
EtOH
t-BuOK (1) EtOH
trace 35
9
K2CO3 (1)
Et3N (1)
K2CO3 (1)
K2CO3 (2)
EtOH
EtOH
EtOH
EtOH
70
62
70
83
63
83
71
80
83
80
85
10
11
12
13
14b
15b
16b
17b
18b
Cs2CO3 (2) EtOH
K2CO3 (2)
K2CO3 (2)
K2CO3 (2)
K2CO3 (2)
K2CO3 (2)
K2CO3 (2)
K2CO3 (2)
K2CO3 (2)
K2CO3 (2)
K2CO3 (2)
CH3CN 80
DMSO
Dioxane 32
CH2Cl2 36
trace trace
53
50
Toluene trace trace
19b, g 1:2
20b, h 1:2
MeCN
MeCN
EtOH
EtOH
EtOH
52
18
10
10
76
62
trace
84
21d
22e
23f
1:2
1:2
1:2
12
80i
a) Reaction conditions: A mixture of disulfide (0.4 mmol)
and K2CO3 (0.4 mmol) in CH3CN (3 mL) was stirred under
an air for 0.5 h, then 1c (0.2 mmol) was added. Stirring
was continued at room temperature for 3 h. b) 2 equivalents
c)
d)
of ethanol was added. Isolated yields. Reaction under
e)
f)
an argon atmosphere. 3a was replaced by thiophenol.
g)
4-Methyl disulfide (3b) was added to replace 3a.
2
This article is protected by copyright. All rights reserved.

10.1002/adsc.202000511
Advanced Synthesis & Catalysis
Scheme 4. Substrate scopes of the Michael addition
reaction.
The phosphate products could be synthesized
smoothly through the P-Michael addition reaction
(Scheme 3I). There is no obvious electronic effect of
the substituent group on the aromatic rings. Thus,
similar yields were obtained for both electron-
withdrawing (4j, 4m) and electron-donating groups
(4f, 4k, 4l). The o-Methyl substituted aromatic
product (4l) was obtained in 68% yield, while
naphthyl product (4n) was obtained in 54% yield. For
the unsubstituted aromatic ring, product 4i was
obtained in 81% yield, which is comparable to the
yields of phenylpropyl and phenylbutyl products (4b,
4c).
Scheme 3. Substrate scope for the synthesis of
phosphonates/phosphinates.
With the optimized reaction conditions in hand,
substrates scope of the reaction was investigated. As
show in scheme 3I, phenylpropyl and phenylbutyl
substituted products 4b and 4c were obtained in
excellent yields, and both of these are all useful and
It is worth emphasizing that the protocol works
well for the synthesis of hypophosphonate
24,
25]
valuable pharmaceutical intermediates.[6,
Notably, the more reactive benzyl substituted
substrate gave product 4d in 64% yield, and the long-
chain heptane substituted phosphanecarboxamide
gave phosphate 4e in 68% yield.
compounds
when
P,P-difunctionalized
phosphanecarboxamides are used as substrate
(Scheme 3II). For example, the desired products (4p,
4s) were obtained in 86% and 80% yields. Notably,
different alcohols (methanol, ethanol and propanol)
could be used as the solvent, and all the reactions
afforded the target products (4f-4h) in good yields. In
addition, compounds 4q and 4r could be isolated in
reasonably good yields (76% and 83% yields,
respectively). Unfortunately, we found that phenol
could not be used as a nucleophilic reagent to obtain
the corresponding target product.
To further increase the diversity of the functional
groups on phosphorus in this C-P bond cleavage
reaction, we prepared a series of P(III) substrates
through the P-Michael addition reaction (Scheme 4).
Such compounds are usually difficult to synthesize by
the conventional methods. Thus, the method of
establishing C-P bond is of great interest to organic
researchers.[26] Although some advances have been
made in this field,[27] the formation of C(sp3)-P bond
is still significantly challenging. Especially, the direct
constructions of C(sp3)-P bond and -PH2 group have
rarely been reported. The method developed in this
study will provide a new alternative approach for the
synthesis of organic P(Ⅲ) compounds.
We next used 1Bl as substrate to carry out the
gram scale reaction (Scheme 5). We found 1Bl could
further undergo a gram-scale reaction to transform
into phosphate ester 4g. Although this scale-up
reaction required a longer reaction time (5h), and the
product 4g was obtained in 71% yield.
3
This article is protected by copyright. All rights reserved.

10.1002/adsc.202000511
Advanced Synthesis & Catalysis
S4 (detected by HRMS), which eventually undergoes
nucleophilic substitution reaction with alcohol to
form desired product 4g (path a). Alternatively,
intermediate S2 can be resulfurized to give the
phosphonodithioate S5, which is subsequently
esterized by EtOH to form 4g (path b). Since we
estimated the molecular weight of the intermediates
S3 and S4 in HRMS, we speculate that the reaction is
more likely to proceed through path a. Furthermore,
since P(Ⅲ)-H was extremely sensitive to air and was
easily oxidized, in the absence of a disulfide,
substrate 1B can be directly oxidized to phosphoric
acid 7.[29c, 29f]
Scheme 5. Gram-scale reaction to prepare single Michael
addition product(1Bl) and phosphonates(4g).
Scheme 7. Proposed mechanism.
Scheme 6. Control experiments.
In summary, we have developed a successful
method to capture PH2(R) fragments generated from
the C-P bond cleavage of a phosphoramide. A series
of phosphonates and phosphinates were synthesized
by this method. This method is operationally simple
under mild conditions with high yields of products,
broad substrate scope, and good practical
applicability. Most importantly, even the byproduct
of this reaction, thioester, is a valuable and useful
intermediate in organic synthesis.
In order to elucidate the reaction mechanism,
several control experiments were conducted (Scheme
6). In the absence of alcohol, substrates 1Bl and 1Bg
gave sole products: phosphoric acids (7) and (8) in
good yields with and without disulfide 3a
respectively. Products 7 and 8 did not react further
with ethanol to give product (4g) (Scheme 6I,
equations 1-4). Therefore, compounds 7 and 8 were
by-products, and not the intermediates of the reaction.
It is evident from scheme 6II that oxidants such as air
or O2 played a crucial role in the generation of the
desired product (Scheme 6II, equation 1).
Furthermore, the reaction in the presence of a free
radical inhibitor (2,2,6,6-tetramethylpiperidin-1-oxyl
(TEMPO)) gave the target product (4g) in high yield
(76%, Scheme 6II, equation 2), suggesting that the
reaction did not proceed through a free-radical
process. Both disulfide and alcohol were
indispensable in this transformation (Scheme 6III,
equations 1-2). Unfortunately, we could not isolate
any phosphorus product in the absence of ethanol
except thioester 5a (84% yield).
Experimental Section
General procedure for the synthesis of phosphonates 4b.
To a solution of disulfide 3a (87.2 mg, 2 equiv), and
K2CO3 (55.2 mg, 2 equiv) in EtOH (3.0 mL) was added N-
(4-methoxyphenyl)-1-(4-
phenylbutyl)phosphanecarboxamide (1c, 63 mg, 0.2 mmol)
at room temperature and stirred for 3 h. After the reaction
reached completion, the reaction mixture was diluted with
ethyl acetate (10 mL). The solvent was removed under
reduced pressure, and the residue was purified by flash
column chromatography on silica gel to give
corresponding thioester 5a (petroleum ether : ethyl acetate
= 8:1) and phosphonates 4b (ethyl acetate).
Based on the above preliminary results and related
literature reports,[28] a plausible reaction mechanism
was proposed (Scheme 7). Initially, the reaction
starting is promoted by disulfide (3a) attacking
substrate 1Bl generating intermediate S1 and
thioester 5a. Then, intermediate S1 is oxidized to S2,
which reacts with EtOH to form intermediate S3
(detected by HRMS). The S3 reacts with 3a to form
Acknowledgements
4
This article is protected by copyright. All rights reserved.

10.1002/adsc.202000511
Advanced Synthesis & Catalysis
We are thankful for financial support from the LongYuan Youth
Innovative and Entrepreneurial Talents Project (the Key Talent
Projects of Gansu Province [2019]39) and National Nature
Science Foundation of China (No. 21562036).
608-617; h) Y. L. Zhao, G. J. Wu, Y. Li, L. X. Gao, F.
S. Han, Chem. Eur. J. 2012, 18, 9622-9627; i) C. Shen,
G. Yang, W. Zhang, Org. Biomol. Chem. 2012, 10,
3500-3505; j) R. Berrino, S. Cacchi, G. Fabrizi, A.
Goggiamani, P. Stabile, Org. Biomol. Chem. 2010, 8,
4815-4818; k) M. Andaloussi, J. Lindh, J. Sävmarker, P.
J. R. Sjöberg, M. Larhed, Chem. Eur. J. 2009, 15,
13069-13074; l) H. Rao, Y. Jin, H. Fu, Y. Jiang, Y.
Zhao, Chem. Eur. J. 2006, 12, 3636-3646; m) D.
Gelman, L. Jiang, S. L. Buchwald, Org. Lett. 2003, 5,
2315-2318; n) K. S. Petrakis, T. L. Nagabhushan, J. Am.
Chem. Soc. 1987, 109, 2831-2633. o) L. Niu, J. Liu, H.
Yi, S. Wang, X.-A. Liang, A. K. Singh, C.-W. Chiang,
A. Lei, ACS Catal. 2017, 7, 7412-7416; p) Y. He, H.
Wu, F. D. Toste, Chem. Sci. 2015, 6, 1194-1198; q) M.
Min, D. Kang, S. Jung, S. Hong, Adv. Synth. Catal.
2016, 358, 1296-1301.
References
[1] a) C. Queffelec, M. Petit, P. Janvier, D. A. Knight, B.
Bujoli, Chem. Rev. 2012, 112, 3777; b) H. Onouchi, T.
Miyagawa, A. Furuko, K. Maeda, E. Yashima, J. Am.
Chem. Soc. 2005, 127, 2960-2965.
[2] a) C. S. Demmer, N. K. Larsen, L. Bunch, Chem. Rev.
2011, 111, 7981-8006; b) P. Guga, Curr. Top. Med.
Chem. 2007, 7, 695-713; c) K. Moonen, O. Laureyn, C.
V. Stevens, Chem. Rev. 2004, 104, 6177-6216.
[3] B. Nowack, Water Res. 2003, 37, 2533-2546.
[11] B. Q. Xiong, G. Wang, C. S. Zhou, Y. Liu, P. L.
[4] a) G. P. Horsman, D. L. Zechel, Chem. Rev. 2017, 117,
5704-5783; b) A. Mucha, P. Kafarski, Ł. Berlicki, J.
Med. Chem. 2011, 54, 5955-5980; c) J. W. McGrath, J.
P. Chin, J. P. Quinn, Nat. Rev. Microbiol. 2013, 11,
412-419.
Zhang, K. W. Tang, J. Org. Chem. 2018, 83, 993-999.
[12] C. Y. Li, Q. Wang, J. Q. Zhang, Q. Xu, L. B. Han,
Green Chem. 2019, 21, 2916-2922.
[13] a) I A. Inoue, H. Shinokubo, K. Oshima, J. Am. Chem.
Soc. 2003, 125, 1484-1485; b) K. Masuda, N.
Sakiyama, R. Tanaka, K. Noguchi, K. Tanaka, J. Am.
Chem. Soc. 2011, 133, 6918-6921; c) B. E. Segelstein,
T. W. Butler, B. L. Chenard, J. Org. Chem. 1995, 60,
12-13; d) D. K. Morita, J. K. Stille, J. R. Norton, J. Am.
Chem. Soc. 1995, 117, 8576-8581; e) B. M. Goodson,
T. I. Wallow, B. M. Novak, J. Am. Chem. Soc. 1997,
119, 12441-12453. f) P. A. Byrne, D. G. Gilheany, J.
Am. Chem. Soc. 2012, 134, 9225-9239.
[5] R. Martin, S. L. Buchwald, Acc. Chem. Res. 2008, 41,
1461-1473.
[6] a) M. B. Geeson, C. C. Cummins, Science. 2018, 359,
1383-1385; b) A. L. Schwan, Chem. Soc. Rev. 2004, 33,
218-224; c) C. S. Demmer, N. Krogsgaard-Larsen, L.
Bunch, Chem. Rev. 2011, 111, 7981-8006; d) J. L.
Montchamp, Acc. Chem. Res. 2014, 47, 77-87; e) F. M.
J. Tappe, V. T. Trepohl, M. Oestreich, Synthesis, 2010,
18, 3037-3062; f) C. A. Bange, R. Waterman, Chem.
Eur. J. 2016, 22, 12598-12605; g) R. Waterman, Chem.
Soc. Rev. 2013, 42, 5629-5641; h) Q. Xu, L. B. Han, J.
Organomet. Chem. 2011, 696, 130-140; i) J. Yang, T.
Chen, L. B. Han, J. Am. Chem. Soc. 2015, 137, 1782-
1785.
[14] a) L. Wang, H. Chen, Z. Duan, Chem. Asian J. 2018,
13, 2164-2173; b) K. Jia, J. Li, Y. Chen, Chem. Eur. J.
2018, 24, 3174-3177.
[15] For selected examples on C-P(III) cleavage, see: a) F.
Y. Kwong, K. S. Chan, Organometallics. 2000, 19,
2058-2060; b) F. Y. Kwong, K. S. Chan, Chem.
Commun. 2000, 1069-1070; c) J. Cao, X. Huang, L.
Wu, Chem. Commun. 2013, 49, 7747-7749; d) K. Baba,
M. Tobisu, N. Chatani, Angew. Chem. Int. Ed. 2013, 52,
11892-11895; Angew. Chem. 2013, 125, 12108-12111;
e) K. Baba, M. Tobisu, N. Chatani, Org. Lett. 2015, 17,
70-73; f) H. Zhou, J. Li, H. Yang, C. Xia, G. Jiang, Org.
Lett. 2015, 17, 4628-4631; g) Y. Zhou, Z. Gan, B. Su,
Z. Duan, F. Mathey, Org. Lett. 2015, 17, 5722-5724. h)
P. M. Scheetz, D. S. Glueck, A. L. Rheingold,
Organometallics, 2017, 36, 3387-3397; i) Z. Lian, B. N.
Bhawal, P. Yu, B. Morandi, Science, 2017, 356, 1059-
1063.
[7] a) B. A. Arbuzov, Pure Appl. Chem. 1964, 9, 307-336;
b) F. R. Atherton, J. Chem. Soc. 1945, 660-663.
[8] a) B. Xiong, X. Feng, L. Zhu, T. Chen, Y. Zhou, C-T.
Au, S-F. Yin, ACS Catal. 2015, 5, 537-543; b) A.
Sakakura, M. Katsukawa, K. Ishihara, Angew. Chem.
Int. Ed. 2007, 46, 1423-1426; Angew. Chem. 2007, 119,
1445-1448.
[9] a) J. Dhineshkumar, K. R. Prabhu, Org. Lett. 2013, 15,
6062-6065; b) C. Y. Li, T. Q. Chen, L.-B. Han, Dalton
Trans. 2016, 45, 14893-14897.
[10] a) T. Hirao, T. Masunaga, Y. Ohshiro, T. Agawa,
Synthesis. 1981, 1, 56-57; b) T. Hirao, T. Masunaga, Y.
Ohshiro, T. Agawa, Tetrahedron Lett. 1980, 21, 3595-
3598. c) C. Liu, M. Szostak, Angew. Chem. Int. Ed.
2017, 56, 12718-12722; Angew. Chem. 2017, 129,
12892-12896; and references cited herein; d) H. Luo, H.
Liu, X. Chen, K. Wang, X. Luo, K. Wang, Chem.
Commun. 2017, 53, 956-958; e) J. Yang, J. Xiao, T.
Chen, S. F. Yin, L. B. Han, Chem. Commun. 2016, 52,
12233-12236; f) C. Fu, C. M. So, F. Y. Kwong, Org.
Lett. 2015, 17, 5906-5909; g) T. Wang, S. Sang, L. Liu,
H. Qiao, Y. Gao, Y. Zhao, J. Org. Chem. 2014, 79,
[16] a) J. E. Baxter, R. S. Davidson, D. G. Stevens, J.
Chem. Soc. Chem. Commun. 1987, 73-75; b) G. W.
Sluggett, C. Turro, M. W. G. V. Koptyug, N. J. Turro, J.
Am. Chem. Soc. 1995, 117, 5148-5153; c) G. W.
Sluggett, P. F. McGarry, I. V. Koptyug, N. J. Turro, J.
Am. Chem. Soc. 1996, 118, 7367-7372.
[17] a) R. R. Yu, X. Y. Chen, S. F. Martin, Z. Q. Wang,
Org. Lett. 2017, 19, 1808-1811; b) R. R. Yu, X. Y.
Chen, Z. Q. Wang, Tetrahedron Lett. 2016, 57, 3404-
3406.
5
This article is protected by copyright. All rights reserved.

10.1002/adsc.202000511
Advanced Synthesis & Catalysis
[18] a) A. R. Jupp, G. Trott, J. D. G. Holl, D. Carmichael, J.
M. Goicoechea, Chem. Eur. J. 2015, 21, 8015-8018; b)
M. B. Geeson, A. R. Jupp, J. E. McGrady, J. M.
Goicoechea, Chem. Commun. 2014, 50, 12281-12284;
c) A. R. Jupp, J. M. Goicoechea, J. Am. Chem. Soc.
2013, 135, 19131-19134.
163-166; c) W.W. Metcalf, W. A. van der Donk, Annu.
Rev. Biochem. 2009, 78, 65-94; d) V. D. Romanenko,
V. P. Kukhar, Chem. Rev. 2006, 106, 3868-3935.
[26] a) H. Y. Zeng, C-J. Li, Org. Lett. 2019, 21, 1301-1305;
b) J. Y. Dong, L. Liu, X. Y. Ji, L-B. Han. Org. Lett.
2019, 21, 3198-3203; c) J. Yuan, W-P. To, C-M. Che.
Org. Lett. 2018, 20, 7816-7820; d) C. Huang, X. Tang,
H. Fu, Y. F. Zhao, J. Org. Chem. 2006, 71, 5020-5022;
e) A. L. Schwan, Chem. Soc. Rev. 2004, 33, 218-224.
[19] a) Y-H. Wu, Z-F. Li, W-P. Wang, X-C. Wang, Z-J.
Quan, Eur. J. Org. Chem. 2017, 5546-5553.
[20] a) Y.-H. Wu, Q.-L. Wu, W.-P. Wang, X.-C. Wang, Z.-
J. Quan, Adv. Synth. Catal. 2018, 360, 2382-2388; b)
X-G. Chen, Q-L. Wu, F. Hou, X-C. Wang, Z-J. Quan,
Synlett. 2019, 30, 73-76.
[27] a) D. Gelman, L. Jiang, S. L. Buchwald, Org. Lett.
2003, 5, 2315-2318; b) T. Hirai, L-B. Han, Org. Lett.
2007, 9, 53-55.
[21] T. Liu, J. Zhu, X. Sun, L. Cheng, L. Wu, Adv. Synth.
Catal. 2019, 361, 3532-3537.
[28] a) S. Song, Y. Zhang, A. Yeerlan, B. Zhu, J. Liu, N.
Jiao, Angew. Chem. Int. Ed. 2017, 56, 2487-2451;
Angew. Chem. 2017, 129, 2527-2531; b) X. Qiu, X. X.
Yang, Y. Q. Zhang, S. Song, N. Jiao, Org. Chem. Front.
2019, 6, 2220-2225; c) O. Berger, J-L. Montchamp, J.
Org. Chem. 2019, 84, 9239-9256; d) P. A. Donets, N.
Cramer, J. Am. Chem. Soc. 2013, 135, 11772-11775; e)
Y. Unoh, K. Hirano, M. Miura, J. Am. Chem. Soc. 2017,
139, 6106-6109; f) T. Yuan, S. Huang, C. Cai, G-P. Lu,
Org. Biomol. Chem. 2018, 16, 30-33; g) J-L.
Montchamp, Acc. Chem. Res. 2014, 47, 77-87; h) E. J.
Corey, K. C. Nicolaou, J. Am. Chem. Soc. 1974, 96,
5614-5616.
[22] a) M. J. Xuan, C. L. Lu, M. N. Liu, B-L. Lin, J. Org.
Chem. 2019, 84, 7694-7701; b) F. H. Xiao, S. S. Yuan,
S. W. Liu, G-J. Deng, Adv. Synth. Catal. 2019, 361,
3331-3336; c) F. H. Lutter, L. Grokenberger, M. S.
Hofmayer, P. Knochel, Chem. Sci. 2019, 10, 8241-8245.
[23] Utilization of this method to preprae the thioesters is
undergoing in our group.
[24] N. G. Anderson, Org. Process Res. Dev. 1997, 1, 315-
319.
[25] a) W.-Q. Liu, M. Vidal, C. Olszowy, E. Million, C.
Lenoir, C. Garbay, J. Med. Chem. 2004, 47, 1223-
1233; b) R. P. McGeary, P. Vella, J. Y. W. Mak, L. W.
Guddat, G. Schenk, Bioorg. Med. Chem. Lett. 2009, 19,
6
This article is protected by copyright. All rights reserved.

10.1002/adsc.202000511
Advanced Synthesis & Catalysis
UPDATE
Disulfide promoted C-P bond cleavage of
phosphoramide: novel “P” surrogates to synthesize
phosphonates and phosphinates
Adv. Synth. Catal. Year, Volume, Page – Page
Fei Hou, Xing-Peng Du, Anwar I. Alduma, Zhi
Feng Li,* Cong-De Huo, Xi-Cun Wang, Xiao-Feng
Wu,* Zheng-Jun Quan*
7
This article is protected by copyright. All rights reserved.