Catalyst- and Solvent-Free Stereoselective Addition of Secondary Phosphine Chalcogenides to Alkynes

Article abstract of DOI:10.1055/s-0034-1379207

The addition of secondary phosphine sulfides and selenides to alkynes proceeds readily (80 °C, 5-13 h) without catalysts or solvents to afford regio- and stereoselectively anti-Markovnikov adducts as tertiary alkenylphosphine chalcogenides of Z-configurat

Full text of DOI:10.1055/s-0034-1379207

SYNTHESIS
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© Georg Thieme Verlag Stuttgart · New York
2015, 47, 263–271
paper
263
A. V. Artem’ev et al.
Paper
Synthesis
Catalyst- and Solvent-Free Stereoselective Addition of Secondary
Phosphine Chalcogenides to Alkynes
Stereoselective Addition of Phosphine Chalcogenides to Alkynes
Alexander V. Artem’ev
Svetlana F. Malysheva
Nina K. Gusarova
Nataliya A. Belogorlova
Vladimir A. Shagun
Alexander I. Albanov
Boris A. Trofimov*
A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch,
Russian Academy of Sciences, 1 Favorsky Str., 664033, Irkutsk,
Russian Federation
+
7
3
(
9
5
2
4
)
1
9
3
4
6
boris_trofimov@irioch.irk.ru
Received: 23.07.2014
Accepted after revision: 03.09.2014
Published online: 23.10.2014
drawbacks such as the use of expensive and moisture/air-
sensitive catalysts (commonly unrecovered), low selectivity,
formation of undesired products, and tedious experimental
procedure (column chromatography is often necessary).
Critically, the high price of both metal sources and support-
ed ligands leads to a significant increase in the cost of the
target organophosphorus products. Furthermore, substrate
scope is often limited because many functional groups are
susceptible to catalyst species or their precursors. In this
context, the development of efficient and general catalysts
and initiator-free versions of alkyne phosphorylation with
P–H reactants are important tasks in modern organic syn-
thesis.
DOI: 10.1055/s-0034-1379207; Art ID: ss-2014-z0459-op
Abstract The addition of secondary phosphine sulfides and selenides
to alkynes proceeds readily (80 °C, 5–13 h) without catalysts or sol-
vents to afford regio- and stereoselectively anti-Markovnikov adducts
as tertiary alkenylphosphine chalcogenides of Z-configuration, in 60–
94% yield.
Key words addition reactions, alkynes, green chemistry, phosphine
chalcogenides, regioselectivity
Hydrofunctionalization of alkynes by diverse P–H ad-
dends attracts considerable attention in modern organic
chemistry.1 The availability of the starting compounds, the
simplicity of the process, its selectivity, and its 100% atom
efficiency (hence, environmental friendliness) make hydro-
phosphorylation of C≡C bonds advantageous over more tra-
ditional (phosphorus halide-based) tools used for P–C(sp2)
bond-formation. Furthermore, the broad substrate applica-
bility, with respect to both alkynes and P–H addends, al-
lows well-defined functional organophosphorus com-
pounds to be synthesized that have a wide number of appli-
cations as synthetic building blocks2 and as ligands.3 As a
result, this field has been growing rapidly and over the past
decade numerous methods for addition of various P–H ad-
dends (e.g., H-phosphines, their chalcogenides, H-phospho-
nates, etc.) to alkynes have been developed.1 These reac-
tions are commonly catalyzed by bases4 and metal com-
plexes5 to give mono- and diadducts, depending on
structure of the reactants, specified conditions, and cata-
lysts. The radical-induced6 and microwave-assisted7 addi-
tion of P–H species to alkynes are also documented. How-
ever, despite impressive progress on the catalyzed (espe-
cially metal-catalyzed) addition of P–H bonds to alkynes, it
should be noted that this methodology suffers from known
To our knowledge, only two separate examples of cata-
lyst-free addition of P–H species to alkynes have been re-
ported. Thus, addition of Ph2PH8 and Ph2P(S)H9 to phenyl-
acetylene has been noted during the study of alkene phos-
phorylation.
In a continuation of our research on non-catalyzed hy-
drophosphorylation of C=C and C≡C bonds, herein we re-
port on catalyst- and solvent-free addition of secondary
phosphine sulfides and selenides to a range of alkynes, af-
fording anti-Markovnikov monoadducts. These secondary
phosphine chalcogenides have been chosen as P–H addends
because they are readily available10 and easy-to-handle
compounds; that is, they are typically air-stable and almost
odorless powders (in contrast to commonly used secondary
phosphines, which are easily oxidizable and malodorous
liquids). Notably, data on the addition of secondary phos-
phine sulfides and selenides to alkynes are scarce. Thus, it
was reported that the radical addition (AIBN or UV initia-
tion) of R2P(X)H (X = S, Se) species to aryl- and hetaryl-acet-
ylenes furnished anti-Markovnikov Z-adducts.11,12 More-
over, under basic conditions [KOH in dimethyl sulfoxide
(DMSO) or KOH in tetrahydrofuran (THF)], the secondary
phosphine sulfides add to alkynes (acetylene and methyl-
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acetylene,13 phenylcyanoacetylene14) to give 1,2-diadducts
in good yields. In case of 4-hydroxy-4-methyl-2-pentyne-
nitrile15 and 1-acyl-2-phenylacetylenes,16 this reaction
stops at the stage of monoadduct formation.
Furthermore, secondary phosphine sulfides and selenides
containing aryl (Ph) and aryl/hetaryl-substituted alkyl
[CH2CH2Ph, CH2CH2(2-furyl)] groups could be successfully
vinylated with the above alkynes.
We have found that under solvent-free conditions, sec-
ondary phosphine sulfides and selenides 1–5 add to termi-
nal alkynes 6–12 without any catalysts or radical initiators.
The reaction proceeds under mild heating (80 °C) for 5–13
hours to afford regio- and stereoselectively (Z)-alkenyl-
phosphine chalcogenides 13a–k in 60–94% yields. The data
presented in Table 1 reveal that the reaction has general
character; thus, it tolerates a diverse range of alkynes 6–12
bearing donor (n-C6H13, CH2OH, CMe2OH), amphoteric (Ph,
p-MeC6H4), acceptor (SiMe3), and strong acceptor (COOMe)
substituents presenting various degrees of steric hindrance.
With respect to possible formation of diadducts in this
reaction, we have found that the heating of alkynes 7and 12
with phosphine sulfide 1 (80 °C, 5 h) does not lead to the
expected diadducts: only monoadducts 13c and 13k were
detectable (31P NMR analysis) in the reaction mixtures,
along with unreacted phosphine sulfide 1. Apparently, the
monoadducts are deactivated toward attack of the second
phosphine chalcogenide molecule due to the lower electro-
philicity in conjunction with the more sterically demanding
structure.
Table 1 Substrate Scope for the Uncatalyzed Addition of Secondary Phosphine Sulfides and Selenides to Alkynesa
X
R1
R1
R1
R1
80 °C, 5–13 h
R2
X
H
P
H
H
R2
+
P
without solvent
and catalyst
6–12
1–5
%
13a–k, 60–94
Entry
1
Phosphine chalcogenide
Alkyne
Time (h)
Product
Yield (%)b
S
S
Se
S
C6H13-n
C6H13-n
Ph
1
2
1
P
P
P
6
8
13a
13b
13c
78
n-C6H13
P
H
Se
H
2
3
6
7
5
5
75
94
n-C6H13
P
S
H
P
S
S
H
P
4
3
7
7
13d
90
P
Ph
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Table 1 (continued)
Entry
Phosphine chalcogenide
Alkyne
Time (h)
Product
Yield (%)b
O
S
S
H
O
P
5
4
7
7
13e
89
Ph
P
O
O
Se
H
Se
P
6
2
7
5
13f
83
Ph
P
(2)
S
H
S
7
1
1
1
1
1
8
5
13g
13h
13i
90
81
60
92
84
P
P
P
P
P
P
S
H
S
OH
8
9
5
P
HO
S
H
S
OH
9
10
11
12
13
OH
P
S
H
S
10
11
SiMe3
7
13j
P
P
Me3Si
O
S
H
O
S
5
13k
MeO
OMe
a Reaction conditions: secondary phosphine chalcogenide 1–5 (1.0 mmol), alkyne 6–12 (1.0 mmol), stirring under inert atmosphere at 80 °C for the mentioned
time.
b Isolated yield.
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Ph
The secondary phosphine oxides were found to be inac-
tive in this reaction: no formation of the tertiary phosphine
oxide was observed after heating bis(2-phenethyl)phos-
phine oxide with alkyne 7 at 80 °C for 20 hours.
Interestingly, bis(2-phenethyl)phosphine did not add to
phenylacetylene even after prolonged heating (80 °C, 20 h),
whereas Ph2PH under similar conditions (70 °C, 10 h) gave
diphenyl(styryl)phosphine in 80% yield.8 Such antipodal be-
havior of these phosphines is probably due to the different
mobility of their phosphinic hydrogen atoms {cf. for exam-
ple, pKa of Ph2PH and Et2PH in THF, 21.7 vs. 33.7}.17
Ph
S
Ph
P
Na
Ph
Ph
P
toluene, reflux, 1 h
Ph
14, 85%
(Z/E ratio ~75:25)
13d
Scheme 2 Reduction of phosphine sulfide 13d with metal sodium
1-oxyl (TEMPO) as a radical scavenger does not inhibit the
addition of phosphine sulfide 4 to phenylacetylene. More-
over, this reaction proceeds in the dark with the same effi-
ciency as in the light.
It should be stressed that the protocol developed here,
apart from its simplicity and green characteristics, provides
several synthetic advantages over known procedures for the
addition of secondary phosphine chalcogenides to alkynes.
Namely, under the elaborated conditions, aliphatic alkynes
6 and acetylenic alcohols 9 and 10 were successfully phos-
phorylated (Table 1), whereas under free-radical conditions
(AIBN initiation or UV-irradiation) the reaction failed for
these alkynes.12 Under basic conditions, unactivated
alkynes 9 and 10 are, as expected, inactive, whereas aryl-
acetylenes 7 and 8, and methyl propiolate (12) should pro-
duce diadducts mainly.14 Besides, secondary phosphine sel-
enides18 and several alkynes (1-octyne, trimethylsilylacet-
ylene) are easily decomposed under the basic conditions.
The obtained adducts 13a–k were fully characterized by
NMR (1H, 13C, 31P, and, when appropriate, 28Si, 77Se) and IR
spectroscopy, and their composition was verified by micro-
To gain an insight into the mechanistic pathway of this
reaction, DFT computations were carried out. Herein, we
present the preliminary results of a theoretical study con-
ducted at the B3LYP/6-311+G(d,p) level19 (gas phase) on the
uncatalyzed reaction between diphenylphosphine sulfide
and phenylacetylene. Given that the R2P(X)H (X = O, S, Se)
species are theoretically able to tautomerize partially in
phosphinous acids, R2PXH,20 we constructed two potential
energy surfaces (PESs) corresponding to the addition of
both Ph2P(S)H (1) and Ph2PSH (1A) forms. It can be noted
that the latter isomer was found to be slightly more stable
than the former by 0.9 kcal/mol.
The calculations indicate that the addition of Ph2P(S)H
to phenylacetylene is a one-step process, affording the ther-
modynamically more favorable E-isomer [the free energy
difference with Z-isomer is 3.6 kcal/mol]. The correspond-
ing free energy profile is plotted in Figure 1 (the geometri-
cal parameters of the structures are given in the Supporting
Information). This channel involves formation of pre-
reaction complex A, which is characterized by a small
(–2.4 kcal/mol) decrease of energy of the initial reagents.
Complex A is further transformed into the stable E-isomer
[(E)-13c] via high-energy transition-state TS1, with an acti-
vation barrier of 66.6 kcal/mol. In the four-centered TS1,
the stretched C≡C bond of alkyne is capped by the hydrogen
of the ruptured P–H bond so that the structure of TS1 re-
sembles that of an ion pair formed by proton transfer from
phosphine sulfide 1 to alkyne. In general, although the exo-
thermicity of the addition Ph2P(S)H to phenylacetylene is
–30.9 kcal/mol, the scanned channel seems to be improba-
ble due to its high activation barrier.
1
analysis. In general, H, 13C and 31P NMR spectra of com-
pounds 13a–k reveal characteristic peaks of the corre-
sponding atoms in their typical regions.
We have demonstrated that functionalized alkenes 13a–
k, if necessary, can be easily converted into the thermody-
namically preferable E-isomers. Thus, by further heating at
80 °C for five hours, adduct 13k was converted into its E-
isomer (E)-13k, which was isolated in 98% yield (Scheme 1).
Ph
S
Ph
Ph
P
O
S
80 °C, 5 h
Ph
P
MeO
O
13k
OMe
E-13k, 98%
Scheme 1 Thermal Z/E-isomerization of adduct 13k
Conversely, addition of the tervalent form, Ph2P-SH, to
phenylacetylene proceeds in two steps to give the experi-
mentally observable Z-isomer (Z)-13c (Figure 2). The for-
mation of a P–C bond in this mechanism takes place in the
first stage, when the pre-reaction complex B is transformed
into the metastable intermediate C via transition state TS2,
with an activation barrier of 33.2 kcal/mol. Essentially, this
stage represents nucleophilic addition of the Ph2P-SH mole-
cule (as P-nucleophile) to phenylacetylene, proceeding as a
trans-selective process. The following intramolecular [1,4-
H] shift within intermediate C occurs via transition state
TS2 with an activation barrier of 27.5 kcal/mol to give prod-
As expected, phosphine chalcogenides 13a–k could be
easily reduced to the corresponding phosphines. For exam-
ple, refluxing of phosphine sulfide 13d with Na wire (tolu-
ene, 1 h) furnished phosphine 14 as mixture of Z/E-isomers
in 85% yield (Scheme 2).
Understanding the mechanism of the disclosed reaction
represents an important fundamental task. On the one
hand, the substrate scope for this reaction (Table 1) sug-
gested its radical character. On the other hand, it was estab-
lished that the inclusion of 2,2,6,6-tetramethylpiperidine-
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A. V. Artem’ev et al.
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TS1
Ph
Ph
S
P
H
66.6
Ph
H
PhC≡CH
+
Ph2P(S)H
–2.4
Ph
reaction coordinate
0.0
A
(E)-13c
Ph
S
Ph
H
P
P
–30.9
Ph
S
Ph
Ph
H
Figure 1 Free-energy profile for the addition of Ph2P(S)H to phenylacetylene according to B3LYP/6-311+G(d,p) computations (gas phase)
uct (Z)-13c. Notably, whereas the total exothermicity of
this pathway is only –26.2 kcal/mol, it is associated with
lower activation barriers than the mechanism with partici-
pation of Ph2P(S)H (33.2 and 27.5 vs. 66.6 kcal/mol). Thus,
the reaction route involving tautomerized secondary phos-
phine chalcogenides, R2P-XH, is preferable because it has a
lower barrier and because it leads to the formation of the
kinetically controlled isomer (Z)-13c, as observed.
been developed. This general reaction proceeds smoothly
under mild heating to afford the anti-Markovnikov
monoadducts of Z-structure in good yields. Preliminary DFT
computations have shown that the formation of these ad-
ducts is a kinetically controlled process that occurs through
tautomerization of secondary phosphine chalcogenides and
subsequent nucleophilic addition of the resulting tervalent
acids to alkynes. The alkenylphosphine chalcogenides thus
prepared can be used as building blocks for organic synthe-
sis, supporting ligands for the stabilization of nanoparticles,
and as prospective materials for switchable devices.
In summary, the regio- and stereoselective addition of
secondary phosphine sulfides and selenides to diverse
alkynes under catalyst- and solvent-free conditions has
Ph
S
H
TS3
S
P
H
Ph
Ph
P
58.9
C
C
C
C
Ph
H
H
TS2
31.9
C
31.4
H
S
Ph
P
PhC≡CH
+
Ph2P-SH
Ph
C
C
H
reaction coordinate
B
0.0
–1.3
H
(Z)-13c
Ph
Ph
Ph
S
S
P
Ph
P
–26.2
Ph
Ph
H
Figure 2 Free-energy profile for the addition of Ph2P-SH (1A) to phenylacetylene according to B3LYP/6-311+G(d,p) computations (gas phase)
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13C NMR (100 MHz, CDCl3): δ = 14.0 (Me), 22.4 (CH2Me), 28.0 (CH2Pr),
1H, 13C, 28Si, 31P, and 77Se NMR spectra were recorded with a Bruker
AV-400 spectrometer at 400.13, 100.62, 79.46, 161.98, and
76.31 MHz, respectively. 1H NMR chemical shifts are expressed with
respect to residual protonated CDCl3 (δ = 7.27 ppm), which served as
an internal standard. 13C NMR shifts are expressed with respect to
CDCl3 (δ = 77.0 ppm). TMS, 85% H3PO4/D2O and Me2Se were used as
external standards for 28Si, 31P, and 77Se NMR, respectively. FTIR spec-
tra were recorded with a Bruker Vertex 70 spectrometer. The C, H mi-
croanalyses were performed with a Flash EA 1112 СHNS-O/MAS ana-
lyzer, and the P content was determined by combustion. Secondary
phosphine sulfides 1 and 3–5, and selenide 2 were synthesized by ox-
idation of the corresponding phosphines with S8 or gray selenium.10
Diphenylphosphine was purchased from Alfa-Aesar; the other phos-
phines were prepared from the corresponding styrenes or 2-vinylfu-
rane and red phosphorus according to a reported procedure.21 All re-
maining reactants and solvents were used as received (Aldrich, Alfa
Aesar, Acros Organics). The reaction was monitored by 31P NMR spec-
troscopic analysis by following the disappearance of the signal of the
initial phosphine chalcogenide and simultaneous appearance of a
new signal, corresponding to the formed adduct.
28.8 (CH2Bu), 30.9 (d, 3JP–C = 9.9 Hz, CH2C=), 31.5 (CH2Et), 121.9 (d, 1JP–C
=
75.9 Hz, PCH=), 128.5 (d, 3JP–C= 12.5 Hz, m-CPh), 131.3 (d, 4JP–C = 2.6 Hz,
2
1
p-CPh), 131.7 (d, JP–C = 11.2 Hz, o-CPh), 133.0 (d, JP–C= 75.4 Hz, ipso-
Ph), 153.3 (=CHCH2).
C
31P NMR (162 MHz, CDCl3): δ = 17.91 (satellites: 1JP–Se = 719 Hz).
77Se NMR (76 Hz, CDCl3): δ = –263 (1JP–Se = 719 Hz).
Anal. Calcd for C20H25PSe: С, 64.00; Н, 6.71; Р, 8.25. Found: С, 63.87; Н,
6.83; Р, 8.10.
Diphenyl[(Z)-2-phenylethenyl]phosphine Sulfide (13c)
Yield: 300 mg (94%); light-yellow oil.
IR (film): 3074, 3056, 3024, 3007, 2925, 2852, 1677, 1594, 1492,
1480, 1437, 1386, 1330, 1308, 1272, 1217, 1181, 1159, 1131, 1100,
1071, 1028, 998, 969, 924, 841, 776, 752, 726, 705, 693, 662, 640, 625,
602, 551, 527, 503, 460 cm–1
.
3
2
1H NMR (400 MHz, CDCl3): δ = 6.38 (dd, JH–H = 13.6, JP–H = 17.9 Hz,
1 H, PCH=), 6.99–7.01 (m, 2 H, o-CPhC), 7.26–7.47 (m, 3 H, m,p-CPhC and
3
3
6 H, m,p-CPhP), 7.81–7.87 (m, 4 H, o-CPhP), 7.41 (d, JH–H = 13.6, JP–H
42.5 Hz, 1 H, PhCH=).
=
Synthesis of Tertiary Phosphine Chalcogenides (Table 1); General
Procedure
13C NMR (100 MHz, CDCl3): δ = 123.1 (d, 1JP–C = 81.7 Hz, PCH=), 127.5
3
(o-CPhC), 128.3 (d, JP–C= 12.6 Hz, m-CPhP), 128.8 (p-CPhC), 130.1 (m-
A mixture of secondary phosphine chalcogenide 1–5 (1.0 mmol) and
alkyne 6–12 (1.0 mmol) was stirred at 80 °C for 5–13 h under an ar-
gon atmosphere. Upon completion of the reaction, the crude product
was purified by flash chromatography (neutral Al2O3; hexane–Et2O,
1:1) to give 13a–k in 60–94% yield.
2
1
C
PhC), 131.2 (d, JP–C = 10.0 Hz, o-CPhP), 131.1 (p-CPhP), 132.9 (d, JP–C
=
=
3
2
85.3 Hz, ipso-CPhP), 134.4 (d, JP–C = 6.9 Hz, ipso-CPhC), 146.5 (d, JP–C
2.3 Hz, PhCH=).
31P NMR (162 MHz, CDCl3): δ = 30.87.
Anal. Calcd for C20H17PS: С, 74.98; Н, 5.35; Р, 9.67. Found: С, 74.84; Н,
5.27; Р, 9.60.
(Z)-1-Octenyl(diphenyl)phosphine Sulfide (13a)
Yield: 255 mg (78%); light-yellow oil.
Diphenethyl[(Z)-2-phenylethenyl]phosphine Sulfide (13d)
IR (film): 3074, 3054, 2955, 2927, 1612, 1480, 1466, 1437, 1378,
1308, 1181, 1159, 1101, 1070, 1027, 999, 765, 750, 738, 719, 708,
Yield: 340 mg (90%); light-yellow oil.
693, 630, 613, 570, 506, 595 cm–1
.
IR (film): 3080, 3057, 3027, 2924, 2851, 1672, 1596, 1574, 1560,
1446, 1407, 1330, 1267, 1214, 1179, 1157, 1132, 1093, 1076, 1015,
966, 950, 922, 870, 843, 806, 775, 762, 737, 700, 655, 619, 603, 583,
1H NMR (400 MHz, CDCl3): δ = 0.80 (t, 3JH–H = 7.0 Hz, 3 H, CH3), 1.08–
1.10 [m, 4 H, (CH2)2Me], 1.15–1.29 (m, 2 H, CH2Pr), 1.24–1.28 (m, 2 H,
568, 513 cm–1
.
3
2
CH2Bu), 2.26–2.31 (m, 2 H, CH2CH=), 6.25 (dd, JH–H = 12.4, JP–H
=
3
3
1H NMR (400 MHz, CDCl3): δ = 2.02–2.12 (m, 4 H, CH2P), 2.72–2.79
(m, 4 H, CH2Ph), 5.92 (dd, 3JH–H = 13.7, 2JP–H = 17.8 Hz, 1 H, PCH=), 7.33
(dd, 3JH–H = 13.7, 3JP–H = 41.3 Hz, 1 H, PhCH=), 6.86–6.88 (m, 4 H, o-CPh),
7.17–7.19 (m, 5 H, m-CPh and p-CPh), 7.39–7.41 (m, 4 H, p-CPh and m-
23.5 Hz, 1 H, PCH=), 6.55 (ddt, JH–H = 12.4, 7.6, JP–H = 43.0 Hz, 1 H,
CH2CH=), 7.40–7.43 (m, 6 H, m,p-CPh), 7.84–7.89 (m, 4 H, o-CPh).
13C NMR (100 MHz, CDCl3): δ = 14.0 (Me), 22.5 (CH2Me), 28.2 (CH2Pr),
28.8 (CH2Bu), 30.9 (d, 3JP–C = 9.5 Hz, CH2C=), 31.5 (CH2Et), 122.9 (d, 1JP–C
=
=
3
2
C
Ph), 7.75–7.77 (m, 2 H, o-CPh).
84.5 Hz, =CHP), 128.5 (d, JP–C = 12.1 Hz, o-CPh), 131.1 (d, JP–C
10.8 Hz, o-CPh), 131.2 (p-CPh), 134.5 (d, 1JP–C= 84.2 Hz, ipso-CPh), 153.5
(=CHCH2).
1
13C NMR (100 MHz, CDCl3): δ = 28.7 (CH2Ph), 33.8 (d, JP–C = 52.0 Hz,
1
CH2P), 122.5 (d, JP–C = 71.5 Hz, PCH=), 126.3 (p-CPh), 128.0 (o-CPh),
3
31P NMR (162 MHz, CDCl3): δ = 27.26.
128.4 and 128.5 (m-CPh), 129.2 (p-CPh), 129.6 (o-CPh), 135.7 (d, JP–C
=
6.7 Hz, ipso-CPh), 140.4 (d, 3JP–C = 14.1 Hz, ipso-CPh), 145.7 (PhCH=).
Anal. Calcd for C20H25PS: С, 73.14; Н, 7.67; Р, 9.43. Found: С, 73.02; Н,
7.54; Р, 9.29.
31P NMR (162 MHz, CDCl3): δ = 36.76.
Anal. Calcd for C24H25PS: С, 76.56; Н, 6.69; Р, 8.23. Found: С, 76.41; Н,
6.75; Р, 8.14.
(Z)-1-Octenyl(diphenyl)phosphine Selenide (13b)
Yield: 282 mg (75%); light-yellow oil.
Bis[2-(2-furyl)ethyl]-(Z)-2-phenylethenylphosphine Sulfide (13e)
IR (film): 3073, 3053, 2954, 2926, 2855, 1713, 1611, 1587, 1573,
1481, 1465, 1436, 1377, 1333, 1309, 1183, 1159, 1097, 1070, 1027,
Yield: 316 mg (89%); light-yellow oil.
998, 747, 735, 705, 692, 619, 597, 553, 540, 504 cm–1
.
IR (film): 3113, 3057, 3026, 2918, 2851, 1595, 1574, 1506, 1492,
1445, 1405, 1384, 1335, 1232, 1215, 1177, 1147, 1073, 1028, 1008,
955, 916, 884, 848, 800, 778, 734, 700, 646, 617, 599, 575, 567,
3
1H NMR (400 MHz, CDCl3): δ = 0.80 (t, JH–H = 7.2 Hz, 3 H, CH3), 1.09
[m, 4 H, (CH2)2Me], 1.18 (m, 2 H, CH2Pr), 1.26 (m, 2 H, CH2Bu), 2.22
511 cm–1
.
3
3
2
(dt, JH–H = 7.2, 7.3 Hz, 2 H, CH2CH=), 6.29 (dd, JH–H = 12.4, JP–H
=
3
3
23.1 Hz, 1 H, PCH=), 6.52 (ddt, JH–H = 12.4, 7.7, JP–H = 43.3 Hz, 1 H,
CH2CH=), 7.42 (m, 6 H, m,p-CPh), 7.86 (m, 4 H, o-CPh).
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A. V. Artem’ev et al.
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Synthesis
1H NMR (400 MHz, CDCl3): δ = 2.08–2.16 (m, 4 H, CH2P), 2.82–2.88
(m, 4 H, CH2Fur), 5.84 (dd, 3JH–H = 13.6, 2JP–H = 18.1 Hz, 1 H, PCH=), 5.89
(dd, 3JH–H= 3.2, 0.7 Hz, 2 H, H-3Fur), 6.21 (dd, 3JH–H = 3.2, 1.8 Hz, 2 H, H-
1H NMR (400 MHz, CDCl3): δ = 4.42–4.44 (m, 2 H, CH2O), 6.18 (dd, 3JH–H
13.9, JP–H = 24.9 Hz, 1 H, PCH=), 6.93 (ddt, JH–H = 4.5, 13.9, JP–H
40.0 Hz, 1 H, CH2CH=), 7.44–7.51 (m, 6 H, m,p-CPh), 7.66–7.71 (m, 4 H,
o-CPh).
=
=
2
3
3
4
Fur), 7.23 (d, 3JH–H = 13.6 Hz, 1 H, PhCH=), 7.23 (dd, 3JH–H = 1.8, 0.7 Hz,
2 H, H-5Fur), 7.34–7.37 (m, 3 H, m,p-CPh), 7.72–7.74 (m, 2 H, o-CPh).
13C NMR (100 MHz, CDCl3): δ = 61.0 (d, 3JP–C = 8.2 Hz, CH2O), 121.1 (d,
13C NMR (100 MHz, CDCl3): δ = 21.4 (d, 2JP–C= 2.2 Hz, CH2Fur), 30.5 (d,
1JP–C = 98.7 Hz, =CHP), 128.7 (d, 3JP–C = 12.1 Hz, m-CPh), 131.1 (d, 2JP–C
=
1
2JP–C= 53.2 Hz, CH2P), 105.8 (C3Fur), 110.4 (C4Fur), 122.5 (d, JP–C
=
10.3 Hz, o-CPh), 132.1 (d, 4JP–C = 1.7 Hz, p-CPh), 131.8 (d, 1JP–C = 84.5 Hz,
ipso-CPh), 153.6 (CH2CH=).
31P NMR (162 MHz, CDCl3): δ = 26.41.
72.0 Hz, PCH=), 128.5 (m-CPh), 129.3 (p-CPh), 129.5 (d, 3JP–C = 1.7 Hz, o-
3
2
C
Ph), 135.7 (d, JP–C = 6.7 Hz, ipso-CPh), 141.6 (C5Fur), 146.1 (d, JP–C =
2.2 Hz, PhCH=), 153.7 (d, 1JP–C = 16.4 Hz, C2Fur).
31P NMR (162 MHz, CDCl3): δ = 36.89.
Anal. Calcd for C15H15OPS: С, 65.68; Н, 5.51; Р, 11.29. Found: С, 65.59;
Н, 5.40; Р, 11.13.
Anal. Calcd for C20H21O2PS: С, 67.40; Н, 5.94; Р, 8.69. Found: С, 67.31;
Н, 6.05; Р, 8.45.
Diphenyl[(Z)-3-methyl-but-1-enyl-3-ol]phosphine Sulfide (13i)
Yield: 180 mg (60%); light-yellow oil.
Diphenyl[(Z)-2-phenylethenyl]phosphine Selenide (13f)
IR (film): 3004, 3056, 2975, 2928, 2869, 1619, 1601, 1591, 1574,
1548, 1481, 1437, 1378, 1359, 1309, 1263, 1166, 1120, 1100, 1070,
1027, 999, 967, 924, 913, 850, 813, 737, 715, 693, 656, 615, 561, 518,
Yield: 305 mg (83%); light-yellow oil.
IR (film): 3073, 3054, 3025, 3067, 2920, 1679, 1594, 1572, 1493,
1479, 1437, 1386, 1330, 1309, 1283, 1215, 1182, 1158, 1096, 1071,
1028, 998, 971, 923, 839, 781, 751, 724, 703, 694, 653, 613, 601, 578,
494 cm–1
.
1H NMR (400 MHz, CDCl3): δ = 1.46 (s, 6 H, Me), 5.93 (dd, 3JH–H = 14.0,
2JP–H = 24.3 Hz, 1 H, =CHP), 6.51 (s, 1 H, OH), 6.85 (dd, 3JH–H = 14.0, 3JP–H
40.2 Hz, 1 H, =CHC), 7.46–7.52 (m, 6 H, m,p-CPh), 7.71–7.74 (m, 4 H, o-
Ph).
559, 528, 500, 487, 456 cm–1
.
=
3
2
1H NMR (400 MHz, CDCl3): δ = 6.41 (dd, JH–H = 13.4, JP–H = 18.0 Hz,
1 H, =CHP), 7.01–7.02 (m, 2 H, o-CPhC), 7.26–7.48 (m, 9 H, m,p-CPhC
,
C
m,p-CPhP), 7.39 (d, 3JH–H = 13.4, 3JP–H = 42.9 Hz, 1 H, =CHPh), 7.83–7.89
(m, 4 H, o-CPhP).
13C NMR (100 MHz, CDCl3): δ = 30.4 (Me), 71.0 (d, JP–C = 7.3 Hz,
Me2C), 117.8 (d, 1JP–C = 98.3 Hz, =CHP), 128.7 (d, 3JP–C= 12.5 Hz, m-CPh),
131.3 (d, 2JP–C = 9.9 Hz, o-CPh), 131.1 (d, 4JP–C = 2.2 Hz, p-CPh), 133.1 (d,
1JP–C = 107.3 Hz, ipso-CPh), 162.0 (d, 2JP–C = 1.4 Hz, =CHC).
3
13C NMR (100 MHz, CDCl3): δ = 122.1 (d, 1JP–C = 74.2 Hz, =CHP), 127.5
3
(o-CPhC), 128.4 (d, JP–C= 12.2 Hz, m-CPhP), 128.8 (p-CPhC), 130.2 (m-
3
2
C
PhC), 131.3 (d, JP–C = 2.7 Hz, p-CPhP), 131.7 (d, JP–C = 10.7 Hz, o-CPhP),
31P NMR (162 MHz, CDCl3): δ = 27.55.
1
3
131.4 (d, JP–C = 77.1 Hz, ipso-CPhP), 134.3 (d, JP–C = 6.9 Hz, ipso-CPhC),
Anal. Calcd for C17H19OPS: С, 67.53; Н, 6.33; Р, 10.24. Found: С, 67.42;
Н, 6.37; Р, 10.04.
145.9 (d, 2JP–C = 2.1 Hz, =CHPh).
31P NMR (162 MHz, CDCl3): δ = 21.07 (satellites: 1JP–Se = 717 Hz).
77Se NMR (76 Hz, CDCl3): δ = –266 (1JP–Se = 717 Hz).
Diphenyl[(Z)-2-(trimethylsilyl)ethenyl]phosphine Sulfide (13j)
Anal. Calcd for C20H17PSe: С, 65.40; Н, 4.67; Р, 8.43. Found: С, 65.51; Н,
4.63; Р, 8.28.
Yield: 290 mg (92%); light-yellow oil.
IR (film): 3074, 3055, 2953, 2896, 1480, 1436, 1308, 1247, 1183,
1160, 1102, 1070, 1027, 999, 843, 739, 718, 708, 692, 659, 609, 567,
536, 492 cm–1
.
(Z)-2-(4-Methylphenyl)ethenyl(diphenyl)phosphine Sulfide (13g)
Yield: 300 mg (90%); light-yellow oil.
1H NMR (400 MHz, CDCl3): δ = 0.15 (s, 9 H, Me), 7.00 (dd, 3JH–H = 17.0,
3JP–H = 57.2 Hz, 1 H, SiCH=), 7.26 (dd, 3JH–H = 17.0 Hz, 1 H, PCH=), 7.43–
7.47 (m, 6 H, m,p-CPh), 7.83–7.85 (m, 4 H, o-CPh).
IR (film): 3073, 3053, 3023, 3006, 2919, 2857, 1673, 1606, 1511,
1492, 1480, 1437, 1310, 1276, 1183, 1101, 1070, 1027, 998, 967, 824,
888, 745, 716, 694, 656, 633, 604, 551, 525, 503, 490 cm–1
.
3
13C NMR (100 MHz, CDCl3): δ = 0.7 (Me), 128.6 (d, JP–C = 12.1 Hz, m-
1H NMR (400 MHz, CDCl3): δ = 2.17 (s, 3 H, Me), 6.31 (dd, 3JH–H = 13.8,
CPh), 131.3 (d, JP–C = 2.2 Hz, p-CPh), 131.5 (d, JP–C = 10.8 Hz, o-CPh),
4
2
3
1
1
2JP–H = 18.0 Hz, 1 H, PCH=), 6.83 (d, JH–H = 8.0 Hz, 2 H, 3,5-CAr), 7.28–
131.9 (d, JP–C = 83.6 Hz, ipso-CPh), 141.0 (d, JP–C = 83.2 Hz, PCH=),
3
3
7.33 (m, 6 H, m,p-CPh), 7.38 (d, JH–H = 13.8, JP–H = 42.4 Hz, 1 H,
156.2 (d, 1JP–C = 10.7 Hz, SiCH=).
PhCH=), 7.39 (d, 3JH–H = 8.0 Hz, 2 H, 2,6-CAr), 7.82–7.85 (m, 4 H, o-CPh).
31P NMR (162 MHz, CDCl3): δ = 32.13.
29Si NMR (80 MHz, CDCl3): δ = 7.09.
13C NMR (100 MHz, CDCl3): δ = 21.3 (Me), 121.3 (d, JP–C = 81.9 Hz,
1
PCH=), 128.3 (3,5-CAr), 128.4 (d, 3JP–C = 12.4 Hz, m-CPh), 131.3 (d, 4JP–C
=
Anal. Calcd for C17H21PSSi: С, 64.52; Н, 6.69; Р, 9.79. Found: С, 64.55;
Н, 6.50; Р, 9.57.
3
3
3.0 Hz, p-CPh), 131.1 (d, JP–C = 10.7 Hz, o-CPh), 130.6 (d, JP–C = 1.2 Hz,
1
1
2,6-CAr), 131.8 (d, JP–C= 6.9 Hz, 1-CAr), 133.5 (d, JP–C = 85.2 Hz, ipso-
C
Ph), 139.2 (4-CAr), 146.8 (d, 2JP–C = 2.3 Hz, PhCH=).
Diphenyl[(Z)-(methylpropenoate)]phosphine Sulfide (13k)
31P NMR (162 MHz, CDCl3): δ = 30.94.
Yield: 254 mg (84%); light-yellow oil.
Anal. Calcd for C21H19PS: С, 75.42; Н, 5.73; Р, 9.26. Found: С, 75.36; Н,
5.63; Р, 9.09.
IR (film): 3059, 2950, 2923, 2850, 1731, 1606, 1584, 1274, 1221,
1171, 1101, 1071, 999, 949, 926, 869, 814, 743, 718, 693, 625, 613,
562, 504 cm–1
.
Diphenyl[(Z)-propenyl-3-ol]phosphine Sulfide (13h)
1H NMR (400 MHz, CDCl3): δ = 3.32 (s, 3 H, Me), 6.65 (dd, 3JH–H = 13.2,
Yield: 222 mg (81%); light-yellow oil.
3
2
3JP–H = 38.2 Hz, 1 H, =CHC), 6.86 (dd, JH–H = 13.2, JP–H = 17.2 Hz, 1 H,
IR (film): 3430, 3077, 2955, 2919, 2851, 1730, 1590, 1437, 1385,
1310, 1261, 1160, 1101, 1027, 1012, 804, 748, 719, 693, 653, 553,
=CHP), 7.41–7.46 (m, 6 H, m,p-CPh), 7.82–7.87 (m, 4 H, o-CPh).
524 cm–1
.
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2015, 47, 263–271

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Synthesis
13C NMR (100 MHz, CDCl3): δ = 51.5 (Me), 128.6 (d, 3JP–C = 12.9 Hz, m-
Supporting Information
C
Ph), 131.1 (d, 2JP–C = 10.8 Hz, o-CPh), 131.4 (d, 1JP–C = 83.2 Hz, ipso-CPh),
131.5 (d, 4JP–C = 2.6 Hz, p-CPh), 134.7 (d, 3JP–C = 3.0 Hz, =CHC), 136.6 (d,
1JP–C = 76.3 Hz, =CHP), 147.5 (C=O).
Supporting information for this article is available online at
http://dx.doi.org/10.1055/s-0034-1379207. Included are copies of
NMR spectra and details of the DFT computations.
S
u
p
p
ortiInfogrmoaitn
S
u
p
p
o
nrtogI
f
rmoaitn
31P NMR (162 MHz, CDCl3): δ = 33.66.
Anal. Calcd for C16H15O2PS: С, 63.56; Н, 5.00; Р, 10.25. Found: С, 63.58;
Н, 5.12; Р, 9.95.
References
(1) (a) Delacroix, O.; Gaumont, A. C. Curr. Org. Chem. 2005, 9, 1851.
(b) Arbuzova, S. N.; Gusarova, N. K.; Trofimov, B. A. ARKIVOC
2006, (v), 12. (c) Honaker, M. T.; Hovland, J. M.; Salvatore, R. N.
Curr. Org. Synth. 2007, 4, 31. (d) Wauters, I.; Debrouwer, W.;
Stevens, C. V. Beilstein J. Org. Chem. 2014, 10, 1064.
(2) (a) Bartels, B.; Martin, C. G.; Nelson, A.; Russell, M. G.; Warren, S.
Tetrahedron Lett. 1998, 39, 1637. (b) Ono, Y.; Han, L.-B. Tetrahe-
dron Lett. 2006, 47, 421. (c) Science of Synthesis, Houben Weyl
Methods of Molecular Transformations; Vol. 33; Georg Thieme
Verlag KG: Stuttgart, 2007, 665–694, 701–710. (d) Gonzalez-
Nogal, A. M.; Cuadrado, P.; Sarmentero, M. A. Tetrahedron 2010,
66, 9610.
Diphenyl[(E)-(methylpropenoate)]phosphine sulfide [(E)-13k]
Synthesized by heating adduct 13k in a sealed tube at 80 °C for 5 h.
Yield: 295 mg (98%); light-yellow oil.
IR (film): 3055, 2949, 2919, 2849, 1729, 1584, 1577, 1480, 1437,
1385, 1356, 1300, 1272, 1234, 1166, 1102, 1071, 1027, 999, 976, 927,
811, 747, 717, 692, 654, 631, 614, 508 cm–1
.
1H NMR (400 MHz, CDCl3): δ = 3.78 (s, 3 H, Me), 6.77 (dd, 3JH–H = 16.4,
3
3
2JP–H = 20.1 Hz, 1 H, =CHP), 7.65 (dd, JH–H = 16.4, JP–H = 19.9 Hz, 1 H,
CCH=), 7.45–7.52 (m, 6 H, m,p-CPh), 7.72–7.92 (m, 4 H, o-CPh).
13C NMR (100 MHz, CDCl3): δ = 52.2 (Me), 128.9 (d, 3JP–C = 12.5 Hz, m-
C
Ph), 131.5 (d, 2JP–C = 10.8 Hz, o-CPh), 131.5 (d, 1JP–C = 85.0 Hz, ipso-CPh),
(3) (a) Julienne, D.; Toulgoat, F.; Delacroix, O.; Gaumont, A.-C. Curr.
Org. Chem. 2010, 14, 1195. (b) Xi, C.; Yu, B.; Yan, X.; Tang, N.
Polyhedron 2013, 52, 1323.
132.1 (d, 4JP–C = 1.7 Hz, p-CPh), 136.2 (d, 3JP–C = 5.6 Hz, CCH=), 138.9 (d,
1JP–C = 77.6 Hz, PCH=), 164.9 (d, 3JP–C = 23.7 Hz, C=O).
31P NMR (162 MHz, CDCl3): δ = 36.10.
(4) (a) Glotova, T. E.; Dvorko, M. Yu.; Arbuzova, S. N.; Ushakov, I. A.;
Verkhoturova, S. I.; Gusarova, N. K.; Trofimov, B. A. Lett. Org.
Chem. 2007, 4, 109. (b) Greenberg, S.; Gibson, G. L.; Stephan, D.
W. Chem. Commun. 2009, 304. (c) Dvorko, M. Yu.; Glotova, T. E.;
Ushakov, I. A.; Gusarova, N. K. Russ. J. Org. Chem. 2010, 46, 485.
(5) For selected reviews, see: (a) Glueck, D. S. Top. Organomet.
Chem. 2010, 31, 65. (b) Xu, Q.; Han, L.-B. J. Organomet. Chem.
2011, 696, 130. (c) Xu, Q.; Zhou, Y.-B.; Zhao, C.-Q.; Yin, S.-F.;
Han, L.-B. Mini-Rev. Med. Chem. 2013, 13, 824. (d) Pullarkat, S.
A.; Leung, P.-H. Top. Organomet. Chem. 2013, 43, 145. (e) Tanaka,
M. Top. Organomet. Chem. 2013, 43, 167. (f) Koshti, V.; Gaikwad,
S.; Chikkali, S. H. Coord. Chem. Rev. 2014, 265, 52.
Anal. Calcd for C16H15O2PS: С, 63.56; Н, 5.00; Р, 10.25. Found: С, 63.41;
Н, 5.13; Р, 10.16.
Diphenethyl[(Z)-2-phenylethenyl]phosphine (14)
Prepared by heating phosphine sulfide 13d (342 mg, 0.9 mmol) to re-
flux with sodium wire (62 mg, 2.7 mmol) in toluene (15 mL) for 1 h
(reaction monitored by TLC). The mixture was then cooled and fil-
tered though Celite. The solvent from the filtrate was removed in vac-
uo to give phosphine 14 (264 mg, 85%) as a mixture of Z/E isomers in
a 75:25 ratio.
(6) (a) Semenzin, D.; Etemad-Moghadam, G.; Albouy, D.; Diallo, O.;
Koenig, M. J. Org. Chem. 1997, 62, 2414. (b) Parsons, A. F.;
Sharpe, D. J.; Taylor, P. Synlett 2005, 1. (c) Jessop, C. M.; Parsons,
A. F.; Routledge, A.; Irvine, D. J. Eur. J. Org. Chem. 2006, 1547.
(7) (a) Mimeau, D.; Gaumont, A.-C. J. Org. Chem. 2003, 68, 7016.
(b) Guenin, E.; Meziane, D. Curr. Org. Chem. 2011, 15, 3465.
(c) Keglevich, G.; Bálint, E.; Takács, J.; Drahos, L.; Huben, K.;
Jankowski, S. Curr. Org. Synth. 2014, 11, 161.
(8) Alonso, F.; Moglie, Y.; Radivoy, G.; Yus, M. Green Chem. 2012, 14,
2699.
(9) Malysheva, S. F.; Gusarova, N. K.; Artem’ev, A. V.; Belogorlova, N.
A.; Albanov, A. I.; Borodina, T. N.; Smirnov, V. I.; Trofimov, B. A.
Eur. J. Org. Chem. 2014, 2516.
(Z)-14
1H NMR (400 MHz, CDCl3): δ = 1.81 (m, 4 H, CH2P), 2.70 (m, 4 H,
CH2Ph), 6.10 (dd, 2JH–P = 3.1, 3JH–H = 12.8 Hz, 1 H, =CHP), 7.07–7.65 (m,
16 H, =CHPh, Ph).
31P NMR (162 MHz, CDCl3): δ = –41.52.
(E)-14
1H NMR (400 MHz, CDCl3): δ = 1.83 (m, 4 H, CH2P), 2.77 (m, 4 H,
CH2Ph), 6.45 (dd, 3JH–P = 3.0, 3JH–H = 17.2 Hz, 1 H, =CHP), 6.98 (dd, 3JH–P
13.0, 3JH–H = 17.2 Hz, 1 H, =CHPh), 7.03–7.56 (m, 15 H, Ph).
=
31P NMR (162 MHz, CDCl3): δ = –26.12.
(10) (a) Gusarova, N. K.; Bogdanova, M. V.; Ivanova, N. I.;
Chernysheva, N. A.; Sukhov, B. G.; Sinegovskaya, L. M.; Kazheva,
O. N.; Alexandrov, G. G.; Dyachenko, O. A.; Trofimov, B. A. Syn-
thesis 2005, 3103. (b) Sukhov, B. G.; Gusarova, N. K.; Ivanova, N.
I.; Bogdanova, M. V.; Kazheva, O. N.; Alexandrov, G. G.;
Dyachenko, O. A.; Sinegovskaya, L. M.; Malysheva, S. F.;
Trofimov, B. A. J. Struct. Chem. 2005, 46, 1066. (c) Malysheva, S.
F.; Artem’ev, A. V.; Gusarova, N. K.; Timokhin, B. V.; Tatarinova,
A. A.; Trofimov, B. A. Russ. J. Gen. Chem. 2009, 79, 1617.
(11) Trofimov, B. A.; Malysheva, S. F.; Gusarova, N. K.; Belogorlova, N.
A.; Vasilevsky, S. F.; Kobychev, V. B.; Sukhov, B. G.; Ushakov, I. A.
Mendeleev Commun. 2007, 17, 181.
Anal. Calcd for C24H25P: С, 83.69; H, 7.32. Found: С, 83.54; H, 7.53.
Acknowledgment
This work was supported by the President of the Russian Federation
(program for the support of leading scientific schools, grant NSh-
156.2014.3).
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2015, 47, 263–271

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Synthesis
(12) Trofimov, B. A.; Gusarova, N. K.; Arbuzova, S. N.; Ivanova, N. I.;
Artem’ev, A. V.; Volkov, P. A.; Ushakov, I. A.; Malysheva, S. F.;
Kuimov, V. A. J. Organomet. Chem. 2009, 694, 677.
(16) Glotova, T. E.; Dvorko, M. Yu.; Gusarova, N. K.; Arbuzova, S. N.;
Ushakov, I. A.; Kazantseva, T. I.; Trofimov, B. A. Phosphorus,
Sulfur Silicon Relat. Elem. 2008, 183, 1396.
(13) Gusarova, N. K.; Malysheva, S. F.; Belogorlova, N. A.; Kuimov, V.
A.; Ushakov, I. A.; Trofimov, B. A. Russ. Chem. Bull. 2009, 58, 234.
(14) Arbuzova, S. N.; Gusarova, N. K.; Bogdanova, M. V.; Ivanova, N. I.;
Ushakov, I. A.; Mal’kina, A. G.; Trofimov, B. A. Mendeleev
Commun. 2005, 15, 183.
(15) Arbuzova, S. N.; Gusarova, N. K.; Bogdanova, M. V.; Ivanova, N. I.;
Ushakov, I. A.; Mal’kina, A. G.; Trofimov, B. A. Mendeleev
Commun. 2007, 17, 325.
(17) Li, J.-N.; Liu, L.; Fu, Y.; Guo, Q.-X. Tetrahedron 2006, 62, 4453.
(18) Trofimov, B. A.; Artem’ev, A. V.; Malysheva, S. F.; Gusarova, N. K.
Dokl. Chem. 2009, 428, 225.
(19) Becke, A. D. J. Chem. Phys. 1993, 98, 5648.
(20) For example, see: Allefeld, N.; Grasse, M.; Ignat’ev, N.; Hoge, B.
Chem. Eur. J. 2014, 20, 8615.
(21) Trofimov, B. A.; Brandsma, L.; Arbuzova, S. N.; Malysheva, S. F.;
Gusarova, N. K. Tetrahedron Lett. 1994, 35, 7647.
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2015, 47, 263–271