Copper(I)-induced sulfenylation of H-phosphonates, H-phosphonites and phosphine oxides with aryl/alkylsulfonylhydrazides as a thiol surrogate

Article abstract of DOI:10.1002/adsc.201400116

Aerobic dehydrogenative sulfenylation of H-phosphonites, and phosphine oxides with aryl/alkylsulfonyl hydrazides catalyzed by a sub-stoichiometric amount of copper iodide has been accomplished. This protocol is compatible with functional groups, and results in various thiophosphate derivatives in good to high yields.

Full text of DOI:10.1002/adsc.201400116

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DOI: 10.1002/adsc.201400116
Copper(I)-Induced Sulfenylation of H-Phosphonates,
H-Phosphonites and Phosphine Oxides with
Aryl/alkylsulfonylhydrazides as a Thiol Surrogate
Gullapalli Kumaraswamya,b,* and Ragam Rajua
a
Organic & Biomolecular Chemistry Division, CSIR – Indian Institute of Chemical Technology, Hyderabad – 500 607,
India
Fax : (+91)-40-2719-3275; phone: (+91)-40-2719-3154; e-mail: gkswamy_iict@yahoo.co.in
Academy of Scientific and Innovative Research (AcSIR), 2 Rafi Marg, New Delhi – 110 001, India
b
Received: January 30, 2014; Revised: March 14, 2014; Published online: && &&, 0000
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201400116.
Abstract: Aerobic dehydrogenative sulfenylation of groups, and results in various thiophosphate deriva-
H-phosphonites, and phosphine oxides with aryl/al- tives in good to high yields.
kylsulfonyl hydrazides catalyzed by a sub-stoichio-
metric amount of copper iodide has been accom- Keywords: copper iodide; sulfenylation; sulfonylhy-
plished. This protocol is compatible with functional drazides; thiol surrogate; thiophosphates
Introduction
action of trisubstituted derivatives of phosphites with
alkyl- or arylsulfonyl chlorides;[7] (ii) reaction of H-
Copper-catalyzed carbon-carbon bond, carbon-heter- phosphonates with various sulfenyl chlorides,[8] sul-
oatom bond, and heteroatom-heteroatom bond form-
fenyl cyanides,[9] and substituted disulfides;[10] and (iii)
ACHTUNGTRENNUNG
ing reactions have emerged as a method of choice condensation of phosphorochloridates with thiols or
and this can be ascribed to the functional group com- their metal salts (Figure 1).[11] Recently, an interesting
patibility of copper metal as well as its easy accessibil- Cu-catalyzed aerobic dehydrogenative coupling of H-
ity, and cost-effectiveness.[1] Recently, single electron phosphonates with various substituted aryl thiols
transfer initiated, Cu-catalyzed dehydrogenative under basic media leading to thiophosphates has been
cross-coupling transformations have been developed reported (Figure 1).[12] However, methods for the syn-
to access various functional molecules.[2]
thesis of the thiophosphate class of compounds are
Furthermore, dioxygen acts as an oxidant in Cu-cat- extremely limited due to oxidative self-dimerizations
alyzed dehydrogenative reactions, thereby generating catalyzed by air/metal complexes in the presence of
a truly environmentally benign water molecule as by- a base. Additionally, the high propensity of metal co-
product. This strategy offers an appealing alternative ordination by sulfur hampers the use of metal cataly-
to cross-coupling reactions whereby activation of the sis, thereby restricting the scope of application.
corresponding cross-coupling reaction partners by Hence, there is still great need for the development
pre-functionalization is circumvented. The copper-cat- of a functional group compatible and convenient pro-
alyzed carbon-carbon bond[3] and carbon-heteroatom tocol to produce various thiophosphate derivatives.
bond[4] forming reactions are fairly well established
but their respective heteroatom-heteroatom bond[5]
À
forming reactions are rather scarce. In particular, P S Results and Discussion
bond formation reactions are limited owing to their
exceptional oxidative reactivity, consequently leading Consistent with our continued interest in developing
[13]
À
to dimerization. The derivatives of thiophosphates base-free Cu-catalyzed P C bond formation routes,
display diverse biological activities, for example, as we report our findings regarding dehydrogenative
pesticides, insecticides, enzyme modifiers, and poten- cross-coupling of H-phosphonates with sulfonylhydra-
tial HIV-1 and ACHE inhibitors.[6]
zides as aryl/alkyl thio surrogates. Initially, 1 equiv. of
The prominent routes for the synthesis of thiophos- diethyl H-phosphonate 1a, and 1.2 equiv. of tosylhy-
phorus compounds include (i) Michaelis–Arbuzov re- drazide 2a were allowed to react in the presence of
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Gullapalli Kumaraswamy and Ragam Raju
molecular iodine (10 mol%) in refluxing ethanol
under an atmosphere of air in analogy to the litera-
ture report.[2b] No trace of the anticipated sulfenylated
product 3a was observed; instead dimerized com-
pounds 3aa and 3ab were isolated (entry 1, Table 1).
Replacing ethanol by 1,4-dioxane, under otherwise
identical conditions, resulted in an identical set of
compounds with varying yields (entry 2, Table 1).[14]
Performing the reaction with a catalytic amount of
PdCl2 in place of I2 under the same conditions also
did no yield of the required compound 3a (entry 3,
Table 1).
After considerable experimentation, use of 1 equiv.
of diethyl H-phosphonate 1a, and 1.2 equiv. of tosyl-
hydrazine 2a in the presence of 10 mol% of CuI in di-
oxane under heating at 808C provided the desired sul-
fenylated product 3a in 88% isolated yield (entry 11,
Table 1). In this process, various copper salts have
been examined. Although all copper salts initiated
the reaction (entries 4–11, Table 1), CuI was found to
À
Figure 1. Prior art in P S bond formation.
Table 1. Screening of various catalysts and conditions for dehydrogenate cross-coupling of diethyl H-phosphonate with tosyl-
hydrazide.[a]
Entry
Catalyst (10 mol%)
Solvent
3a (yield [%])[b]
1
I2
EtOH
3aa (20), 3ab (30)
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
I2
PdCl2
CuACTHNGURETNNU(G OAc)2
CuCl2
CuCN
dioxane
dioxane
dioxane
dioxane
dioxane
dioxane
dioxane
dioxane
dioxane
dioxane
dioxane
CH3CN
DMF
3aa (10), 3ab (20)
NR[c]
64
58
80
76
72
Cu
(CH3CN)4PF6
CuCl
CuBr
CuI
CuI
CuI(5)
CuI
CuI
CuI
CuI
83
50[d]
88[e]
50[f]
60
40
45
52
80
toluene
DCE
neat
CuI
[a]
All reactions were carried out using 1 mmol scale using 1a (1 mmol), 2a (1.2 mmol), CuI (0.1 mmol) in 2 mL of dioxane
heating at 808C for 4 h in the open air.
Isolated yield, but not optimized.
NR=No reaction.
Reaction carried out at 508C.
[b]
[c]
[d]
[e]
[f]
This reaction also carried out 20 mmol scale with heating at 808C for 12 h in the open air.
Reaction carried out with 5 mol% catalyst at 808C.
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Copper(I)-Induced Sulfenylation of H-Phosphonates, H-Phosphonites
phates, 3o and 3p (Table 2), were efficiently generated
employing the respective alkylsulfonylhydrazides.
These examples reveal the potential utility of this
methodology for the preparation of various alkyl thio-
phosphates that are used as pesticides.[6e] Also, ben-
zylhydrazide 2q underwent the sulfenylation reaction
with good yield (3q, Table 2).
This methodology was extended to coupling of vari-
ous aryl-/alkylphosphine oxides. Bis(meta-methoxy)-
phenylphosphine oxide 2t and even dibutylphosphine
oxide 2u participated in the sulfenylation reaction
Scheme 1. Cu(I)-promoted dehydrogenative cross-coupling
of N-substituted sulfonyl hydrazines.
be the most effective catalyst regarding the observed under otherwise identical conditions as above and de-
product 3a formation (88% yield). Meanwhile, livered the corresponding thiophosphates 3t and 3u in
5 mol% catalyst loading led to a reduced yield excellent yields (Table 2). Ethyl phenylphosphinate
(entry 12, Table 1). Solvent screening revealed that di- 2w underwent coupling yielding the thiophosphate 3w
oxane is optimal (entries 13–16, Table 1). Remarkably, in 85%. Menthyl phenylphosphinate 2x[15] also served
the reaction proceeded under solvent-free conditions, as good substrate to produce the corresponding thio-
resulting in 3a, albeit in lower yield (entry 17, phosphate 3x as a diastereomeric mixture (65:35) in
Table 1). The reaction proved to be fairly sensitive to high yield (Table 2). Interestingly, diphenylphosphine-
temperature, yielding 50% when the temperature was borane, 2y proceeded well for sulfenylation, giving
reduced from 80 to 608C, whereas with higher tem- rise to thiophosphine-borane 3y in 85% yield
perature (>808C) product decomposition was ob- (Table 2).
served. Using deaerated dioxane under an argon at-
Nucleophilic substitution reactions of chiral tetra-
mosphere furnished the product 3a in low yield coordinate secondary phosphorus compounds having
[13a,16]
À
(15%), indicating participation of dioxygen in the re- a P H bond can possibly result in racemiz6ation.
action. In a blank reaction in the absence of CuI, no In the light of these observations, we explored wheth-
trace of product 3a was observed.
er the copper-catalyzed dehydrogenative cross-cou-
À
In order to appraise the necessity of the NHNH2 pling reaction proceeds with retention or inversion of
functionality, a Boc-protected sulfonylhydrazide, 2aa, the configuration at phosphorus. Consequently, enan-
was prepared and subjected to the standard reaction tioenriched (R)-2v was reacted with 2b under the typ-
conditions in the presence of 1a. No trace of the re- ical reaction conditions. The desired product (Æ)-3z
quired compound 3a was observed. Only starting ma- was obtained in 86% yield with racemization indicat-
terials were recovered. Similarly, the reaction of ben- ing that the configuration of phosphorus is not pre-
zenesulfonamide 2ab with 1a also resulted in no reac- served during the transformation (Scheme 2).
À
tion, indicating that the NHNH2 group is indispensa-
ble for the reaction to proceed (Scheme 1).
A plausible mechanism is proposed by analogy with
dehydrogenative cross-coupling reactions.[2b,c] Initially,
With the optimum conditions in hand, the scope of the oxidation of Cu(I) by molecular oxygen generates
this new reaction was investigated and the corre- the copper(II) peroxo species, [A] which then dissoci-
sponding results are summarized in Table 2. Looking ates in the presence of sulfonylhydrazide resulting in
at the tabulated results, the sulfenylation substrate metallo-organic peroxide [B] and HO-Cu(II). Then,
scope is well established. The reaction is not only sequential removal of hydrogen and oxygen atoms
compatible with various substitutions on phosphorus, from the putative intermediate [B] could lead to thio-
but also maintains the substitution pattern of the sul- diazonium [C]. The nucleophilic substitution reaction
fonylhydrazine aromatic nucleus. Moreover, the sulfo- of phosphite anion, [D], on thiodiazonium [C] eventu-
nylhydrazide aromatic nucleus functional group sub- ally results in the desired thiophosphate, 3a
stitution proved to be inconsequential to the reaction (Scheme 3).
outcome, as both 2f and 2k, bearing electron-donating
methyl and electron-withdrawing fluoride groups, re-
spectively, resulted in good yields (3f and 3k,
Table 2).
Significantly, a highly polar carboxylic acid substi-
tuted arylsulfonylhydrazide performed well under the
standard protocol, affording carboxylic acid possess-
ing thiophosphate 3m in 75% yield (Table 2). Also,
1,3-disulfonylhydrazide 2n underwent the sulfenyla-
tion reaction with moderate yield (3n, Table 2). It is
noteworthy that methyl as well as butyl thiophos- Scheme 2. Sulfenylation of a chiral phosphine oxide.
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Gullapalli Kumaraswamy and Ragam Raju
Table 2. Synthesis of thiophosphonatederivatives.[a,b,c]
[a]
All reactions were carried out using 1 equiv. of phosphorus compound, 1.2 equiv. of aryl/alkylsulfonyl-
hydrazide and 0.1 equiv. of CuI in dioxane heating at 808C for 4 h in the open air.
Isolated yields.
[b]
[c]
[d]
All compounds were fully characterized.
Diastereomeric ratio was determined by 31P NMR and also analyzed on a chiral AS column by
HPLC.
Conclusions
sulfonylhydrazides as a thiol surrogate. A series of
sterically and electronically divergent phosphorus de-
In conclusion, we have successfully developed a mild rivatives and aryl/alkylsulfonylhydrazides participated
and base-free sulfenylation of aryl/alkyl H-phospho- in the coupling reaction and the corresponding prod-
nates and phosphine oxides using odourless, air-stable ucts were obtained in high yields. The striking feature
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Copper(I)-Induced Sulfenylation of H-Phosphonates, H-Phosphonites
chromatography was carried out using Silica gel 100–200
mesh (commercial suppliers).
Typical Procedure for Synthesis of O,O-Diethyl S-
para-Tolyl Phosphorothioate (3a) [4143-38-8]
To a stirred solution of sulfonylhydrazide 2a (1.2 mmol) in
1,4-dioxane (2 mL) were added diethyl H-phosphonate, 1a
(1.0 mmol) and CuI (10 mol%) successively. The resulting
reaction mixture was heated at the 808C for 4 h. Subse-
quently, the reaction mixture was allowed to reach ambient
temperature, and the solvent was evaporated to furnish a res-
idue which was purified by silica gel chromatography, elut-
ing with hexane/ethyl acetate (10:1 to 2:1) to afford the
phosphorothioate 3a as a yellow liquid; yield: 2.29 g (88%).
1H NMR (300 MHz, CDCl3): d=7.44 (d, J=7.7 Hz, 2H),
7.16 (d, J=7.7 Hz, 2H), 4.29–4.10 (m, 4H), 2.35 (s, 3H),
1.31 (t, J=7.0 Hz, 6H); 13C NMR (75 MHz, CDCl3): d=
139.2 (d, J=2.7 Hz), 134.5 (d, J=4.9 Hz), 130.1, 122.7 (d,
J=7.1 Hz), 63.9 (d, J=6.0 Hz), 21.1, 16.0 (d, J=7.1 Hz);
31P NMR (200 MHz, CDCl3): d=23.4; IR (neat): n=2999,
2908, 1712, 1247 (P=O), 1215, 1012, 744 cmÀ1; HR-MS:
m/z=261.0706, calculated for C11H17O3PS (M+H):
261.0708.
Scaled-Up Reaction of 3a
To a stirred solution of sulfonylhydrazide 2a (24.0 mmol) in
1,4-dioxane (60 mL) were added diethyl H-phosphonate, 1a
(20.0 mmol) and CuI (10 mol%) successively. The resulting
reaction mixture was heated at the 808C for 12 h. Subse-
quently, the reaction mixture was allowed to reach ambient
temperature, and the solvent was evaporated to afford a resi-
due which was purified by silica gel chromatography, eluting
with hexane/ethyl acetate (10:1 to 2:1) furnishing the phos-
phorothioate 3a as yellow liquid; yield: 45.8 g (88%).
The following S-aryl/alkyl phosphorothioate compounds
were generated employing 1 mmol of phosphorus com-
pound, 1.2 mmol of aryl/alkylsulfonylhydrazide and
0.1 mmol of CuI in dioxane under heating at 808C for 4 h in
Scheme 3. Proposed Cu(I)-promoted dehydrogenative cross-
coupling cycle.
of this reaction is that alkyl thiophosphates are readi-
ly accessible through this protocol. To the best of our
knowledge this is the first report on sulfenylation of
phosphorus through aryl/alkylsulfonylhydrazides. Fur-
ther work is in progress to broaden the scope of this the open air.
O,O-Diethyl S-phenyl phosphorothioate (3b) [1889-58-3]:
reaction.
Yellow liquid; yield: 211 mg (86%); 1H NMR (300 MHz,
CDCl3): d=7.59–7.55 (m, 2H), 7.38–7.32 (m, 3H), 4.29–410
(m, 4H), 1.31 (t, J=7.0 Hz, 6H); 13C NMR (75 MHz,
CDCl3): d=134.5 (d, J=4.5 Hz), 129.3, 129.0, 64.0 (d, J=
6.6 Hz), 16.0 (d, J=6.6 Hz); 31P NMR (200 MHz, CDCl3):
d=22.8; IR (neat): n=3482, 2984, 2925, 2853, 1644, 1581,
1475, 1441, 1247 (P=O), 1161, 1007, 970, 746 cmÀ1; HR-MS:
m/z=247.0549, calculated for C10H15O3PS (M+H):
247.0552.
Experimental Section
General Methods
All reactions were conducted under an open air atmosphere.
Apparatus used for reactions are oven-dried. 1,4-Dioxane
and other solvents were used as received. H NMR spectra
O,O-Dimethyl S-para-tolyl phosphorothioate (3c) [93116-
00-8]: Yellow liquid; yield: 197.2 mg (85%); 1H NMR
(300 MHz, CDCl3): d=7.44 (dd, J=8.3 Hz, J=2.3 Hz, 2H),
7.17 (d, J=8.3 Hz), 3.84 (s, 3H), 3.80 (s, 3H), 2.35 (s, 3H);
13C NMR (125 MHz, CDCl3): d=139.4 (d, J=2.7 Hz), 134.5
(d, J=5.5 Hz), 131.1 (d, J=1.8 Hz), 128.4, 128.1, 122.0 (d,
J=7.3 Hz), 54.0 (d, J=5.5 Hz), 21.0; 31P NMR (200 MHz,
CDCl3): d=26.7; IR (neat): n=3019, 2921, 1725, 1492, 1257
(P=O), 1215, 1018, 757 cmÀ1; HR-MS: m/z=233.0394, calcu-
lated for C9H13O3PS (M+H): 233.0395.
1
were recorded at 300, 400 and 500 MHz and 13C NMR 75
and 125 MHz in CDCl3. 31P spectra were recorded at
200 MHz in CDCl3. J values were recorded in hertz and ab-
breviations used were s=singlet, d=doublet, m=multiplet,
br=broad, dd=doublet of doublet. Chemical shifts (d) are
reported relative to TMS (d=0.0) as an internal standard.
IR (FT-IR) spectra were measured as KBr pellets or as
films. Mass spectral data were compiled using MS (ESI),
HR-MS mass spectrometers. Optical rotations were record-
ed on a high sensitive polarimeter with 10 mm cell. Column
O,O-Diisopropyl S-para-tolyl phosphorothioate (3d)
1
[145586-66-9]: Yellow liquid; yield: 242 mg (84%); H NMR
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(300 MHz, CDCl3): d=7.47 (dd, J=8.3 Hz, J=2.3 Hz, 2H),
7.14 (d, J=8.3 Hz, 2H), 4.87–4.68 (m, 2H), 2.34 (s, 3H),
1.33 (d, J=6.0 Hz, 6H), 1.26 (d, J=6.0 Hz, 6H); 13C NMR
(125 MHz, CDCl3): d=138.7 (d, J=2.7 Hz), 134.1 (d, J=
4.5 Hz), 129.8 (d, J=1.8 Hz), 123.1 (d, J=6.4 Hz), 73.0 (d,
J=7.3 Hz), 23.6 (d, J=4.5 Hz), 23.4 (d, J=5.5 Hz), 21.0;
31P NMR (200 MHz, CDCl3): d=20.9; IR (neat): n=2979,
2927, 1729,1689, 1492, 1252 (P=O), 979, 768 cmÀ1; HR-MS:
m/z=289.1019, calculated for C13H21O3PS (M+H):
289.1021.
S-2,5-Dimethylphenyl O,O-diethyl phosphorothioate (3e):
Yellow liquid; yield: 230 mg (84%); 1H NMR (500 MHz,
CDCl3): d=7.41 (s, 1H), 7.18–7.01 (m, 2H), 4.23–4.08 (m,
4H), 2.47 (s, 3H), 2.30 (s, 3H), 1.35–1.24 (m 6H); 13C NMR
(125 MHz, CDCl3): d=138.9 (d, J=5.4 Hz), 136.6 (d, J=
4.5 Hz), 136.1 (d, J=2.7 Hz), 130.5 (d, J=2.7 Hz), 130.2 (d,
J=2.7 Hz), 124.9 (d, J=7.3 Hz), 63.9 (d, J=7.3 Hz), 20.7,
20.5, 16.0 (d, J=7.3 Hz); 31P NMR (200 MHz, CDCl3): d=
23.3; IR (neat): n=2981, 2923, 1738, 1490, 1253 (P=O),
1215, 1014, 971, 750 cmÀ1; HR-MS: m/z=275.0860, calculat-
ed for C12H19O3PS (M+H): 275.0865.
O,O-Diethyl S-mesityl phosphorothioate (3f): Yellow
liquid; yield: 245 mg (85%); 1H NMR (300 MHz, CDCl3):
d=6.94 (s, 2H), 4.17–4.04 (m, 4H), 2.53 (d, J=1.5 Hz, 6H),
2.25 (d, J=2.4 Hz, 3H), 1.29 (dt, J=7.1 Hz, J=0.8 Hz, 6H);
13C NMR (125 MHz, CDCl3): d=143.9 (d, J=5.4 Hz), 139.4
(d, J=4.5 Hz), 129.4 (d, J=2.7 Hz), 122.2 (d, J=8.2 Hz),
64.1 (d, J=7.3 Hz), 22.4, 20.1, 16.0 (d, J=7.3 Hz); 31P NMR
(200 MHz, CDCl3): d=23.6; IR (neat): n=3743, 3396, 2981,
2923, 2853, 1601, 1550, 1443, 1247 (P=O), 1162, 1012, 966,
771, 603 , cmÀ1; HR-MS: m/z=289.1017, calculated for
C13H21O3PS (M+H): 289.1021.
IR (neat): n=3445, 2976, 2834, 1732, 1467, 1387, 1242 (P=
O), 1013, 976, 765 cmÀ1; HR-MS: m/z=295.0317, calculated
for C11H16O3ClPS (M+H): 295.0319.
S-4-Bromophenyl O,O-diethyl phosphorothioate (3j)
1
[15224-36-9]: Yellow liquid; yield: 279 mg (86%); H NMR
(300 MHz, CDCl3): d=7.50–7.41 (m, 4H), 4.29–4.10 (m,
4H), 1.32 (t, J=6.8 Hz, 6H); 13C NMR (125 MHz, CDCl3):
d=135.9 (d, J=5.5 Hz), 132.4 (d, J=1.8 Hz), 125.7 (d, J=
6.4 Hz), 123.6 (d, J=2.7 Hz), 64.2 (d, J=6.4 Hz), 16.0 (d, J=
7.3 Hz); 31P NMR (200 MHz, CDCl3): d=21.9; IR (neat):
n=3744, 3610, 2922, 2851, 1709, 1472, 1389, 1255 (P=O),
1219, 1009, 974, 772 cmÀ1; HR-MS: m/z=346.9467, calculat-
ed for C10H14O3BrPS (M+Na): 346.9477.
O,O-Diethyl S-2-fluoro-5-methylphenyl phosphorothioate
(3k): Yellow liquid; yield: 234 mg (84%); 1H NMR
(300 MHz, CDCl3): d=7.41–7.34 (m, 1H), 7.24–7.19 (m,
1H), 7.04–6.94 (m, 1H) 4.29–4.09 (m, 4H), 2.47 (s, 3H) 1.31
(t, J=6.8 Hz, 6H); 13C NMR (125 MHz, CDCl3): d=160.4
(d, J=247.0 Hz), 137.5 (d, J=13.6 Hz), 131.5 (d, J=5.4 Hz),
127.0 (t, J=7.3 Hz), 122.2 (d, J=22.7 Hz), 116.2 (d, J=
19.9 Hz), 64.2 (d, J=6.4 Hz), 20.3, 15.8 (d, J=6.4 Hz);
31P NMR (200 MHz, CDCl3): d=22.1; IR (neat): n=3765,
3018, 2987, 1487, 1214 (P=O), 1009, 974, 742 cmÀ1; HR-MS:
m/z=279.0611, calculated for C11H16FO3PS (M+H):
279.0615.
O,O-Diethyl S-2-methyl-5-nitrophenyl phosphorothioate
(3l): Yellow liquid; yield: 256 mg (84%); 1H NMR
(300 MHz, CDCl3): d=8.49 (t, J=2.3 Hz, 1H), 8.13 (m,
1H), 7.43 (d, J=8.3 Hz, 1H), 4.27–4.14 (m, 4H), 2.61 (s,
3H), 1.33 (t, J=8.3 Hz, 6H); 13C NMR (75 MHz, CDCl3):
d=149.5 (d, J=5.5 Hz), 145.7, 130.9 (d, J=1.1 Hz), 130.0 (d,
J=3.8 Hz), 127.6 (d, J=7.1 Hz), 123.4 (d, J=1.6 Hz), 64.1
(d, J=6.6 Hz), 21.1, 15.4 (d, J=7.1 Hz); 31P NMR
(200 MHz, CDCl3): d=21.0; IR (neat): n=2984, 2923, 2852,
O,O-Diethyl S-naphthalen-2-yl phosphorothioate (3g)
1
[109161-61-7]: Yellow liquid; yield: 225 mg (76%); H NMR
(300 MHz, CDCl3): d=8.53 (d, J=8.3 Hz, 1H), 7.92–7.84
(m, 3H), 7.64–7.43 (m, 3H), 4.22–4.03 (m, 4H), 1.21–1.16
(dt, J=7.0 Hz, J=0.7 Hz, 6H); 13C NMR (75 MHz, CDCl3):
d=135.2 (d, J=5.5 Hz), 134.6, 134.2, 130.3 (d, J=3.3 Hz),
128.5, 127.0, 126.4, 125.8, 125.6 (d, J=2.7 Hz), 64.2 (d, J=
6.6 Hz), 15.9 (d, J=7.1 Hz); 31P NMR (200 MHz, CDCl3):
d=22.7; IR (neat): n=3743, 3610, 3056, 2984, 2906, 1741,
1502, 1254 (P=O), 1014, 772 , cmÀ1; HR-MS; m/z=297.0705,
calculated for C14H17O3PS (M+H): 297.0708.
S-4-Chlorophenyl O,O-diethyl phosphorothioate (3h)
[4524-70-3]: Yellow liquid; yield: 241 mg (86%); 1H NMR
(300 MHz, CDCl3): d=7.49 (dd, J=8.5 Hz, J=1.9 Hz, 2H),
7.31 (d, J=8.5 Hz, 2H), 4.27–4.08 (m, 4H), 1.30 (t, J=
7.0 Hz, 3H); 13C NMR (125 MHz, CDCl3): d=135.7 (d, J=
4.5 Hz), 135.5 (d, J=3.6 Hz), 129.5, 125.1 (d, J=7.3 Hz),
64.2 (d, J=6.4 Hz), 16.0 (d, J=6.4 Hz); 31P NMR (200 MHz,
CDCl3): d=22.2; IR (neat): n=3484, 2983, 2923, 2852, 1728,
1475, 1390, 1253 (P=O), 1009, 973, 772 cmÀ1; HR-MS: m/z=
281.0158, calculated for C10H14O3ClPS (M+H): 281.0162.
S-2-Chloro-4-methylphenyl O,O-diethyl phosphorothioate
(3i): Yellow liquid; yield: 232 mg (79%); 1H NMR
(300 MHz, CDCl3): d=7.54 (dd, J=8.3 Hz, J=2.3 Hz, 1H),
7.26 (s, 1H), 7.16 (dd, J=8.3 Hz, J=2.3 Hz, 1H), 4.26–4.07
(m, 4H), 2.50 (s, 3H), 1.31 (t, J=7.0 Hz, 3H); 13C NMR
(75 MHz, CDCl3): d=144.0 (d, J=5.5 Hz), 137.3 (d, J=
3.8 Hz), 135.4 (d, J=3.8 Hz), 130.7 (d, J=2.2 Hz), 126.9 (d,
J=2.2 Hz), 124.3 (d, J=7.2 Hz), 64.3 (d, J=6.6 Hz), 21.3,
16.0 (d, J=7.2 Hz); 31P NMR (200 MHz, CDCl3): d=22.5;
1580, 1520, 1470, 1346, 1256
739 cmÀ1
HR-MS: m/z=306.0556,
C11H16NO5S (M+H): 306.0557.
ACHTUNGTRENNUNG
;
3-(Diethoxyphosphorylthio)benzoic acid (3m) [103647-17-
2]: White solid; yield: 217 mg (75%), mp 110–1128C;
1H NMR (300 MHz, CDCl3): d=8.16 (d, J=15.9 Hz 1H),
8.02 (d, J=7.7 Hz, 1H), 7.88 (d, J=7.7 Hz, 1H), 7.76–7.66
(m, 1H), 7.49–7.39 (m, 1H), 4.24–4.04 (m, 4H), 1.31(t,
J=6.8 Hz, 6H); 13C NMR (125 MHz, CDCl3): d=165.9 (d,
J=2.7 Hz), 137.4 (dd, J=10.9 Hz, J=4.5 Hz), 135.8, 134.6
(d, J=5.4 Hz), 131.3 (d, J=1.8 Hz), 131.1, 130.3 (d, J=
11.8 Hz), 129.2 (m), 128.3 (m), 125.9 (d, J=7.3 Hz), 63.2 (d,
J=6.4 Hz), 62.4, 15.0; 31P NMR (200 MHz, CDCl3): d=26.3;
IR (neat): n=3331, 2945, 2833, 1704, 1660, 1450, 1415, 1219
(P=O), 1112, 1017, 772 cmÀ1; HR-MS: m/z=313.0261, calcu-
lated for C11H14O5NaPS (M+H): 313.0270.
S,S’-1,3-Phenylene O,O,O’,O’-tetraethyl diphosphoro-
thioate (3n) [109592-17-8]: Yellow liquid; yield: 232 mg
1
(56%); H NMR (300 MHz, CDCl3): d=7.78–7.21 (m, 4H),
4.27–4.09 (m, 8H), 1.35–1.26 (m, 12H); 13C NMR (125 MHz,
CDCl3): d=139.8, 137.9, 134.9, 133.2, 132.6, 130.0, 129.8,
128.1, 127.7, 125.8, 125.0, 64.2 (dd, J=9.1 Hz, J=6.4 Hz),
16.0 (d, J=7.3 Hz); 31P NMR (200 MHz, CDCl3): d=22.0
(d, J=22.4 Hz); IR (neat): n=2983, 2907, 1729, 1566, 1459,
1255 (P=O), 1012, 772 cmÀ1; HR-MS: m/z=437.0373, calcu-
lated for C14H23O6NaP2S2 (M+H): 437.0382.
O,O-Diethyl S-methyl phosphorothioate (3o) [2404-05-9]:
Yellow liquid; yield: 144 mg (78%); 1H NMR (300 MHz,
6
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Copper(I)-Induced Sulfenylation of H-Phosphonates, H-Phosphonites
CDCl3): d=4.28–4.09 (m, 4H), 2.31–2.26 (d, J=15.1 Hz,
3H), 1.38 (t, J=6.8 Hz, 6H); 13C NMR (75 MHz, CDCl3):
d=63.5 (d, J=5.5 Hz), 16.0 (d, J=7.2 Hz), 12.3 (d, J=
4.4 Hz); 31P NMR (200 MHz, CDCl3): d=28.6; IR (neat):
n=2983, 2932, 1741, 1644, 1442, 1245 (P=O), 1007, 957, 754 ,
cmÀ1; HR-MS: m/z=207.0213, calculated for C5H13O3PS
(M+Na): 207.0215.
S-Butyl O,O-diethyl phosphorothioate (3p) [20195-07-7]:
Yellow liquid; yield: 194 mg (86%); 1H NMR (300 MHz,
CDCl3): d=4.26–4.07 (m, 4H), 2.84 (m, 2H), 1.72–1.62 (m,
2H), 1.49–1.39 (m, 2H), 1.37 (t, J=6.8 Hz, 6H), 0.93 (t, J=
7.6 Hz, 3H); 13C NMR (125 MHz, CDCl3): d=63.4 (d, J=
5.5 Hz), 32.7 (d, J=5.5 Hz), 30.5 (d, J=4.5 Hz), 21.6, 16.0
(d, J=7.3 Hz), 13.4; 31P NMR (200 MHz, CDCl3): d=21.4;
(d, J=7.9 Hz, 2H), 7.17 (d, J=7.9 Hz, 2H), 2.35 (s, 3H),
1.93–1.83 (m, 4H), 1.73–1.51 (m, 6H), 0.95–0.87 (m, 6H);
13C NMR (75 MHz, CDCl3): d=139.3 (d, J=1.8 Hz), 135.4
(d, J=3.6 Hz), 130.2 128.5 31.2, 30.6, 24.4 (d, J=3.6 Hz),
23.9, 23.8, 21.2, 13.6; 31P NMR (200 MHz, CDCl3): d=59.3;
IR (neat): n=3727, 2957, 2931, 2854, 1513, 1461, 1243 (P=
O), 974, 778 cmÀ1; HR-MS: m/z=285.1434, calculated for
C15H27OPS (M+H): 285.1436.
S-para-Tolyl tert-butylACTHNUTRGENU(GN phenyl)phosphinothioate (3v):
Yellow liquid; yield: 258 mg (85%); 1H NMR (500 MHz,
CDCl3): d=7.88–7.84 (m, 2H), 7.47–7.33 (m, 5H), 6.96 (d,
J=7.9 Hz, 2H), 2.20 (s, 3H), 1.23 (d, J=16.9 Hz, 9H);
13C NMR (125 MHz, CDCl3): d=139.3, 135.4 (d, J=2.7 Hz)
133.0 (d, J=9.1 Hz) 131.7 (d, J=2.7 Hz), 130.3, 129.7, 128.7
IR (neat): n=3747, 2957, 2921, 2852, 1509, 1461, 1219 (P= (d, J=11.8 Hz), 127.8 (d, J=11.8 Hz), 121.8 (d, J=5.4 Hz),
O), 967, 772 cmÀ1; HR-MS: m/z=227.0865, calculated for
C8H19O3PS (M+H): 227.0865.
29.5, 24.8, 20.9; 31P NMR (200 MHz, CDCl3): d=55.4; IR
(neat): n=2957, 2921, 2852, 1515, 1463, 1216 (P=O), 1166,
S-Benzyl O,O-diethyl phosphorothioate (3q) [13286-32-
909, 771 cmÀ1
; HR-MS: m/z=305.1122, calculated for-
1
3]: Yellow liquid; yield: 224 mg (86%); H NMR (500 MHz,
C17H21OPS (M+H): 305.1124.
CDCl3): d=7.36–7.24 (m, 5H), 4.15–3.98 (m, 6H), 1.28 (t,
J=7.0 Hz, 6H); 13C NMR (125 MHz, CDCl3): d=137.4 (d,
J=5.5 Hz), 128.8, 128.5, 127.5, 63.4 (d, J=5.5 Hz), 34.8, 15.8
(d, J=6.4 Hz); 31P NMR (200 MHz, CDCl3): d=26.7; IR
(neat): n=3482, 2984, 2922, 2843, 1654, 1581, 1445, 1421,
1223 (P=O), 1141, 1017, 970, 746 cmÀ1; HR-MS: m/z=
261.0706, calculated for C11H17O3PS: 261.0709.
O-Ethyl S-para-tolyl phenylphosphonothioate (3w)
[681460-69-5]: Yellow liquid; yield: 248 mg (85%);1H NMR
(300 MHz, CDCl3): d=7.68–7.63 (m, 2H), 7.51–7.47 (m,
1H), 7.38–7.34 (m, 2H), 7.16 (dd, J=7.9 Hz, J=1.5 Hz,
2H), 7.01 (d, J=7.9 Hz, 2H), 4.40–4.28 (m, 2H), 2.28 (s,
3H), 1.39 (t, J=7.0 Hz, 3H); 13C NMR (125 MHz, CDCl3):
d=139.1 (d, J=2.7 Hz), 135.3 (d, J=3.6 Hz), 132.3 (d, J=
2.7 Hz), 131.3 (d, J=10.9 Hz), 129.8 (d, J=1.8 Hz), 128.1,
128.0, 122.6 (d, J=6.4 Hz), 62.3 (d, J=6.4 Hz), 21.0 16.2 (d,
J=6.4 Hz); 31P NMR (200 MHz, CDCl3): d=42.4; IR
(neat): n=3476, 2922, 1592, 1439, 1232 (P=O), 1118, 1018,
953, 749 , cmÀ1; HR-MS: m/z=293.0754, calculated for
C15H17O2PS (M+H): 293.0759.
S-(7,7-Dimethyl-2-oxobicycloACTHNUGRTNEUNG[2.2.1]heptan-1-yl)methyl
O,O-diethyl phosphorothioate (3r): Yellow liquid; yield:
275 mg (86%), [a]25: 9 (c 1, CHCl3); 1H NMR (300 MHz,
CDCl3): d=4.28–4D.09 (m, 4H), 2.31–2.26 (d, J=15.1 Hz,
3H), 1.38 (t, J=6.8 Hz, 6H); 13C NMR (100 MHz, CDCl3):
d=216.7, 63.6 (d, J=5.9 Hz), 60.4 (d, J=5.9 Hz), 43.7, 43.0,
29.7, 26.9, 22.7, 21.1, 19.8, 16.0 (d, J=8.8 Hz), 14.2 (d, J=
5.9 Hz); 31P NMR (200 MHz, CDCl3): d=28.5; IR (neat):
n=3744, 3610, 2959, 2917, 2849, 1741, 1514, 1245 (P=O),
1218, 1017, 754 cmÀ1; HR-MS: m/z=321.1282, calculated for
C14H25O4PS (M+H): 321.1289.
O-(1R,2S,5R)-2-Isopropyl-5-methylcyclohexyl
S-para-
tolyl phenylphosphonothioate (3x): Yellow liquid; yield:
1
342 mg (85%); [a]25: 74 (c 1, CHCl3); H NMR (300 MHz,
CDCl3): d=7.74–7.D66 (m, 2H), 7.52–7.34 (m, 3H), 7.25–7.21
(m, 2H), 7.03–6.99 (m, 2H), 4.56–4.41 (m, 1H), 2.28 (s, 3H),
1.75–1.33 (m, 5H), 1.29–1.18 (m, 2H), 0.96–0.80 (m, 11H);
13C NMR (75 MHz, CDCl3): d=138.9, 135.3, 132.1, 131.4,
129.8, 128.2, 128.0, 79.8 (d, J=8.8 Hz), 48.7 (d, J=6.6 Hz),
43.3 (d, J=7.2 Hz), 34.0, 31.6 (d, J=2.7 Hz), 29.7, 25.6, 22.9
(d, J=4.9 Hz), 22.0 (d, J=10.5 Hz), 21.1 (d, J=16.0 Hz),
16.0; 31P NMR (200 MHz, CDCl3): d=39.9, 40.2; IR (neat):
n=3052, 2953, 2923, 2867, 1898, 1727, 1491, 1454, 1235 (P=
O), 1117, 978, 807, 714, 692 cmÀ1; HR-MS: m/z=403.1858,
calculated for C23H31O2PS (M+H): 403.1855.
S-para-Tolyl diphenylphosphinothioate (3s) [5510-81-6]:
1
White solid; yield: 279 mg (86%); mp 112–1138C; H NMR
(500 MHz, CDCl3): d=7.87–7.83 (m, 4H), 7.53–7.42 (m,
6H), 7.32 (d, J=7.8 Hz, 2H), 7.01 (d, J=7.8 Hz, 2H), 2.26
(s, 3H); 13C NMR (75 MHz, CDCl3): d=139.1 (d, J=
2.2 Hz), 135.3 (d, J=3.9 Hz), 133.1 (d, J=7.2 Hz), 132.2 (d,
J=2.8 Hz), 131.6 (d, J=10.5 Hz), 129.9 (d, J=1.7 Hz), 128.4
(d, J=13.2 Hz), 122.0 (d, J=5.0 Hz), 21.1; 31P NMR
(200 MHz, CDCl3): d=41.9; IR (neat): n=3056, 3021, 2922,
2852, 1720, 1490, 1437, 1203 (P=O), 1114, 808, 750, 724,
695 cmÀ1; HR-MS: m/z=325.0809, calculated for C19H17OPS
(M+H): 325.0810.
Diphenyl(p-tolylthio)phosphine·borane
(3y):
Yellow
liquid; yield: 274 mg (85%); 1H NMR (300 MHz, CDCl3):
d=7.91–7.87 (m, 4H), 7.56–7.46 (m, 6H), 7.36 (d, J=7.9 Hz,
2H), 7.04 (d, J=7.9 Hz, 2H), 2.29 (s, 3H); 13C NMR
(75 MHz, CDCl3): d=139.1, 135.2 (d, J=4.4 Hz), 132.2 (d,
J=4.4 Hz), 131.6, 131.5, 129.9, 128.5, 128.3, 21.1; 31P NMR
(200 MHz, CDCl3): d=41.5; IR (neat): n=3056, 2921, 2852,
1726, 1490, 1437, 1200 (P=O), 1114, 1071, 808, 750,
S-para-Tolyl bis(3-methoxyphenyl)phosphinothioate (3t):
1
White solid; yield: 326 mg (85%), mp: 146–1488C; H NMR
(300 MHz, CDCl3): d=7.59–7.33 (m, 8H), 7.05–7.02 (m,
4H), 3.80 (s, 3H), 2.27 (s, 3H); 13C NMR (75 MHz, CDCl3):
d=139.2 (d, J=2.7 Hz), 135.4 (d, J=3.9 Hz), 133.1, 130.0 (d,
J=2.2 Hz), 129.7, 129.5, 128.5 128.3 123.7, 123.8, 118.8 (d,
J=2.8 Hz), 116.2, 116.1, 55.4, 21.1; 31P NMR (200 MHz,
CDCl3): d=41.8; IR (neat): n=3749, 3610, 2923, 2852, 1591,
694 cmÀ1
;
HR-MS:
m/z=325.0781,
calculated
for
C19H20BPS: 322.1116.
S-Phenyl tert-butylAHCTUNGTERG(NNNU phenyl)phosphinothioate (3z): Yellow
1481, 1420, 1250 (P=O), 1201, 1183, 1038, 781, 692 , cmÀ1
;
liquid; yield: 235 mg (81%); 1H NMR (500 MHz, CDCl3):
d=7.88–7.83 (m, 2H), 7.48–7.44 (m, 5H), 7.20–7.14 (m,
3H), 1.24 (d, J=16.9 Hz, 9H); 13C NMR (125 MHz, CDCl3):
d=139.2, 135.3 (d, J=3.6 Hz) 133.1 (d, J=9.1 Hz) 131.8 (d,
J=1.8 Hz), 128.9, 128.5, 128.0 (d, J=11.8 Hz), 125.9 (d, J=
HR-MS: m/z=385.1010, calculated for C21H21O3PS (M+H):
385.1027.
S-para-Tolyl dibutylphosphinothioate (3u): Yellow liquid;
1
yield: 239 mg (84%); H NMR (300 MHz, CDCl3): d=7.46
Adv. Synth. Catal. 0000, 000, 0 – 0
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Gullapalli Kumaraswamy and Ragam Raju
5.4 Hz), 29.6, 24.9; 31P NMR (200 MHz, CDCl3): d=65.2; IR
(neat): n=2962, 2928, 2912, 1531, 1483, 1246 (P=O), 1166,
Cejka, M. Hocek, Org. Biomol. Chem. 2013, 11, 5189–
5193; f) X. Mi, M. Huang, J. Zhang, C. Wang, Y. Wu,
Org. Lett. 2013, 15, 6266–6269; g) C. Zhang, Z. Li, L.
Zhu, L. Yu, Z. Wang, C. Li, J. Am. Chem. Soc. 2013,
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Plietker, Chem. Commun. 2011, 47, 11113–11115.
ˇ
909, 771 cmÀ1
;
HR-MS: m/z291.0969, calculated for
C16H19OPS (M+H): 291.0968.
Supporting Information
[5] a) X. Jin, K. Yamaguchi, N. Mizuno, Org. Lett. 2013,
15, 418–421; b) J. Fraser, L. J. Wilson, R. K. Blundell,
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Full experimental details along with copies of 1 H, 13C and
31P NMR spectra of all compounds are available in the Sup-
porting Information.
Acknowledgements
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Wittine, K. Beci, Z. Rajic, B. Zorc, M. Kralj, M. Marja-
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India (Grant no: SR/S1/OC-08/2011), and ORGIN (CSC-
0108) program (CSIR) of XII Five year plan. UGC & CSIR
(New Delhi) are gratefully acknowledged for awarding the
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found to be 60:40 and the same was subjected to sulfe-
nylation.
[16] T. Oshiki, T. Imamoto, J. Am. Chem. Soc. 1992, 114,
3975–3977.
ˇ
Lett. 2013, 15, 4202–4205; e) M. Klecka, R. Pohl, J.
8
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Copper(I)-Induced Sulfenylation of H-Phosphonates, H-
Phosphonites and Phosphine Oxides with Aryl/
alkylsulfonylhydrazides as a Thiol Surrogate
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ÞÞ
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