Efficient Pd-Catalyzed Dehydrogenative Coupling of P(O)H with RSH: A Precise Construction of P(O)-S Bonds

Article abstract of DOI:10.1021/jacs.6b03112

A Pd-catalyzed dehydrogenative phosphorylation of thiols is developed. A variety of thiols dehydrogenatively couple readily with all three kinds of P(O)-H compounds, i.e., H-phosphonates, H-phosphinates, and secondary phosphine oxides, providing a general access to the valuable phosphorothioates including the P-chiral compounds. A plausible mechanism is proposed.

Full text of DOI:10.1021/jacs.6b03112

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Communication
Efficient Pd-Catalyzed Dehydrogenative Coupling of
P(O)H with RSH: a Precise Construction of P(O)-S Bonds
Yueyue Zhu, Tieqiao Chen, Shan Li, Shigeru Shimada, and Li-Biao Han
J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/jacs.6b03112 • Publication Date (Web): 29 Apr 2016
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Efficient Pd-Catalyzed Dehydrogenative Coupling of P(O)H
with RSH: a Precise Construction of P(O)-S Bonds
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Yueyue Zhu,† Tieqiao Chen,†* Shan Li,† Shigeru Shimada,‡ Li-Biao Han‡*
†State Key Laboratory of Chemo/Biosensing and Chemometrics, College of Chemistry and Chemical Engineering, Hunan
University, Changsha 410082, China.
‡National Institute of Advanced Industrial Science and Technology (AIST), Tsukuba, Ibaraki 305-8565, Japan.
Supporting Information Placeholder
P-chiral phosphorothioates and phosphorothioates 1 with OH and
NH2 groups, that could hardly be prepared by the old nucleophilic
substitutions,2,3 were readily obtained by this new method.
Mechanistic studies showed that this transformation would
proceed via a Pd(0)/Pd(II) process involving oxidative addition,
ligand exchange releasing dihydrogen and reductive elimination.
ABSTRACT: A Pd-catalyzed dehydrogenative phosphorylation
of thiols is developed. A variety of thiols dehydrogenatively
couple readily with all three kinds of P(O)-H compounds, i.e. H-
phosphonates, H-phosphinates and secondary phosphine oxides,
providing a general access to the valuable phosphorothioates
including the P-chiral compounds. A plausible mechanism is
proposed.
Scheme 2. Efficient synthesis of phosphorothioates.
Phosphorothioates 1 are an important class of molecules in
biological chemistry.1 A number of well-known medicines and
insecticides are based on these compounds (Scheme 1).1a-1e Their
applications in organic synthesis are also well recognized.1b,1f-1h
However, efficient and precise preparations of these compounds
are rather unexplored (Scheme 2).2-5 These compounds are
traditionally prepared by nucleophilic substitution of the toxic and
moisture sensitive halides (RO)2P(O)Cl or RSX directly or
indirectly.2-3 However, in addition to safety and efficiency
problems, these old methods also have severe limitations towards
the co-presence of functional groups in the molecules.
In the presence of 2.5 mol% Pd2(dba)3 and 5 mol% dppf (1,1'-
bis(diphenylphosphino)ferrocene), diethyl phosphonate 3a reacted
with an equivalent amount of 4-(tert-butyl)benzenethiol 2a in
o
dioxane at 100 C for 20 h, producing the coupling product 1a in
40% yield (Table 1, entry 1).9 By adding 2 equiv styrene to the
reaction mixture, the yield of 1a increased to 80% (Table 1, entry
2).10 Further elevating the reaction temperature to 120 C did not
o
improve the yield of the product; whereas only 41% yield of 1a
was obtained when the reaction was conducted at 80 C (Table 1,
Scheme 1. Selected examples of drugs and insecticides of
phosphorothioates.
o
entries 4 and 5). The choice of a suitable phosphine ligand was the
key factor for this transformation (Table 1, entries 6-14) since
only a trace amount of 1a was detected with Ph3P, Cy3P, 1,1-
bis(diphenylphosphino)methane (dppm), 1,2-bis(diphenylph-
osphino)ethane
(dppe),
1,3-bis(diphenylphosphino)propane
(dpph), 1,2-
(dppp), 1,6-bis(diphenylphosphino)hexane
bis(dicyclohexylphosphino)ethane (dcype). The yields were low
with 1,4-bis(diphenylphosphino)butane (dppb) and xantphos too.
The coupling reaction also proceeded in other solvents with
toluene being the best choice (Table 1, entries 15-17). A very high
yield (93%) of phosphorothioate 1a was produced when 1.2 equiv
2a was employed (Table 1, entry 18).10
Herein, we report an efficient Pd-catalyzed dehydrogenative
phosphorylation of the readily available P(O)H compounds with
thiols 2 to produce phosphorothioates 1 in high yields (Scheme
2).4,6-8 This reaction is general and a variety of substrates, i.e. all
the three kinds of P(O)-H compounds 3 (H-phosphonates, H-
phosphinates and secondary phosphine oxides) can couple with
both aromatic and aliphatic thiols. This new method also easily
overcomes the limitations of the traditional methods. For example,
This Pd-catalyzed dehydrogenative phosphorylation was a
rather general reaction for the synthesis of phosphorothioates. A
variety of thiols readily coupled with P(O)-H compounds under
the present reaction conditions to produce the corresponding
phosphorothioates 1 in good to excellent yields. Thus, aromatic
thiols with tert-butyl, methyl, methoxyl and amide group on the
benzene ring all gave the corresponding coupling products in
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good yields (Table 2, entries 1-4). A substrate bearing a highly
process.12 It was noted that the classical Atherton-Todd reaction
coordinative methylthio group also produced the product 1e in
79% yield (Table 2, entry 5). Functional groups such as the free
amine, hydroxyl and even the easily hydrolyzed OCF3 groups
were tolerated well under the current reaction conditions (Table 2,
entries 6-8). A halogen like fuloro and chloro group also survived,
facilitating further functionalization of the products (Table 2,
entries 9 and 10). The substrates with electron-withdrawing
groups like CF3 and NO2 groups coupled readily with diethyl
phosphonate, generating the coupling products in moderate yields
(Table 2, entries 11 and 12). Naphthalene-1-thiol was also proved
to be a good substrate (Table 2, entry 13).
could not produce such products but gave those with inversed
3
4
5
6
7
8
9
configuration at phosphorus.3c,3d
Table 2. Pd-catalyzed dehydrogenative phosphorylation of
thiols.a
O
P
O
P
cat Pd/dppf
styrene
Z1
H
H
SR
Z1
SR
+
Z2
Z2
3
2
1
10
11
12
13
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Entry
SH,
2
P(O)H,
3
Product, (isolated yield)
1
SH
S
P(O)(OEt)2
Table 1. Pd-catalyzed dehydrogenative coupling of diethyl
R
R
phosphonate with 4-(tert-butyl)benzenethiol.a
1
2
2a, R = 4-t-Bu 3a, (EtO)2P(O)H
1a, R = 4-t-Bu, 90%
1b, R = 4-Me, 84%
1c, R = 4-OMe, 85%
1d, R = 4-NHAc, 70%
2b, R = 4-Me
3b 2c, R = 4-OMe
4b 2d, R = 4-NHAc
5
2e, R = 4-SMe
1e, R = 4-SMe, 79%
1f, R = 4-NH2, 76%
1g, R = 4-OH, 74%
6b 2f, R = 4-NH2
7b 2g, R = 4-OH
8
9
2h
, R = 4-OCF3
1h
, R = 4-OCF3, 74%
2i, R = 4-F
1i, R = 4-F, 87%
10 2j, R = 4-Cl
11c 2k, R = 4-CF3
12d 2l, R = 4-NO2
1j, R = 4-Cl, 79%
1k, R = 4-CF3, 54%
1l, R = 4-NO2, 49%
SH
S
P(O)(OEt)2
13
t-Bu
2m
2a
1m
, 81%
SH
t-Bu
S [P]
14
15
16
17
18c
3b, (i-PrO)2P(O)H 1n, [P] = (i-PrO)2P(O), 70%
3c, (Me CO) P(O)H 1o
, [P] = (Me2CO)2P(O), 49%
, [P] = Ph(EtO)P(O), 73%
, [P] = Ph2P(O), 62%
2
2
3d, Ph(EtO)P(O)H 1p
3e, Ph2P(O)H
1q
1r
3f, n-Bu2P(O)H
, [P] = n-Bu2P(O), 42%
O
PH
O
O
O
P
t-Bu
S
S
19
3g
1s, 59%
aReaction conditions: 0.2 mmol 2a, 0.2 mmol 3a, 0.4 mmol
styrene, 2.5 mol% Pd2dba3/phosphine ligand (Pd/P = 1:2) and 1
mL solvent were heated in a 25 mL glass tube at the indicated
temperature for 20 h. b31P yield using triphenylphosphine oxide as
O
O
SH
(-)MenO
Ph
P H
P
Ph
OMen(-)
, R = 4-t-Bu, 94%
SP-1u, R = 4-OMe, 97%
R
R
c
d
20
21
22
2a
RP-3h
S -1t
P
, R = 4-t-Bu
an internal standard. without styrene. 1 mol% Pd2(dba)3 was
loaded. e120 oC. f80 oC. g1.2 equiv 2a was used.
2c, R = 4-OMe
2d
S -1v
, R = 4-NHAc
, R = 4-NHAc, 77%
P
Interestingly, all the three kinds of hydrogen phosphoryl
compounds were applicable to this reaction. Thus, in addition to
diethyl phosphonate, diisopropyl phosphonate and even the easily
hydrolyzed five-membered H-phosphonate 3c also coupled
readily with 4-(tert-butyl)benzenethiol 2a under similar reaction
conditions (Table 2, entries 14 and 15). This Pd-catalyzed
dehydrogenative phosphorylation also took place efficiently with
H-phosphinates and secondary phosphine oxides (Table 2, entries
16-22).
3a
SH
S
S
P(O)(OEt)2
P(O)(OEt)2
23
24
2n
C8H17 SH
2o
1w, 79%
C8H17
1x, 87%
aReaction conditions: 0.24 mmol 2, 0.2 mmol 3, 0.4 mmol
styrene, 2.5 mol% Pd2dba3/dppf (Pd/P = 1:2) and 1 mL toluene
o
b
were heated in a 25 mL glass tube at 100 C for 20 h. Dioxane
Notably, by using the present Pd-catalyzed dehydrogenative
phosphorylation strategy, the P-chiral phosphorothioates 1 were
synthesized stereoselectively in high yields with retention of
configuration at phosphorus (Table 2, entries 20-22).11 This is the
first synthesis of P-chiral phosphorothioates via catalytic
c
d
was used as solvent. 5 mol% Pd2(dba)3 was loaded. 0.4 mmol
scale, 0.5 mL toluene was used.
Importantly, aliphatic thiols were also phosphorylated
efficiently under the current reaction conditions (Table 2, entries
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23 and 24). Thus, both cyclohexanethiol and octane-1-thiol
aliphatic thiols coupled with H-phosphonates. All the three kinds
of hydrogen phosphoryl compounds served well in the catalytic
system. This reaction provides a general method for the synthesis
of valuable phosphorothioates including the P-chiral phosphorus
compounds.
coupled readily with diethyl phosphonate, producing the coupling
product 1w and 1x in 79% and 87% yields, respectively. It was
noted that the traditional Atherton-Todd reaction was not
applicable to the synthesis of these compounds.3d
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ASSOCIATED CONTENT
Supporting Information
General information, experimental procedures, CIF files of 5a,
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1
characterization data, copies of H, 13C and 31P NMR spectra for
products. This material is available free of charge via the Internet
at http://pubs.acs.org.
Mechanistic studies show that the oxidative addition of five-
membered H-phosphonate 3c to Pd(PEt3)4 produced
a
hydridopalladium complex 4a quantitatively at room temperature.
Subsequent addition of an equivalent benzenethiol 2a to a solution
of 4a readily generated an unsymmetrical phosphoryl
thiopalladium complex 5a (Figure 1) with H2 evolution (eq 1).
This reaction can be achieved in one pot. Thus, Pd(PEt3)4 reacted
with a mixture of benzenethiol and 3c smoothly at room
temperature to produce 5a in 86% isolated yield.13,14 The structure
of complex 5a was also determined by X-ray analysis.
AUTHOR INFORMATION
Corresponding Author
*E-mail: chentieqiao@hnu.edu.cn
*E-mail: libiao-han@aist.go.jp
Notes
The authors declare no competing financial interests.
ACKNOWLEDGMENT
Partial financial supports from NFSC (21403062, 21373080),
HNNSF 2015JJ3039, the Fundamental Research Funds for the
Central Universities (Hunan University) are gratefully
acknowledged.
REFERENCES
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would be appreciated and still remains a great challenge. (a) Wang, J.;
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phosphonates are applicable).
Figure 1. ORTEP drawing of complex 5a. Hydrogen atoms are
omitted for clarity; Ellipsoids are drawn at 50% probability.
Therefore, it is reasonable to propose that the current cross
dehydrogenative coupling proceeds via a catalytic cycle as shown
in Scheme 3. A Z-H bond first oxidatively adds to Pd(0) to
produce a hydridometal complex 4, which subsequently reacts
with E-H, generating a species 5 and dihydrogen.15 Reductive
elimination of complex 5 affords the products and regenerates
Pd(0) complex.
Scheme 3. Proposed mechanism for the Pd-catalyzed
dehydrogenative phosphorylation of thiols. The ligands
were omitted for clarity.
In summary, we have developed
a
Pd-catalyzed
dehydrogenative phosphorylation of thiols. Both aromatic and
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(5) Other methods: (a) Ouyang, Y.-J.; Li, Y.-Y.; Li, N.-B.; Xu, X.-H.
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1623.
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(6) Dehydrogenative coupling is emerging as an important
methodology for chemical bond formation. The transformation obviates
the need for prefunctionalization of starting materials and is recognized to
be viable alternative to traditional coupling strategy with concomitant salt
elimination. For book and reviews, see: (a) Li, C.-J. From C-H to C-C
bonds: Cross-Dehydrogenative-Coupling; Royal Society of Chemistry,
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Girard, S. A.; Knauber, T.; Li, C.-J. Angew. Chem. Int. Ed. 2014, 53, 74;
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formation, the construction of phosphorus-element bonds by using
dehydrogenative coupling strategy though grows quickly seems immature,
few general and practically useful reactions have been established yet. For
review, see: Chen, T.; Zhang, J.-S.; Han, L.-B. Dalton. Trans. 2016, 45,
1843.
(8) For selected examples, see: (a) Baslé, O.; Li, C.-J. Chem. Commun.
2009, 4124. (b) Feng, C.-G.; Ye, M.; Xiao, K.-J.; Li, S.; Yu, J.-Q. J. Am.
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L.; Xu, P.; Zhao, Y.; Zhou, Y.; Han, L.-B. J. Am. Chem. Soc. 2009, 131,
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Commun. 2015, 51, 3549; (f) Yang, J.; Chen, T.; Zhou, Y.; Yin, S.-F.;
Han, L.-B. Organometallics 2015, 34, 5095; (g) Wang, T.; Chen, S.; Shao,
A.; Gao, M.; Huang, Y.; Lei, A. Org. Lett. 2015, 17, 118; (h) Fraser, J.;
Wilson, L. J.; Blundell, R.; Hayes, C. J. Chem. Commun. 2013, 49, 8919;
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Y.; Yin, S.; Gao, Y.; Zhao, Y.; Goto, M.; Han, L.-B. Angew. Chem. Int.
Ed. 2010, 49, 6852. All these reactions are oxidatively dehydrogenative
couplings.
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(9) The generation of dihydrogen in the reaction could be detected by
GC, see SI.
(10) Under the standard reaction conditions, 70% yield of ethylbenzene
was generated (GC yield using tridecane as an internal standard).
(11) The configuration of the P-chiral phosphorothioates was
confirmed by comparison with samples generated from Atherton-Todd
reaction. For detailed information, see SI.
(12) Prof. Kumaraswamy tried to prepare P-chiral phosphorothioates
via copper-mediated sulfenylation of P-chiral hydrogen phosphoryl
compounds with sulfonylhydrazides, a racemic mixture was afforded, see
Ref. 5c.
(13) To the best of our knowledge, no synthesis of phosphoryl Pd(II)
complexes with such H2 evolution was reported.
(14) 5a could also be produced by reaction of 3c and equivalent
PhSPd(PEt3)2H with H2 evolution, which was generated from oxidative
addition of Pd(PEt3)4 to PhSH.
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