Bu4NI-Catalyzed Dehydrogenative Coupling of Diaryl Phosphinic Acids with C(sp3)-H Bonds of Arenes

Article abstract of DOI:10.1021/acs.joc.7b02422

An efficient phosphorylation of C(sp³)-H bonds of arenes with diaryl phosphinic acids via Bu₄NI-catalyzed dehydrogenative coupling has been developed. This transformation proceeds efficiently under transition-metal-free reaction conditions and represents a straightforward method to prepare valuable organophosphorus compounds from readily available arenes and diaryl phosphinic acids.

Full text of DOI:10.1021/acs.joc.7b02422

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Note
Bu4NI Catalyzed Dehydrogenative Coupling of Diaryl
Phosphinic Acids with Csp3-H Bonds of Arenes
Bi-Quan Xiong, Gang Wang, Congshan Zhou, Yu Liu, Pan-Liang Zhang, and Ke-Wen Tang
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.7b02422 • Publication Date (Web): 25 Dec 2017
Downloaded from http://pubs.acs.org on December 25, 2017
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The Journal of Organic Chemistry
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Bu NI Catalyzed Dehydrogenative Coupling of
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Diaryl Phosphinic Acids with Csp -H Bonds of
Arenes
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Biquan Xiong,* Gang Wang, Congshan Zhou, Yu Liu, Panliang Zhang, Kewen Tang*
Department of Chemistry and Chemical Engineering, Hunan Institute of Science and Technology,
Yueyang, 414006, P.R.China.
xiongbiquan@126.com; tangkewen@sina.com.
RECEIVED DATE (to be automatically inserted after your manuscript is accepted if required
according to the journal that you are submitting your paper to)
Abstract
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An efficient phosphorylation of Csp ꢀH bonds of arenes with diaryl phosphinic acids via Bu NI
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catalyzed dehydrogenative coupling has been developed. This transformation proceeds efficiently under
transition metalꢀfree reaction conditions, and represents a straightforward method to prepare valuable
organophosphorus compounds from the readily available arenes and diaryl phosphinic acids.
As fundamental starting materials, organophosphorus compounds are versatile substrates in organic
transformations. Especially some phosphate esters are very useful in functional materials and industrial
science (e.g.,tris(2ꢀethylhexyl) phosphate is used as a plasticizer for vinyl polymers and triaryl
phosphates are also manufactured commercially and used as additives for gasoline, polymer
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ꢀ3
plasticizers.). Phosphoric acid esters are of great commercial importance, and a valuable summary has
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been prepared by Toy and Walsh. The increasing interest of these compounds is mainly related to the
wide presence of the phosphonic functionality (acid or ester) in many natural or synthetic bioactive
compounds. Nonetheless, they are costly due to rare availability from nature. As depicted in Scheme 1,
the most straightforward method of preparing such compounds is the straightforward transformation
pathway between a P(O)ꢀH/P(O)ꢀX compounds and a nucleophiles, apart from the conventional
nucleophilic substitution protocols.
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Scheme 1 Traditional methods for the synthesis of phosphonate/phosphate esters.
The direct phosphorylation of nucleophiles is extensively used for the synthesis of organophosphorus
compounds, but these approaches suffer from the low tolerance of functional groups and substrate
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a
limitations (e.g., AthertonꢀTodd reaction, nucleophilic substitutions). In 2013, Prabhu et al. reported a
green, direct crossꢀcoupling of phosphites with alcohols in the presence of I /H O at room
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temperature. In 2016, Chen and Han et al. further reported an efficient procedure based on ironꢀ
catalyzed dehydrogenative coupling of P(O)ꢀH compounds with alcohols, using Fe(AcAc) as iron
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source and toluene as solvent, under N atmosphere. Nolan et al. disclosed the direct synthesis of
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phosphorus esters by transesterification mediated by Nꢀheterocyclic carbenes in 2005. Later, Tang and
Zhao et al. investigated the phosphorylation of benzyl CꢀH bonds via a crossꢀdehydrogenative coupling
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e
path of using P(O)ꢀH compounds as the starting materials. Although there are a large number of
studies on the phosphorylation of nucleophiles, the use of P(O)ꢀOH compounds as starting materials is
rare. Indeed, literatures about the metalꢀcatalyzed crossꢀcoupling reaction of P(O)ꢀOH compounds with
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Csp ꢀH bonds of arenes have not been reported. Thus, to develop an efficient and convenient method for
the selective functionalization of P(O)ꢀOH compounds is highly desired in organophosphorus chemistry.
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To avoid the prefunctionalization of reactants, the direct dehydrogenative coupling of Csp ꢀH bonds
of arenes with organophosphorus compounds containing a P(O)ꢀOH moiety under mild conditions will
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become an efficient and promising strategy for the formation of phosphinic and phosphoric esters.
Very rencently, we have reported the direct esterification of P(O)ꢀOH compounds with alcohols or
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phenols under mild reaction conditions. As an ongoing effort on the activation of P(O)ꢀOH compounds,
we herein report an efficient and simple oxidative dehydrogenative coupling of P(O)ꢀOH compounds
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with Csp ꢀH bonds of arenes under mild conditions using a cheap quaternary ammonium salt catalyst.
Compared with P(O)ꢀH or PꢀCl compounds, P(O)ꢀOH compounds are more airꢀ and/or moistureꢀstable,
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and the use of them is more costꢀsaving and environmentꢀbenign.
The reaction of diphenyl phosphinic acid (1a) with toluene (2a) with the addition of TBHP (tertꢀbutyl
hydroperoxide, 2.0 equivalent), Bu NI (tetrabutylammonium iodide, 10 mol%) and 1.0 mL of toluene
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under air gave the desired product of benzyl diphenyl phosphonate (3a) in 67% yield. In the reaction,
toluene was in excess and served as solvent. Then we concentrated on the optimization of reaction
conditions. At the initial, we screened several catalysts for the reaction, and found that Bu NI was the
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best. To our surprise, Bu NBr, 18ꢀcrownꢀ6ꢀether and I showed negative to the reaction (Table 1,
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entries1ꢀ4). Different oxidants such as K S O , TBPB (tertꢀbutyl peroxybenzoate), TBHP (tertꢀbutyl
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hydroperoxide), H O , mꢀCPBA (3ꢀchloroperoxybenzoic), H K O S and DTPB (diꢀtertꢀbutyl peroxide)
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18 4
were further tested for the reaction. It was worth noting that the organic oxidants were much more
effective than the inorganic oxidants. This phenomenon may be ascribe to the reaction of inorganic
bases with P(O)ꢀOH compounds to form the corresponding salts in the reaction, which inhibited the
crossꢀcoupling process (Table 1, entries 5ꢀ10). With the addition of TBHP increased to 3.0 equivalents,
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the yield of 3a was increased from 67% to 76%. Further increasing the addition of TBHP did not result
in the raise for the yield of 3a significantly, so we adopted the 3.0 equivalents of TBHP as the oxidant
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for the reaction. The catalyst loading also affected the reaction obviously. With the amount of Bu NI
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increased from 20 mol% to 30 mol%, the expected coupling product of 3a was gained in 83% and 85%
yields, so we chose 20 mol% of Bu NI as the best catalyst loading (Table 1, entries 11ꢀ14). When the
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reaction was operated in 60 C, it was only 47% yield of 3a generated after the reaction. Further
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increasing the temperature from 80 C to 100 C, the yield of 3a was decreased from 83% to 61%. In
order to expand the applications of the reaction, different solvents were investigated (CH Cl , Dioxane,
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DMF, ClCH CH Cl, CH CN, CH OH, THF), and CH Cl was found to be the best, affording 3a in 98%
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yield (Table 1, entries 17ꢀ23). Therefore, the optimal reaction conditions are as follows: diphenyl
phosphinic acid (0.5 mmol), toluene (0.5 mmol), TBHP (1.5 mmol), Bu NI (20 mol%), CH Cl (0.5
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2
o
mL), 80 C, 12 h.
a)
Table1 Optimization of the reaction conditions .
b)
Entry
Cat. (mol%)
Oxidant (equiv)
TBHP (2.0)
TBHP (2.0)
TBHP (2.0)
TBHP (2.0)
K S O (2.0)
Solvent
Yield
67%
0%
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Bu NI (10)
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
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Bu NBr (10)
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18ꢀcrownꢀ6ꢀether (10)
I2 (10)
0%
0%
Bu NI (10)
26%
36%
trace
trace
0%
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Bu NI (10)
TBPB (2.0)
H O (2.0)
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Bu NI (10)
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Bu NI (10)
mꢀCPBA (2.0)
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Bu NI (10)
H K O S (2.0)
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18 4
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Bu NI (10)
DTBP (2.0)
TBHP (3.0)
TBHP (4.0)
TBHP (3.0)
TBHP (3.0)
TBHP (3.0)
TBHP (3.0)
TBHP (3.0)
0%
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Bu NI (10)
76%
78%
83%
85%
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12
Bu NI (10)
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3
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5
Bu NI (20)
4
Bu NI (30)
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c)
Bu NI (20)
47%
61%
98%
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d)
16
Bu NI (20)
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Bu NI (20)
CH Cl2
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Bu NI (20)
TBHP (3.0)
TBHP (3.0)
TBHP (3.0)
TBHP (3.0)
TBHP (3.0)
TBHP (3.0)
Dioxane
DMF
0%
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Bu NI (20)
0%
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Bu NI (20)
DCE
<10%
trace
<5%
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Bu NI (20)
CH CN
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Bu NI (20)
CH OH
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Bu NI (20)
THF
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a
Diphenyl phosphinic acid (0.5 mmol), toluene (1.0 mL for entries 1ꢀ16, 0.5 mmol for entries 17ꢀ23), catalyst, and
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oxidant, solvent (0.5 mL), air, 80 C, 12h. Yield was determined by GC analysis, and decane was used as the internal
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standard. 60 C. 100 C.
a)
Table 2 Scope of methyl substituted arenes .
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Reaction conditions: Ph P(O)OH (0.5 mmol), arenes (0.5mmol), TBHP (1.5 mmol), Bu NI (0.1 mmol), CH Cl (0.5
2
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b
c
mL), air, 80 °C, 12 h. Isolated yields. GC yield, decane was used as the internal standard.
As shown in Table 2, the present esterification reaction can be applied to a variety of methyl
substituted arenes. It is clear that mꢀxylene, pꢀxylene and 1ꢀtertꢀbutylꢀ4ꢀmethyl benzene can react
efficiently with diphenyl phosphinic acid (1a) under the optimized reaction conditions, affording the
corresponding coupling products of 3b-3d in 91ꢀ96% yields. Electronꢀdonating group substituted arenes
such as 1ꢀmethoxyꢀ4ꢀmethyl benzene and 1ꢀmethoxyꢀ3ꢀmethyl benzene only gave the desired products
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of 3e and 3f in 55% and 42% yields. It was worth noting that the electronꢀwithdrawing groups
substituted arenes such as 1ꢀchloroꢀ4ꢀmethylbenzene, 1ꢀchloroꢀ3ꢀmethylbenzene, 1ꢀbromoꢀ4ꢀ
methylbenzene, 1ꢀiodoꢀ4ꢀmethylbenzene, 1ꢀfluoroꢀ4ꢀmethylbenzene, 1ꢀnitroꢀ4ꢀmethylbenzene and 3ꢀ
methylbenzonitrile were also well tolerated on the reaction, producing the corresponding coupling
products of 3gꢀ3m in 74ꢀ91% yields. Interestingly, 1ꢀmethylnaphthalene and 2ꢀmethylnaphthalene both
showed high activities toward the reaction, yielding the expected products of naphthalenꢀ1ꢀylmethyl
diphenylphosphinate (3n) and naphthalenꢀ2ꢀylmethyl diphenylphosphinate (3o) in 93% and 87% yields.
Moreover, heterocyclic organophosphorus compounds such as benzo[d]thiazolꢀ2ꢀylmethyl
diphenylphosphinate (3p) could also be synthesized from diphenyl phosphinic acid and 2ꢀ
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methylbenzo[d]thiazole in 88% yield via the Bu NI catalyzed dehydrogenative coupling reaction.
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a)
Table 3 Scope of P(O)OH compound .
a
Reaction conditions: diaryl phosphinic acids (0.5 mmol), toluene (0.5 mmol), TBHP (1.5 mmol), Bu NI (0.1 mmol),
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CH Cl (0.5 mL), air, 80 °C, 12 h. Isolated yield.
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As depicted in Table 3, different substituted diaryl phosphinic acids such as diꢀ(4ꢀmethyl phenyl)
phosphinic acid, diꢀ(3ꢀmethyl phenyl) phosphinic acid, diꢀ(4ꢀmethoxyphenyl) phosphinic acid, diꢀ(4ꢀ
trifluoromethylphenyl) phosphinic acid and diꢀ(1ꢀmethylnaphthalene) phosphinic acid (4c) could react
efficiently with toluene under the optimized reaction conditions, affording the expected coupling
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products of 4a-4d in 78ꢀ95% yields. To our delight, diꢀ(1ꢀmethylnaphthalene) phosphinic acid and diꢀ(2ꢀ
methylnaphthalene) phosphinic acid also showed positive to the reaction, and the corresponding
coupling phosphinic esters of benzyl di(naphthalenꢀ1ꢀyl)phosphinate (4e) and benzyl di(naphthalenꢀ2ꢀ
yl)phosphinate (4f) were generated in 89% and 83% yields, respectively.
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Scheme2 Control experiments.
In order to clarify the reaction mechanism, we operated the reaction of diphenyl phosphinic acid with
benzaldehyde or phenylmethanol in the presence of Bu NI and TBHP under the optimized reaction
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conditions. At the beginning of this study, benzyl alcohol or benzyl aldehyde was assumed to be a
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1
potential intermediate in the reaction. As confirmed by GC, GCꢀMS, and P NMR analysis, there was
no detection of the coupling product (Scheme 2, path 1). When the radical scavenger 2,2,6,6ꢀ
tetramethylpiperidine Nꢀoxyl (TEMPO) was added in the reaction, only a trace amount of 3a was
observed. It is hence deduced that the reaction possibly occurs through an oxidative dehydrogenative
coupling path rather than the esterification path. When diphenyl hydrogen phosphate or dibutyl
hydrogen phosphate was used to the reaction, the corresponding dehydrogenative coupling products of
benzyl diphenyl phosphate (4g) or benzyl dibutyl phosphate (4h) could not be detected after the reaction.
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This phenomenon may be ascribed to the strong acidity of this type of compounds. If the reaction
operated without the use of catalyst, the reaction could not proceed as we expected. In addition, the
catalytic amount of TBHP (20 mol%) could only give 3a in 6% yield under the optimized conditions.
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A plausible catalytic cycle is presented in scheme 3. Bu NI (A) first attacks tertꢀbutyl hydroperoxide
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(B) to afford the intermediate radicals of C and D or the corresponding adducts of E and F. Then these
intermediates take the hydrogen atom from arenes (G) and diaryl phosphinic acids (H) to generate the
benzyl radical J and phosphoryl radical K. Meanwhile, one molecule of tertꢀbutyl alcohol (I) is
generated. Finally, the oxidative dehydrogenation coupling path is completed via the reaction of
activated intermediate radicals of J and K to yield the desired phosphinates (L).
Scheme3. Proposed reaction mechanism.
Conclusions
In summary, we develop an efficient method for the preparation of phosphinates via Bu NI catalyzed
4
oxidative dehydrogenation coupling of diary phosphinic acids with methyl substituted arenes. Both diary
phosphinic acids and methyl substituted arenes are commercially available and easily synthesized. The
method avoids the use of moisture/airꢀsensitive substrates and metal catalysts. Moreover, the method is
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tolerant of many substrates, operationally simple, and can be performed under ambient conditions. The
above superiority of this method renders it a powerful complement to traditional approaches for the
synthesis of phosphinic acid esters.
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Experimental Section
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General Considerations:
All solvents used in the reactions were freshly distilled. The other reagents were recrystallized or
1
distilled as necessary. All reactions were performed under air atmosphere unless specified otherwise. H
1
3
(
400 MHz), C (100 MHz) spectra were recorded on a 400MHz spectrometer with the sample dissolved
1
13
in CDCl . H NMR chemical shifts were reported using TMS as internal standard while C NMR
3
chemical shifts were reported relative to CDCl . The electron ionization method was used for HRMS
3
measurements, and the mass analyzer type was doubleꢀfocusing.
General procedure:
A mixture of P(O)ꢀOH compounds (0.5 mmol), arenes (0.5 mmol), Bu NI (0.1 mmol) and TBHP (1.5
4
o
mmol) was dissolved in CH Cl under air atmosphere, stirred at 80 C for 12h. Removal of the solvent
2
2
under a reduced pressure gave the crude product; pure product was obtained by passing the crude
product through a short silica gel column using Hexane/EtOAc (1:1ꢀ5:1) as eluent.
O-benzyl diphenylphosphinate (3a): According to the general procedure, workꢀup and flash column
chromatography (Hexane/EtOAc = 2:1) gave product 3a (146.0 mg, 0.474 mmol, 95 %) as a yellow
1
1a 1
o
oil.
H NMR (400 MHz, CDCl , 25 C, TMS): δ= 7.72ꢀ7.77 (m, 4H), 7.40ꢀ7.44 (m, 2H), 7.34ꢀ7.37
3
13
o
(
m, 4H), 7.17ꢀ7.27 (m, 5H), 4.98 (d, J = 6.4 Hz, 2H); C NMR (100 MHz, CDCl , 25 C, TMS): δ=
3
1
1
1
1
1
36.3 (d, J (C,P) = 7.6 Hz), 132.3 (d, J (C,P) = 2.8 Hz), 131.7 (d, J (C,P) = 10.2 Hz), 131.3 (d, J
1
1
(C,P) = 136.0 Hz), 128.7 (s), 128.6 (d, J (C,P) = 4.0 Hz), 128.3 (s), 127.9 (s), 66.4 (d, J (C,P) = 5.6
3
1
o
Hz); P NMR (160 MHz, CDCl , 25 C): δ= 32.46.
3
O-3-methylbenzyl diphenylphosphinate (3b): According to the general procedure, workꢀup and flash
column chromatography (Hexane/EtOAc = 1:1) gave product 3b (146.5 mg, 0.455 mmol, 91 %) as a
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5
c 1
o
yellow oil. H NMR (400 MHz, CDCl , 25 C, TMS): δ= 7.81ꢀ7.86 (m, 4H), 7.44ꢀ7.51 (m, 6H), 7.21ꢀ
3
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
1
3
7
.25 (m, 1H), 7.11ꢀ7.17 (m, 3H), 5.02ꢀ5.03 (d, J = 6.4 Hz, 2H), 2.32 (s, 3H); C NMR (100 MHz,
o
1
1
CDCl , 25 C, TMS): δ= 138.2 (s), 136.2 (d, J (C,P) = 7.4 Hz), 132.2 (d, J (C,P) = 2.8 Hz), 131.8 (d,
3
1
1
J (C,P) = 10.1 Hz), 131.4 (d, J (C,P) = 135.0 Hz), 129.1 (s), 128.7 (s), 128.6 (s), 128.5 (s), 125.0 (s),
1
31
o
6
6.4 (d, J (C,P) = 5.5 Hz), 21.4 (s); P NMR (160 MHz, CDCl , 25 C): δ= 32.31.
3
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
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0
O-4-methylbenzyl diphenylphosphinate (3c): According to the general procedure, workꢀup and flash
column chromatography (Hexane/EtOAc = 2:1) gave product 3c (148.1 mg, 0.46 mmol, 92 %) as a
1
1a 1
o
yellow oil.
H NMR (400 MHz, CDCl , 25 C, TMS): δ= 7.80ꢀ7.85 (m, 4H), 7.50ꢀ7.53 (m, 2H), 7.42ꢀ
3
1
3
7
.46 (m, 4H), 7.24ꢀ7.26 (m, 2H), 7.14ꢀ7.16 (m, 2H), 5.02 (d, J = 6.8, 2H), 2.34 (s, 3H); C NMR (100
o
1
1
1
MHz, CDCl , 25 C, TMS): δ= 138.2 (s), 132.2 (d, J = 2.8 Hz), 131.7 (d, J = 10.2 Hz), 131.4 (d, J
3
1
31
(
C,P) = 135.9 Hz), 129.2 (s), 128.6 (s), 128.5 (s), 128.1 (s), 66.3 (d, J (C,P) = 5.6 Hz), 21.2 (s); P
o
NMR (160 MHz, CDCl , 25 C): δ= 32.2.
3
O-4-(tert-butyl)benzyl diphenylphosphinate (3d): According to the general procedure, workꢀup and
flash column chromatography (Hexane/EtOAc = 2:1) gave product 3d (174.9 mg, 0.48 mmol, 96 %) as
1
1b 1
o
a yellow oil.
H NMR (400 MHz, CDCl , 25 C, TMS): δ= 7.81ꢀ7.85 (m, 4H), 7.49ꢀ7.53 (m, 2H),
3
13
7
.42ꢀ7.45 (m, 4H), 7.36ꢀ7.37 (m, 2H), 7.29ꢀ7.31 (m, 2H), 5.04 (d, J = 6.4Hz, 2H), 1.31 (s, 9H); C
o
1
1
NMR (100 MHz, CDCl , 25 C, TMS): δ= 151.4 (s), 133.3 (d, J (C,P) = 7.4 Hz), 132.2 (d, J (C,P) =
3
1
1
1
2
1
3
.7 Hz), 131.8 (d, J (C,P) = 10.1 Hz), 131.4 (d, J (C,P) = 135.9 Hz), 128.6 (d, J (C,P) = 13.1 Hz),
1
31
o
27.8 (s), 125.5 (s), 66.2 (d, J = 5.4 Hz), 34.6 (s), 31.3 (s); P NMR (160 MHz, CDCl , 25 C): δ=
3
2.2.
O-4-methoxybenzyl diphenylphosphinate (3e): According to the general procedure, workꢀup and
flash column chromatography (Hexane/EtOAc = 2:1) gave product 3e (87.9 mg, 0.26 mmol, 52 %) as
8b 1
o
colorless oil. H NMR (400 MHz, CDCl , 25 C, TMS): δ= 7.71ꢀ7.76 (m, 4H), 7.39ꢀ7.43 (m, 2H),
3
1
3
7
.31ꢀ7.35 (m, 4H), 7.13ꢀ7.17 (m, 1H), 6.73ꢀ6.85 (m, 3H), 4.94 (d, J = 6.8 Hz, 2H), 3.66 (s, 3H); C
o
1
1
NMR (100 MHz, CDCl , 25 C, TMS): δ= 159.7 (s), 137.8 (d, J (C,P) = 7.4 Hz), 132.3 (d, J (C,P) =
3
1
1
1
2
.8 Hz), 131.7 (d, J (C,P) = 10.2 Hz), 131.3 (d, J (C,P) = 135.9 Hz), 128.6 (d, J (C,P) = 13.1 Hz),
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1
1
31
1
20.1 (s), 113.6 (d, J (C,P) = 7.4 Hz), 66.2 (d, J (C,P) = 5.5 Hz), 55.2 (s); P NMR (160 MHz, CDCl ,
3
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
o
2
5 C): δ= 32.5.
O-3-methoxybenzyl diphenylphosphinate (3f): According to the general procedure, workꢀup and
flash column chromatography (Hexane/EtOAc = 1:1) gave product 3e (70.9 mg, 0.21 mmol, 42 %) as a
1
o
yellow oil. H NMR (400 MHz, CDCl , 25 C, TMS): δ= 7.73ꢀ7.78 (m, 4H), 7.37ꢀ7.45 (m, 6H), 7.16ꢀ
3
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
3
7
.20 (m, 1H), 6.83ꢀ6.87 (m, 2H), 6.77ꢀ6.79 (m, 1H), 4.97 (d, J = 6.4 Hz, 2H), 3.70 (s, 3H); C NMR
o
1
1
(100 MHz, CDCl , 25 C, TMS): δ= 159.7 (s), 132.3(d, J (C,P) = 2.6Hz), 131.7 (d, J (C,P) = 10.2 Hz),
3
1
1
1
31.3 (d, J (C,P) = 136.0 Hz), 129.6 (s), 128.7 (s), 128.5 (s), 120.1 (s), 113.9 (s), 113.3 (s), 66.2 (d, J
3
1
o
(
C,P) = 5.5 Hz), 55.3 (s); P NMR (160 MHz, CDCl , 25 C): δ= 32.5. HRMS (EI) m/z: calcd. for
3
C H O P: 338.1072, found: 338.1069.
2
0
19
3
O-4-chlorobenzyl diphenylphosphinate (3g): According to the general procedure, workꢀup and flash
column chromatography (Hexane/EtOAc = 2:1) gave product 3g (152.2 mg, 0.445 mmol, 89 %) as a
5
c 1
o
yellow oil. H NMR (400 MHz, CDCl , 25 C, TMS): δ= 7.79ꢀ7.84 (m, 4H), 7.45ꢀ7.53 (m, 6H), 7.30ꢀ
3
1
3
o
1
7.34 (m, 4H), 5.03 (d, J = 6.8 Hz, 2H); C NMR (100 MHz, CDCl , 25 C, TMS): δ= 134.9 (d, J (C,P)
3
1
1
1
=
7.0 Hz), 134.2 (s), 132.4 (d, J (C,P) = 2.7 Hz), 131.7 (d, J (C,P) = 10.2 Hz), 131.1 (d, J (C,P) =
1
1
31
1
36.1 Hz), 129.3 (s), 128.7 (d, J (C,P) = 5.7 Hz), 128.6 (s), 65.6 (d, J (C,P) = 5.5 Hz); P NMR (160
o
MHz, CDCl , 25 C): δ= 32.8.
3
O-3-chlorobenzyl diphenylphosphinate (3h): According to the general procedure, workꢀup and flash
column chromatography (Hexane/EtOAc = 1:1) gave product 3h (147.1 mg, 0.43 mmol, 86 %) as a
1
o
yellow oil. H NMR (400 MHz, CDCl , 25 C, TMS): δ= 7.81ꢀ7.86 (m, 4H), 7.46ꢀ7.54 (m, 6H), 7.25ꢀ
3
1
3
o
1
7.34 (m, 4H), 5.04 (d, J = 6.8 Hz, 2H); C NMR (100 MHz, CDCl , 25 C, TMS): δ= 138.3 (d, J (C,P)
3
1
1
1
=
7.8 Hz), 134.4 (s), 132.4 (d, J (C,P) = 2.6 Hz), 131.7 (d, J (C,P) = 10.3 Hz), 130.3 (s), 129.2 (d, J
1
1
(
C,P) = 142.8 Hz), 128.7 (d, J (C,P) = 13.1 Hz), 127.9 (s), 125.9 (s), 100.0(s), 65.5 (d, J (C,P) = 5.5
3
1
o
Hz); P NMR (160 MHz, CDCl , 25 C): δ= 33.0. HRMS (EI) m/z: calcd. for C H ClO P: 342.0576,
3
19 16
2
found: 342.0574.
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O-4-bromobenzyl diphenylphosphinate (3i): According to the general procedure, workꢀup and flash
column chromatography (Hexane/EtOAc = 2:1) gave product 3i (175.6 mg, 0.455 mmol, 91 %) as a
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
8
b 1
o
yellow oil. H NMR (400 MHz, CDCl , 25 C, TMS): δ= 7.79ꢀ7.84 (m, 4H), 7.51ꢀ7.55 (m, 2H), 7.45ꢀ
3
1
3
o
7
.47 (m, 6H), 7.22ꢀ7.26 (m, 2H), 5.01 (d, J = 7.2 Hz, 2H); C NMR (100 MHz, CDCl , 25 C, TMS):
3
1
1
1
δ= 135.4 (d, J (C,P) = 7.0 Hz), 132.4 (d, J (C,P) = 2.8 Hz), 131.7 (d, J (C,P) = 1.2 Hz), 131.6 (s),
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
1
31
1
31.0 (d, J (C,P) = 117.8 Hz), 129.6 (s), 128.6 (d, J (C,P) = 13.2 Hz), 122.4 (s), 65.6 (s); P NMR
o
(160 MHz, CDCl , 25 C): δ= 32.9.
3
O-4-iodobenzyl diphenylphosphinate (3j): According to the general procedure, workꢀup and flash
column chromatography (Hexane/EtOAc = 2:1) gave product 3i (175.4 mg, 0.405 mmol, 81 %) as a
5
e 1
o
yellow oil. H NMR (400 MHz, CDCl , 25 C, TMS): δ= 7.79ꢀ7.84 (m, 4H), 7.66ꢀ7.68 (m, 2H), 7.45ꢀ
3
1
3
o
7
.55 (m, 6H), 7.09ꢀ7.11 (m, 2H), 5.00 (d, J = 7.2 Hz, 2H); C NMR (100 MHz, CDCl , 25 C, TMS):
3
1
1
1
δ= 137.7 (s), 136.0 (s), 132.4 (d, J (C,P) = 2.7 Hz), 131.7 (d, J (C,P) = 10.3 Hz), 131.1 (d, J (C,P) =
1
1
31
1
36.0 Hz), 129.7 (s), 128.6 (d, J (C,P) = 13.1 Hz), 94.0 (s), 65.7 (d, J (C,P) = 5.4 Hz); P NMR (160
o
MHz, CDCl , 25 C): δ= 32.8.
3
O-4-fluoro-benzyl phenyl (phenyl) phosphinate (3k): According to the general procedure, workꢀup
and flash column chromatography (Hexane/EtOAc = 2:1) gave product 3k (149.9 mg, 0.46mmol, 92 %)
1
1a 1
o
as a colorless oil.
H NMR (400 MHz, CDCl , 25 C, TMS): δ= 7.80ꢀ7.86 (m, 4H), 7.48ꢀ7.52 (m, 2H),
3
1
3
7
.41ꢀ7.45 (m, 4H), 7.31ꢀ7.35 (m, 2H), 6.99ꢀ7.03 (m, 2H), 5.03 (d, J = 7.2 Hz, 2H); C NMR (100 MHz,
o
1
1
1
CDCl , 25 C, TMS): δ= 162.6 (d, J (C,F) = 245.5 Hz), 132.3 (d, J (C,P) = 2.8 Hz), 132.2 (dd, J (C,P)
3
2
1
1
1
=
3.2 Hz, J (C,F) = 3.1 Hz), 131.6 (d, J (C,P) = 10.2 Hz), 131.2 (d, J (C,P) = 135.9 Hz), 129.9 (d, J
1
1
1
(C,P) = 8.3 Hz), 128.5 (d, J (C,P) = 13.2 Hz), 115.4 (d, J (C,P) = 21.5 Hz), 65.6 (d, J (C,P) = 5.4 Hz);
3
1
o
P NMR (160 MHz, CDCl , 25 C): δ= 33.6.
3
O-4-nitrobenzyl diphenylphosphinate (3l): According to the general procedure, workꢀup and flash
column chromatography (Hexane/EtOAc = 2:1) gave product 3l (144.7 mg, 0.41 mmol, 82 %) as a
1
1a 1
o
yellow oil.
H NMR (400 MHz, CDCl , 25 C, TMS): δ= 8.21 (d, J = 8.0 Hz, 2H), 7.81ꢀ7.86 (m, 4H),
3
13
o
7
.48ꢀ7.58 (m, 8H), 5.16 (d, J = 7.2 Hz, 2H); C NMR (100 MHz, CDCl , 25 C, TMS): δ= 147.8 (s),
3
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1
1
1
1
1
43.6 (d, J (C,P) = 7.0 Hz), 132.6 (d, J (C,P) = 2.7 Hz), 131.6 (d, J (C,P) = 10.3 Hz), 130.7 (d, J
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
1
1
31
(
C,P) = 136.0 Hz), 128.7 (d, J (C,P) = 13.2 Hz), 128.1 (s), 123.8 (s), 64.9 (d, J (C,P) = 5.3 Hz); P
o
NMR (160 MHz, CDCl , 25 C): δ= 33.6.
3
O-3-cyanobenzyl diphenylphosphinate (3m): According to the general procedure, workꢀup and flash
column chromatography (Hexane/EtOAc = 1:1) gave product 3m (123.2 mg, 0.37 mmol, 74 %) as a
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
o
yellow oil. H NMR (400 MHz, CDCl , 25 C, TMS): δ= 7.80ꢀ7.85 (m, 4H), 7.54ꢀ7.64 (m, 5H), 7.44ꢀ
3
1
3
o
1
7.50 (m, 5H), 5.10 (d, J = 7.6 Hz, 2H); C NMR (100 MHz, CDCl , 25 C, TMS): δ= 138.0 (d, J (C,P)
3
1
1
1
=
7.3 Hz), 132.6 (d, J (C,P) = 2.8 Hz), 131.9 (d, J (C,P) = 9.6 Hz), 131.7 (d, J (C,P) = 10.2 Hz), 131.1
1
1
1
(
s), 130.8 (d, J (C,P) = 135.8 Hz), 129.4 (s), 128.7 (d, J (C,P) = 13.2 Hz), 118.5 (d, J (C,P) = 2.7 Hz),
1
31
o
112.8 (s), 65.0 (d, J (C,P) = 5.3 Hz), 13.8 (s); P NMR (160 MHz, CDCl , 25 C): δ= 33.4. HRMS (EI)
3
m/z: calcd. for C H NO P: 333.0919, found: 333.0917.
2
0
16
2
O-naphthalen-1-ylmethyl diphenylphosphinate (3n): According to the general procedure, workꢀup
and flash column chromatography (Hexane/EtOAc = 2:1) gave product 3n (166.5 mg, 0.465 mmol, 93
1
1a 1
o
%) as a yellow oil.
H NMR (400 MHz, CDCl , 25 C, TMS): δ= 8.09 (d, J = 8.0 Hz, 1H), 7.78ꢀ7.86
3
1
3
o
(
m, 6H), 7.37ꢀ7.54 (m, 10H), 5.53 (d, J = 6.4 Hz, 2H); C NMR (100 MHz, CDCl , 25 C, TMS): δ=
3
1
1
1
1
33.7 (s), 132.3 (d, J (C,P) = 2.7 Hz), 131.8 (d, J (C,P) = 7.5 Hz), 131.7 (d, J (C,P) = 10.2 Hz), 131.3
1
(
d, J (C,P) = 135.8 Hz), 129.4 (s), 128.7 (s), 128.6 (s), 128.5 (s), 127.0 (s), 126.6 (s), 126.0 (s), 125.2
1
31
o
(
s), 123.7 (s), 66.8 (d, J (C,P) = 5.5 Hz); P NMR (160 MHz, CDCl , 25 C): δ= 32.6.
3
O-naphthalen-2-ylmethyl diphenylphosphinate (3o): According to the general procedure, workꢀup
and flash column chromatography (Hexane/EtOAc = 2:1) gave product 3n (155.7 mg, 0.435 mmol, 87
5
e 1
o
%) as a yellow oil. H NMR (400 MHz, CDCl , 25 C, TMS): δ= 7.77ꢀ7.88 (m, 8H), 7.47ꢀ7.53 (m,
3
1
3
o
1
9
H), 5.22 (d, J = 6.8 Hz, 2H); C NMR (100 MHz, CDCl , 25 C, TMS): δ= 133.8 (d, J (C,P) = 7.4
3
1
1
1
Hz), 133.2 (d, J (C,P) = 2.1 Hz), 132.3 (d, J (C,P) = 2.7 Hz), 131.8 (s), 131.7 (s), 131.3 (d, J (C,P) =
1
1
35.8 Hz), 128.7 (s), 128.5 (s), 128.4 (s), 128.0 (s), 127.7 (s), 127.1 (s), 126.3 (s), 125.7 (s), 66.6 (d, J
3
1
o
(C,P) = 5.5 Hz); P NMR (160 MHz, CDCl , 25 C): δ= 32.5.
3
1
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O-benzo[d]thiazol-2-ylmethyl diphenylphosphinate (3p): According to the general procedure, workꢀ
up and flash column chromatography (Hexane/EtOAc = 5:1) gave product 3n (160.6 mg, 0.44 mmol, 88
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
1
o
%) as a yellow oil. H NMR (400 MHz, CDCl , 25 C, TMS): δ= 8.00 (d, J = 8.0 Hz, 1H), 7.87ꢀ7.92 (m,
3
1
3
o
5
H), 7.39ꢀ7.52 (m, 8H), 5.43 (d, J = 6.8 Hz, 2H); C NMR (100 MHz, CDCl , 25 C, TMS): δ= 135.1
3
1
1
1
(
s), 134.9 (s), 132.7 (d, J (C,P) = 2.7 Hz), 132.0 (d, J (C,P) = 192.1 Hz), 131.8 (d, J (C,P) = 10.4 Hz),
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
1
1
28.8 (d, J = 13.2 Hz), 126.3 (s), 125.4 (s), 123.3 (s), 121.8 (s), 108.2 (d, J (C,P) = 6.7 Hz), 63.6 (d, J
3
1
o
(C,P) = 4.6 Hz); P NMR (160 MHz, CDCl , 25 C): δ= 34.1. HRMS (EI) m/z: calcd. for
3
C H NO PS: 365.0639, found: 365.0635.
2
0
16
2
O-benzyl di-p-tolylphosphinate (4a): According to the general procedure, workꢀup and flash column
chromatography (Hexane/EtOAc = 2:1) gave product 4a (154.6 mg, 0.46 mmol, 92 %) as a yellow oil.
1
o
H NMR (400 MHz, CDCl , 25 C, TMS): δ= 7.69ꢀ7.74 (m, 4H), 7.32ꢀ7.35 (m, 5H), 7.24ꢀ7.26 (m, 4H),
3
13
o
1
5
.04 (d, J = 6.4 Hz, 2H), 2.37 (s, 6H); C NMR (100 MHz, CDCl , 25 C, TMS): δ= 142.7(d, J (C,P) =
3
1
1
1
2
.9 Hz), 131.7 (d, J (C,P) = 10.6 Hz), 129.4 (d, J (C,P) = 118.9 Hz), 129.3 (d, J (C,P) = 13.5 Hz),
1
31
128.5 (s), 128.2 (s), 127.8 (s), 127.4 (s), 66.2 (d, J (C,P) = 5.4 Hz), 21.6 (s); P NMR (160 MHz,
o
CDCl , 25 C): δ= 33.6. HRMS (EI) m/z: calcd. for C H O P: 336.1279, found: 336.1277.
3
21 21
2
O-benzyl di-m-tolylphosphinate (4b): According to the general procedure, workꢀup and flash column
chromatography (Hexane/EtOAc = 2:1) gave product 4b (142.8 mg, 0.425 mmol, 85 %) as a yellow oil.
1
o
H NMR (400 MHz, CDCl , 25 C, TMS): δ= 7.58ꢀ7.67 (m, 4H), 7.26ꢀ7.36 (m, 9H), 5.05 (d, J = 6.8 Hz,
3
13
o
1
2
H), 2.35 (s, 6H); C NMR (100 MHz, CDCl , 25 C, TMS): δ= 138.5 (s), 138.4 (s), 133.1 (d, J (C,P)
3
1
1
1
=
2.9 Hz), 132.2 (d, J (C,P) = 10.3 Hz), 131.2 (d, J (C,P) = 135.2 Hz), 128.8 (d, J (C,P) = 10.0 Hz),
1
1
31
128.5 (s), 128.3 (d, J (C,P) = 14.9 Hz), 127.9 (s), 100 (s), 66.3 (d, J (C,P) = 5.5 Hz), 21.4 (s); P NMR
o
(
160 MHz, CDCl , 25 C): δ= 33.2. HRMS (EI) m/z: calcd. for C H O P: 336.1279, found: 336.1275.
3
21 21
2
O-benzyl bis(4-methoxyphenyl)phosphinate (4c): According to the general procedure, workꢀup and
flash column chromatography (Hexane/EtOAc = 2:1) gave product 4c (143.5 mg, 0.39 mmol, 78 %) as a
5
e 1
o
yellow oil. H NMR (400 MHz, CDCl , 25 C, TMS): δ= 7.64ꢀ7.69 (m, 4H), 7.24ꢀ7.27 (m, 5H), 6.85ꢀ
3
13
o
6
.87 (m, 4H), 4.94 (d, J = 6.4 Hz, 2H), 3.74 (s, 6H); C NMR (100 MHz, CDCl , 25 C, TMS): δ=
3
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1
1
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62.6 (d, J (C,P) = 3.0 Hz), 136.7 (d, J (C,P) = 7.9 Hz), 133.6 (d, J (C,P) = 11.5 Hz), 128.5 (s), 128.2
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
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1
2
2
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2
2
2
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2
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3
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(
s), 127.8 (s), 122.9 (d, J (C,P) = 143.5 Hz), 114.1 (d, J = 14.1 Hz), 66.0 (d, J = 5.3 Hz), 55.3 (s); P
o
NMR (160 MHz, CDCl , 25 C): δ= 33.3.
3
O-benzyl bis(4-(trifluoromethyl)phenyl)phosphinate (4d): According to the general procedure, workꢀ
up and flash column chromatography (Hexane/EtOAc = 2:1) gave product 4d (210.9 mg, 0.475 mmol,
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
o
9
5 %) as a colorless oil. H NMR (400 MHz, CDCl , 25 C, TMS): δ= 7.92ꢀ7.97 (m, 4H), 7.70ꢀ7.72 (m,
3
1
3
o
4H), 7.27ꢀ7.35 (m, 5H), 5.12 (d, J = 7.6Hz, 2H); C NMR (100 MHz, CDCl , 25 C, TMS): δ= 135.0
3
1
1
1
(
d, J (C,P) = 135.2 Hz), 135.5 (d, J (C,P) = 6.7 Hz), 132.2 (d, J (C,P) = 10.5 Hz), 128.8 (s), 128.7 (s),
1
2
1
1
28.2 (s), 125.6 (dd, J (C,P) = 9.7 Hz, J (C,F) = 17.1 Hz), 124.7 (s), 122.1 (s), 66.2 (d, J (C,P) = 5.2
3
1
o
Hz); P NMR (160 MHz, CDCl , 25 C): δ= 28.4. HRMS (EI) m/z: calcd. for C H F O P: 444.0714,
3
21 15
6
2
found: 444.0711.
O-benzyl di(naphthalen-1-yl)phosphinate (4e): According to the general procedure, workꢀup and
flash column chromatography (Hexane/EtOAc = 2:1) gave product 4e (181.2 mg, 0.445 mmol, 89 %) as
7
d 1
o
a colorless oil. H NMR (400 MHz, CDCl , 25 C, TMS): δ= 8.6 (d, J = 8.0 Hz, 2H), 8.16ꢀ8.21 (m,
3
2
H), 8.05 (d, J = 8.2 Hz, 2H), 7.86 (d, J = 6.8 Hz, 2H), 7.40ꢀ7.52 (m, 6H), 7.24ꢀ7.34 (m, 5H), 5.15ꢀ5.17
13
o
1
(
d, J = 8.0 Hz, 2H); C NMR (100 MHz, CDCl , 25 C, TMS): δ= 138.2 (d, J (C,P) = 8.0 Hz), 134.2
3
1
1
1
(
d, J (C,P) = 10.1 Hz), 133.7 (d, J (C,P) = 3.0 Hz), 132.7 (s), 132.0 (d, J (C,P) = 10.1 Hz), 130.0 (s),
1
1
1
1
28.9 (d, J (C,P) = 1.3 Hz), 128.5 (s), 128.2 (d, J (C,P) = 3.4 Hz), 127.5 (s), 127.6 (d, J (C,P) = 138.0
1
1
1
Hz), 126.6 (d, J (C,P) = 4.9 Hz), 126.4 (s), 124.7 (d, J (C,P) = 14.9 Hz), 66.7 (d, J (C,P) = 5.5 Hz);
3
1
o
P NMR (160 MHz, CDCl , 25 C): δ= 35.0.
3
O-benzyl di(naphthalen-2-yl)phosphinate (4f): According to the general procedure, workꢀup and
flash column chromatography (Hexane/EtOAc = 2:1) gave product 4f (169.3 mg, 0.415 mmol, 83 %) as
1
o
a yellow oil. H NMR (400 MHz, CDCl , 25 C, TMS): δ= 8.50ꢀ8.54 (m, 2H), 7.79ꢀ7.91 (m, 8H), 7.51ꢀ
3
1
3
7
.58 (m, 4H), 7.36ꢀ7.42 (m, 2H), 7.24ꢀ7.34 (m, 3H), 5.15 (d, J = 7.2 Hz, 2H); C NMR (100 MHz,
o
1
1
1
CDCl , 25 C, TMS): δ= 136.4 (d, J (C,P) = 8.0 Hz), 135.0 (d, J (C,P) = 2.4 Hz), 134.0 (d, J (C,P) =
3
1
1
1
0.0 Hz), 132.6 (s), 132.4 (s), 129.1 (s), 128.6 (s), 128.5 (s), 128.4 (d, J (C,P) = 1.9 Hz), 128.3 (d, J
1
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(
C,P) = 137.0 Hz), 127.9 (s), 127.0 (s), 126.5 (s), 126.4 (s), 66.6 (d, J (C,P) = 5.6 Hz); P NMR (160
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
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3
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4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
o
MHz, CDCl , 25 C): δ= 32.9. HRMS (EI) m/z: calcd. for C H O P: 408.1279, found: 408.1276.
3
27 21
2
Acknowledgments. This work was supported by National Natural Science Foundation of China
(
21606080, 21676077, 21476068), Scientific Research Fund of Hunan Provincial Education Department
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(16B111).
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Supporting Information Available: Copies of H, C and P NMR spectra. This material is
available free of charge via the Internet at http://pubs.acs.org.
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