Four-Component Reaction between Secondary Phosphines, Primary Amines, Aldehydes, and Chalcogens: A Facile Access to Functionalized α-Aminophosphine Chalcogenides

Article abstract of DOI:10.1055/s-0036-1588127

The original four-component reaction between secondary phosphines, primary amines, aldehydes, and elemental sulfur or selenium occurs chemoselectively under mild conditions (60 °C, benzene, 3-9 h) to afford the hitherto unknown functionalized α-aminophosphine sulfides and selenides in good to excellent yields.

Full text of DOI:10.1055/s-0036-1588127

SYNTHESIS
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© Georg Thieme Verlag Stuttgart · New York
2016, 48, A–H
paper
A
A. V. Artemev et al.
Paper
Synthesis
Four-Component Reaction between Secondary Phosphines,
Primary Amines, Aldehydes, and Chalcogens: A Facile Access to
Functionalized α-Aminophosphine Chalcogenides
Alexander V. Artem’eva
Nikita A. Kolyvanova
Ludmila A. Oparinaa
Nina K. Gusarovaa
Anastasiya O. Sutyrinaa
Irina Yu. Bagryanskayab,c
Boris A. Trofimov*a
X
P
R1
R1
R2
NH
O
H
60 °C
– H2O
R2 NH2
+
R3
R1
R1
P
H
+
+ S8 or Se
R3
•
•
•
C–P/C–N/P–X bond formation in one-pot
Highly chemoselective and atom-economic
Catalyst-free process
12 examples
up to 90% yield
a A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch,
Russian Academy of Sciences, 1 Favorsky Str., Irkutsk 664033,
Russian Federation
boris_trofimov@irioch.irk.ru
b N. N. Vorozhtsov Novosibirsk Institute of Organic Chemistry,
Siberian Branch of Russian Academy of Sciences, 9, Akad.
Lavrentiev Ave., Novosibirsk 630090, Russian Federation
c Novosibirsk State University (National Research University),
Department of Natural Sciences, 2, Pirogova Str., Novosibirsk
630090, Russian Federation
Received: 26.07.2016
Accepted after revision: 04.12.2016
Published online: 19.12.2016
phonium enolate zwitterions.7 Subsequently, the versatile
methodology based on interaction of tertiary phosphines
with electron-deficient alkynes (enynes, diynes) and a third
component (e.g., aldehydes, imines, isocyanates, alkenes,
etc.) has been successfully employed for the syntheses of
the functionalized phosphoranes.8 In this avenue, less stud-
ied are multicomponent reactions with participation of pri-
mary or secondary phosphines, although they are also of a
great importance. Thus, the rapid atom-economic method
for the synthesis of diselenophosphinates, Cat[Se2PR2]
DOI: 10.1055/s-0036-1588127; Art ID: ss-2016-n0525-op
Abstract The original four-component reaction between secondary
phosphines, primary amines, aldehydes, and elemental sulfur or seleni-
um occurs chemoselectively under mild conditions (60 °C, benzene, 3–
9 h) to afford the hitherto unknown functionalized α-aminophosphine
sulfides and selenides in good to excellent yields.
Key words chemoselectivity, C–P and C–N bond formation, one-pot
synthesis, aldehydes, amines, chalcogens, phosphines
+
(Cat = Li+, Na+, K+, NH4 , etc.), has been elaborated using re-
action of secondary phosphines with elemental selenium
and various bases.9 The primary phosphines in the similar
reaction gave trithiophosphonates, Cat2[S3PR], in good
yields.10 In addition, the convenient four-component syn-
thesis of thioselenophosphinates, Cat[Se(S)PR2], from sec-
ondary phosphines, elemental sulfur, selenium, and bases
should be mentioned.11 The recent application of secondary
phosphines in multicomponent reactions has been exem-
plified by one-pot synthesis of tertiary phosphine chalco-
genides, R2P(X)CH2CH2R′, from secondary phosphines,
alkenes, and sulfur or selenium.12 Noteworthy, performing
this reaction with two equivalents of selenium gave Se-es-
ters of diselenophosphinic acids, R2P(Se)SeCH(Me)R′, in ex-
cellent yields.13 Therefore, the design of new multicompo-
nent reactions, which lead to the formation of C–P bond is a
recognized challenge in organophosphorus chemistry.
Herein we report the original four-component reaction
between secondary phosphines, primary amines, alde-
hydes, and elemental chaclogens, providing a facile and ef-
ficient route to α-aminophosphine sulfides and selenides.
Multicomponent reactions represent one of the most ef-
ficient tools in the sustainable and target-oriented organic
synthesis.1 These reactions feature a reduction in the num-
ber of the preparative steps, simple and rapid implementa-
tion, high energy and atom economy, as well as environ-
mental friendliness.1
In organophosphorus chemistry, the multicomponent
reactions have attracted a special attention for a long time.
Among famous multicomponent reactions leading to the
organophosphorus products are the well-known Kabach-
nik–Fields2 and Atherton–Todd3 reactions as well as Clay–
Kinnear–Perren condensation.4 Over the past decade, a
plethora of novel multicomponent procedures for the syn-
thesis of diverse organophosphorus compounds have been
developed.5 For instance, stabilized phosphoranes were ob-
tained from the three-component reaction between tri-
phenylphosphine, dialkyl acetylenedicarboxylates, and
urea.6 The replacement of urea in this reaction by 4-pyri-
dinecarboxaldehyde delivers the stable tetravalent phos-
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2016, 48, A–H

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A. V. Artemev et al.
Paper
Synthesis
The latter can be regarded as S/Se- and C–P congeners of α-
aminophosphonates, which, being structural analogues of
α-amino acids, received wide attention in medicinal, bioor-
ganic, and agricultural chemistry.14 It is relevant for the
subject of this work to note that the data on α-aminophos-
phine oxides15 and especially, sulfides16 and selenides,16 are
very limited (in contrast to α-aminophosphonates).
As a first result, we have found that the secondary phos-
phines 1a–c, primary amines 2a–e, aldehydes 3a–e, and el-
emental sulfur or selenium interact in a four-component
type reaction, occurring under mild conditions (60 °C, ben-
zene, 3–9 h), to afford N-substituted α-aminophosphine
sulfides and selenides 4a–k in 52–90% isolated yields (Table
1). The stoichiometric ratio of the reactants was found to be
optimal to achieve the higher yields of the products. The or-
der of mixing the reactants affects chemoselectivity of the
four-component reaction just negligibly. Importantly, this
reaction, involving the formation of new C–P, C–N, and P–X
bonds (X = S, Se) in a one-pot, avoids usual application of
metal-based catalysts. The common side products of the re-
action, according to 31P{1H} NMR monitoring, are α-hy-
droxyphosphine chalcogenides, R1 P(X)CH(OH)R3 (X = S,
2
Se), formed in up to 10 mol% due to the competitive addi-
tion of the intermediate R1 P(X)H species (vide infra) to C=O
2
bond of the aldehydes.17 These impurities, however, can be
easily separated from the main products 4a–k by recrystal-
lization from ethanol or by column chromatography.
Table 1 Four-Component Synthesis of α-Aminophosphine Chalcogenides 4a–ka
X
R1
R1
R2
O
H
60 °C, 3–9 h
benzene
P
R2 NH2
+
+
1/8S8 or Se
R3
R1
R1
P
H
+
NH
R3
4a–k (52–90%)
3a–e
1a–c
2a–e
Entry Phosphine
Amine
Aldehyde
X
Time (h)
Product
Yield (%)b
71
S
Ph
Ph
H
N
O
P
P
P
NH2
PH
PH
Ph
1
S
4
3
H
2a
Ph
Ph
1a
Ph
4a
3a
Se
Ph
Ph
H
N
O
NH2
Ph
2
Se
83
90
H
2a
2b
Ph
Ph
1a
Ph
4b
3a
S
Ph
Ph
H
N
Ph
O
NH2
PH
O
3
S
3
9
O
O
H
O
Ph
1a
3b
4c
S
Ph
H
N
P
Ph
O
(1-naphthyl)NH2
2c
PH
4
S
S
72
66
Ph
Ph
3c
H
Ph
1a
Ph
4d
t-Bu
t-Bu
S
H
P
N
O
NH2
PH
Ph
5
3
Ph
H
2a
3a
t-Bu
t-Bu
1b
4e
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2016, 48, A–H

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A. V. Artemev et al.
Paper
Yield (%)b
69
Synthesis
Table 1 (continued)
Entry Phosphine
t-Bu
Amine
Aldehyde
X
Time (h)
Product
t-Bu
Se
H
N
P
O
NH2
PH
Ph
6
Se
3
Ph
H
2a
3a
3b
3b
t-Bu
t-Bu
1b
4f
t-Bu
t-Bu
S
H
N
P
O
H
Ph
PhNH2
2d
PH
7
S
3
74
O
O
t-Bu
t-Bu
1b
4g
t-Bu
t-Bu
Se
H
N
P
O
H
Ph
PhNH2
2d
PH
8
Se
3
69
O
O
t-Bu
t-Bu
1b
4h
t-Bu
O
t-Bu
O
S
H
P
N
O
H
Ph
PhNH2
2d
PH
9
S
3
63
O
O
3b
O
O
t-Bu
t-Bu
1c
4i
S
H
Ph
O
P
N
Ph
PhNH2
2d
PH
10
11
S
3.5
52
64
N
H
Ph
1a
N
3d
4j
Se
N
H
N
Ph
O
P
HC≡CCH2NH2
2e
N
PH
Se
3
H
Ph
1a
3e
4k
a Conditions: phosphine 1 (1 mmol), amine 2 (1 mmol), aldehyde 3 (1 mmol), elemental chalcogen (1 mmol), and benzene (4 mL) were stirred at 60 °С for 3–9 h.
b Isolated yields.
Table 1 displays that the reaction has a general charac-
ter over the primary amines bearing aromatic and unsatu-
rated substituents. On the other hand, the reaction tolerates
aryl-, hetaryl-, and alkenyl-substituted aldehydes as well as
elemental sulfur and selenium. The aliphatic aldehyde, bu-
tyraldehyde, was found to be ineffective in the reaction (ex-
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2016, 48, A–H

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A. V. Artemev et al.
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Synthesis
emplified by interaction of n-PrCHO with phosphine 1a, S8
or Se, and aniline under the elaborated conditions).
As seen from Table 1, the secondary phosphines 1a–c
show almost the same reactivity. Notably, diphenylphos-
phine, when reacted with allylamine, benzaldehyde, and
selenium under the same conditions, gave a mixture of dif-
ficult to separate organophosphorus compounds, among
which the target N-allyl-α-aminophosphine selenide was
1
identified by 31P NMR spectroscopy (δP = 46.1, JP,Se = 748
Hz). The structure of the amines 2a–e has little effect on
the time required for reaction completion, which is defined
mainly by the structure of aldehydes. Generally, cinnamal-
dehyde was less reactive than benzaldehyde and furfural.
The preparation of bis(α-aminophosphine sulfide) 4l in
35% yield (unoptimized) from p-phenylenediamine (2f),
phosphine 1c, aldehyde 3a, and elemental sulfur under the
same conditions (Scheme 1) additionally confirmed the
generality of the reaction, indicating that diamines could
also be involved into the synthesis.
Figure 1 X-ray crystal structure of α-aminophosphine sulfide 4d (see
Supporting Information for details)
mines B, which are in situ produced by the condensation of
amines 2 with aldehydes 3 (Scheme 2). Thus, the reaction
studied can be also considered as the first example of the
addition of secondary phosphine sulfides and selenides to
C=N bonds (some examples of the addition of R2PH species
to imines are known16a,18).
2 R2PH + 1,4-C6H4(NH2)2 + 2 PhC(O)H + 1/4 S8
2f
3a
1c
benzene,
60 °C, 5 h
OBu-t
O
H
H2O
R2 NH2
R3
t-BuO
+
2
3
X
P
R2
R1
R1
(B)
R1
X
H
R3
R2
NH
S or Se
N
Ph
HN
Ph
NH
S
P
H
R1
R1
P
P
P
R1
R3
S
1
A
4
Scheme 2 Possible reaction pathway
4l (35%)
OBu-t
t-BuO
It should be stressed that the developed method meets
some of principles of green chemistry,19 namely, high atom
economy, absence of any catalyst, and high energy efficien-
cy (reaction takes place under mild heating). Furthermore,
as starting secondary phosphines, we have used those syn-
thesized from elemental phosphorus and easily available
styrene (as well as substituted styrenes) by a one-pot pro-
cedure.20 The phosphine 1c was prepared for the first time
by this way in 56% yield.
To summarize, the efficient one-pot access to hitherto
unknown α-aminophosphine sulfides and selenides has
been elaborated based on original four-component reaction
between secondary phosphines, primary amines, alde-
hydes, and elemental sulfur or selenium, respectively. The
reaction proceeds under mild metal-free conditions in a
chemoselective manner to give diverse α-aminophosphine
chalcogenides in good to excellent yields. The diamines (ex-
emplified by p-phenylenediamine) also participate in the
four-component reaction to furnish the corresponding
bis(α-aminophosphine) dichalcogenides. The synthesized
compounds are prospective hemilabile N,S- and N,Se-
Scheme 1 Synthesis of bis(α-aminophosphine sulfide) 4l
The prepared phosphine sulfides are air- and moisture-
stable powders or oils. The selenides, however, are slowly
oxidized in air with release of red selenium, but under inert
atmosphere, they are quite stable. All compounds are well
soluble (expect for 4l) in dichloromethane, chloroform, and
tetrahydrofuran, and insoluble in diethyl ether and hexane.
The structures of the products were unambiguously proved
by X-ray crystal analysis (for 4d, Figure 1), NMR (1H, 13C,
31P), and FT-IR spectroscopy.
The 31P{1H} NMR monitoring of the reaction has shown
that its actual intermediates are secondary phosphine chal-
cogenides, which are generated in situ by initial oxidation
of phosphines 1 with elemental sulfur or selenium. Taking
into account this observation, the formation of α-amino-
phosphine chalcogenides 4a–l in the four-component reac-
tion could have originated through the addition of the sec-
ondary phosphine chalcogenides A to C=N bond of the aldi-
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A. V. Artemev et al.
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Synthesis
ligands for new metal complexes, promising extraction
agents of noble metals, and attractive building blocks for
design of new functional compounds. Investigations to ex-
tend the scope of the reaction (over natural amines and al-
dehydes) and to develop further its application in organic
synthesis are in progress.
FT-IR (KBr): 3290 (NH), 1641 (C=C), 1176 (C–N), 752 (P–C), 519, 500
cm–1 (P=Se).
1H NMR (400.13 MHz, CDCl3): δ = 7.46–7.04 (m, 15 H, 3 × C6H5), 5.88–
5.78 (m, 1 H, CH=), 5.13, 5.11 (2 br s, 2 H, CH2=), 4.17 (d, 2J = 9.8 Hz, 1
H, СH), 3.29 (dd, J = 14.1, 4.2 Hz, 1 H, CH2N), 3.13–2.59 (m, 6 H, CH2N,
CH2Ph, NH), 2.40–1.81 (m, 4 H, CH2P).
13C NMR (100.61 MHz, CDCl3): δ = 140.7, 140.5 (2 d, 3J = 15.0 Hz, i-C in
Ph), 135.7 (CH=), 135.2 (i-C in Ph), 128.7, 128.6, 128.4, 128.4, 128.2,
128.1, 126.6, 122.2 (o,m,p-C in Ph), 116.9 (CH2=), 61.0 (d, 1J = 50.7 Hz,
All reactions were performed under an argon atmosphere. The sol-
vents were distillated prior to use. Secondary phosphines 1a,b were
synthesized by hydrophosphination of styrene and 4-tert-butylsty-
rene, correspondingly, as previously described.18 The procedure for
the synthesis of earlier unknown phosphine 1c is given in the Sup-
porting Information. The 1H, 13C, and 31P NMR spectra were recorded
on Bruker DPX 400 and Bruker AV-400 spectrometers (400.13,
100.62, and 161.98 MHz, respectively). Chemical shifts were reported
in δ (ppm) relative to CDCl3 (1H, 13C) as internal standard or H3PO4
3
1
CH), 49.4 (d, J = 14.7 Hz, CH2), 30.7 (d, J = 40.7 Hz, CH2P), 29.7, 29.4
(CH2Ph), 28.9 (d, 1J = 39.1 Hz, CH2P).
31P NMR (161.98 MHz, CDCl3): δ = 48.55 (satellites: d, 1JP,Se = 702 Hz).
Anal. Calcd for C26H30NPSe (466.46): C, 66.95; H, 6.48; N, 3.00. Found:
С, 67.12; H, 6.25; N, 3.19.
Bis(2-phenylethyl)({[2-(ethenyloxy)ethyl]amino}(furan-2-
yl)methyl)phosphine Sulfide (4c)
(
31P) as external standard. Standard abbreviations are used to denote
Yield: 396 mg (90%); light yellow oil.
the signal multiplicities; nr m = near multiplet. The CHN microanaly-
ses were performed on a Flash EA 1112 Series elemental analyzer. FT-
IR spectra were recorded on a Bruker Vertex 70 spectrometer. Melting
points (uncorrected) were measured using a Kofler micro hot stage.
FT-IR (film): 3284 (NH), 3114 (=CH), 1634, 1618 (C=C), 1172 (C–N),
741 (P–C), 598 cm–1 (P=S).
1H NMR (400.13 MHz, CDCl3): δ = 7.47 (s, 1 H, H-5 in fur), 7.34–7.14
(m, 10 H, 2 × C6H5), 6.52–6.45 (m, 3 H, OCH=, H-3,4 in fur), 4.23–4.17
(m, 2 H, =CHtrans, CHN), 4.02 (d, 3J = 6.6 Hz, 1 H, =CHcis), 3.78 (nr m, 2 H,
OCH2), 3.09–2.78 (m, 6 H, NCH2, PhCH2), 2.59 (br s, 1 H, NH), 2.31–
1.88 (m, 4 H, PCH2).
One-Pot Synthesis of α-Aminophosphine Chalcogenides 4a–l; Gen-
eral Procedure
To a solution of secondary phosphine 1a–c (1 mmol), amine 2a–e (1
mmol), and aldehyde 3a–e (1 mmol) in benzene (4 mL) was added
powdered sulfur (S8) or amorphous Se (1 mmol). The mixture was
stirred at 60 °C for the time required to complete the reaction (Table
1). After complete conversion of the starting phosphine and interme-
diate secondary phosphine chalcogenide, the reaction mixture was
filtered and evaporated in vacuo. The crude product was purified by
recrystallization from EtOH or by column chromatography (silica gel,
EtOH–EtOAc, 3:1 v/v) and dried in vacuo (1 Torr) to give the desired
phosphine chalcogenides 4a–l.
13C NMR (100.61 MHz, CDCl3): δ = 150.4 (OCH=), 148.4 (d, 2J = 2.8 Hz,
C-2 in fur), 141.5 (d, 5J = 2.2 Hz, C-5 in fur), 139.8, 139.6 (2 d, 3J = 15.6
Hz, i-C in Ph), 127.4, 127.3 (o-C in Ph), 127.1, 127.0 (m-C in Ph), 125.2,
3
125.1 (p-C in Ph), 109.9 (C-4 in fur), 108.4 (d, J = 6.2 Hz, C-3 in fur),
85.5 (CH2=), 66.0 (OCH2), 56.6 (d, 1J = 59.9 Hz, CHN), 45.8 (d, 3J = 13.1
Hz, NCH2), 29.9, 28.9 (2 d, 1J = 47.2, 46.7 Hz, PCH2), 27.4, 27.2 (2 d,
2J = 2.0, 1.8 Hz, PhCH2).
31P NMR (161.98 MHz, CDCl3): δ = 55.93.
Anal. Calcd for С25H30NO2PS (439.55): C, 68.31; H, 6.88; N, 3.19.
Found: С, 68.45; H, 6.58; N, 3.41.
Bis(2-phenylethyl)[phenyl(prop-2-en-1-ylamino)methyl]phos-
phine Sulfide (4a)
Bis(2-phenylethyl)[(2E)-1-(naphthalen-1-ylamino)-3-phenylprop-
2-en-1-yl]phosphine Sulfide (4d)
Yield: 298 mg (71%); white powder; mp 87–88 °С.
FT-IR (KBr): 3279 (NH), 1642 (C=C), 1180 (C–N), 742 (P–C), 592 cm–1
(P=S).
Yield: 382 mg (72%); light yellow powder; mp 128–129 °С.
FT-IR (KBr): 3301 (NH), 1604, 1594, 1579 (C=CPh), 1281 (C–N), 757
(C–P), 674, 606 cm–1 (P=S).
1H NMR (400.13 MHz, CDCl3): δ = 7.45–7.03 (m, 15 H, 3 × C6H5), 5.89–
5.79 (m, 1 H, CH=), 5.14, 5.10 (2 br s, 2 H, CH2=), 4.11 (d, 2J = 10.2 Hz, 1
H, CH), 3.29 (dd, J = 14.0, 4.7 Hz, 1 H, CH2N), 3.10–2.59 (m, 6 H, CH2Ph,
CH2N, NH), 2.33–2.23, 2.17–2.07, 2.02–1.91, 1.83–1.73 (4 m, each 1 H,
CH2P).
13C NMR (100.61 MHz, CDCl3): δ = 140.9, 140.8 (2 d, 3J = 15.0, 14.3 Hz,
i-C in Ph), 135.8 (CH=), 135.5 (i-C in Ph), 128.7, 128.6, 128.5, 128.4,
128.2, 128.1, 126.4, 126.3 (o,m,p-C in Ph), 116.8 (H2C=), 61.9 (d,
1J = 57.3 Hz, CH), 49.6 (d, 3J = 14.6 Hz, CH2N), 31.0, 29.4 (2 d, 1J = 47.8,
46.2 Hz, CH2P), 28.8, 28.4 (2 d, 2J = 1.7 Hz, CH2Ph).
1H NMR (400.13 MHz, CDCl3): δ = 8.15 (d, 3J = 8.0 Hz, 1 H, H-8 in
naphth), 7.84 (d, 3J = 8.0 Hz, 1 H, H-5 in naphth), 7.58–7.51 (m, 2 H, H-
6,7 in naphth), 7.40–7.14 (m, 17 H, 3 × C6H5, H-3,4 in naphth), 6.80
(dd, J = 15.9, 4.3 Hz, 1 H, PhCH=), 6.68 (d, 3J = 6.6 Hz, 1 H, H-2 in
3
naphth), 6.34–7.27 (m, 1 H, CH=), 5.86 (t, J = 7.6 Hz, 1 H, NH), 4.54–
4.47 (m, 1 H, NCH), 3.10–3.04 (m, 4 H, CH2Ph), 2.49–2.17 (m, 4 H,
PCH2).
13C NMR (100.61 MHz, CDCl3): δ = 141.7 (d, 3J = 11.2 Hz, C-1 in
naphth), 140.4, 140.2 (2 d, 3J = 13.2 Hz, i-C in Ph), 135.6 (i-C in Ph),
134.6 (d, 3J = 11.0 Hz, =CHPh), 134.3 (C-10 in naphth), 128.7 (6 C, C-
3,5 in 3Ph), 128.6 (C-5 in naphth), 128.3, 128.2, 126.6 (9 C, o,p-C in
3Ph), 126.1, 126.0, 125.3, 124.4 (C-3,6,7,9 in naphth), 123.6 (=CH),
120.4 (C-8 in naphth), 118.9 (C-4 in naphth), 106.7 (C-2 in naphth),
55.7 (d, 1J = 55.2 Hz, CHN), 31.3, 31.0 (2 d, 1J = 45.9, 46.0 Hz, PCH2),
28.7 (CH2Ph).
31P NMR (161.98 MHz, CDCl3): δ = 55.78.
Anal. Calcd for C26H30NPS (419.56): C, 74.43; H, 7.21; N, 3.34. Found:
С, 74.61; H, 7.08; N, 3.45.
Bis(2-phenylethyl)[phenyl(prop-2-en-1-ylamino)methyl]phos-
phine Selenide (4b)
31P NMR (161.98 MHz, CDCl3): δ = 58.52.
Yield: 388 mg (83%); white powder; mp 91–92 °С.
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A. V. Artemev et al.
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Synthesis
Anal. Calcd for С35H34NPS (531.69): C, 79.06; H, 6.45; N, 2.63. Found:
С, 78.78; H, 6.12; N, 2.80.
127.9, 127.8 (C-2,6 in Ar), 125.6, 125.5 (C-3,5 in Ar), 119.1 (p-C in Ph),
3
114.3 (o-C in Ph), 111.3 (C-4 in fur), 109.3 (d, J = 5.7 Hz, C-3 in fur),
51.6 (d, 1J = 55.5 Hz, CHN), 34.3 [C(CH3)3], 32.0 (d, 1J = 45.8 Hz, PCH2),
31.3 [C(CH3)3], 30.8 (d, 1J = 46.8 Hz, PCH2), 28.2, 27.8 (2 d, 2J = 2.9, 2.6
Hz, ArCH2).
Bis[2-(4-tert-butylphenyl)ethyl][phenyl(prop-2-en-1-ylami-
no)methyl]phosphine Sulfide (4e)
31P NMR (161.98 MHz, CDCl3): δ = 59.28.
Yield: 350 mg (66%) white powder; mp 104–105 °С.
FT-IR (KBr): 3298 (NH), 1643 (C=C), 775 (P–C), 590 cm–1 (P=S).
Anal. Calcd for C35H44NOPS (557.77): C, 75.37; H, 7.95; N, 2.51. Found:
С, 75.27; H, 7.74; N, 2.40.
1H NMR (400.13 MHz, CDCl3): δ = 7.45–6.96 (m, 13 H, Ar, C6H5), 5.88–
5.78 (m, 1 H, CH=), 5.14, 5.10 (2 br s, 2 H, CH2=), 4.10 (d, 2J = 10.1 Hz, 1
H, CH), 3.28 (dd, J = 14.0, 4.7 Hz, 1 H, CH2N), 3.09–2.56 (m, 6 H, CH2Ar,
CH2N, NH), 2.30–1.71 (4 m, each 1 H, CH2P), 1.31, 1.28 (2 s, 18 H, 2 × t-
C4H9).
Bis[2-(4-tert-butylphenyl)ethyl][furan-2-yl(phenylamino)meth-
yl]phosphine Selenide (4h)
Yield: 416 mg (69%); grey powder; mp 99–100 °С.
13C NMR (100.61 MHz, CDCl3): δ = 149.3, 149.1 (C-4 in Ar), 137.8,
137.7 (2 d, 3J = 14.8, 13.9 Hz, C-1 in Ar), 135.9 (CH=), 135.6 (d, 2J = 2.4
Hz, i-C in Ph), 128.7 (o-C in Ph), 128.5, 128.4 (p,m-C in Ph), 127.9,
127.8 (C-3,5 in Ar), 125.5, 125.4 (C-2,6 in Ar), 116.8 (CH=), 61.9 (d,
1J = 57.0 Hz, CH), 49.6 (d, 3J = 14.6 Hz, CH2N), 34.3 [C(CH3)3], 31.3
[C(CH3)3], 30.9, 29.4 (2 d, 1J = 47.7, 46.2 Hz, CH2P), 28.3, 27.9 (2 d,
2J = 3.0, 2.8 Hz, CH2Ar).
FT-IR (KBr): 3320 (NH), 1180 (C–N), 748 (P–C), 564 cm–1 (P=Se).
1H NMR (400.13 MHz, CDCl3): δ = 7.45 (s, 1 H, H-5 in fur), 7.32–7.11
(m, 8 H, Ar), 7.03 (d, 3J = 7.8 Hz, 2 H, m-H in C6H5), 6.79 (t, 3J = 7.3 Hz, 1
H, p-H in C6H5), 6.68 (d, 3J = 7.9 Hz, 2 H, o-H in C6H5), 6.47, 6.39 (2 nr
m, each 1 H, H-3,4 in fur), 5.12 (t, 3J = 8.2 Hz, 1 H, NH), 4.88 (dd,
J = 10.6, 8.1 Hz, 1 H, CH), 3.05–2.80 (m, 3 H, CH2Ar), 2.52–2.36 (m, 3 H,
CH2Ar, PCH2), 2.16–2.01 (m, 2 H, PCH2), 1.30 (s, 18 H, 2 × t-C4H9).
13C NMR (100.61 MHz, CDCl3): δ = 149.5 (d, 3J = 3.3 Hz, C-2 in fur),
149.4 (p-C in Ph), 146.0 (d, 3J = 11.1 Hz, i-C in Ph), 142.4 (d, J = 2.6 Hz),
137.2, 137.1 (2 d, 3J = 26.2, 24.4 Hz, C-1 in Ar), 129.2 (m-C in Ph),
127.9 (d, J = 16.0 Hz, C-2,6 in Ar), 125.5 (d, J = 8.6 Hz, C-3,5 in Ar),
119.2 (p-C in Ph), 114.4 (o-C in Ph), 111.4 (o-C in Ph), 109.5 (d, 3J = 5.5
Hz, C-3 in fur), 50.5 (d, 1J = 49.4 Hz, CHN), 34.3 [C(CH3)3], 31.7 (d,
1J = 38.5 Hz, PCH2), 31.3 [C(CH3)3], 30.4 (d, 1J = 39.3 Hz, PCH2), 29.0,
28.7 (CH2Ar).
31P NMR (161.98 MHz, CDCl3): δ = 55.98.
Anal. Calcd for C34H46NPS (531.78): C, 76.79; H, 8.72; N, 2.63. Found:
С, 76.05; H, 8.55; N, 2.49.
Bis[2-(4-tert-butylphenyl)ethyl][phenyl(prop-2-en-1-ylami-
no)methyl]phosphine Selenide (4f)
Yield: 400 mg (69%); white powder; mp 104–105 °С.
FT-IR (KBr): 3302 (NH), 1642 (C=C), 1177 (C–N), 762 (P–C), 563 cm–1
(P=Se).
31P NMR (161.98 MHz, CDCl3): δ = 53.45 (satellites: d, 1JP,Se = 721 Hz).
Anal. Calcd for C35H44NOPSe (604.66): C, 69.52; H, 7.33; N, 2.32.
Found: С, 69.32; H, 7.15; N, 2.11.
1H NMR (400.13 MHz, CDCl3): δ = 7.46–6.95 (m, 13 H, Ar, C6H5), 5.88–
5.78 (m, 1 H, CH=), 5.13, 5.10 (2 nr m, each 1 H, CH2=), 4.16 (d, 2J = 9.6
Hz, 1 H, CH), 3.29 (dd, J = 14.0, 4.6 Hz, 1 H, CH2N), 3.09–2.87 (m, 3 H,
CH2N, NH, CH2Ar), 2.77–2.56 (m, 3 H, CH2Ar), 2.38–1.79 (m, 4 H,
CH2P), 1.30 (18 H, 2 × t-C4H9).
Bis[2-(4-tert-butoxyphenyl)ethyl][furan-2-yl(phenylamino)meth-
yl]phosphine Sulfide (4i)
Yield: 371 mg (63%); grey powder; mp 119–120 °С.
FT-IR (KBr): 3313 (NH), 1175 (N–C), 750 (P–C), 691 cm–1 (P=S).
13C NMR (100.61 MHz, CDCl3): δ = 149.3, 149.2 (C-4 in Ar), 137.6,
137.4 (2 d, 3J = 15.0 Hz, C-1 in Ar), 135.8 (CH=), 135.3 (d, 2J = 2.6 Hz, i-
4
5
C in Ph), 128.7 (d, J = 2.0 Hz, m-C in Ph), 128.5 (d, J = 2.8 Hz, p-C in
Ph), 128.4 (d, 3J = 5.0 Hz, o-C in Ph), 127.9, 127.8, 125.4, 125.3 (C-
2,3,5,6 in Ar), 116.9 (CH=), 60.9 (d, 1J = 50.6 Hz, CH), 49.5 (d, 2J = 14.9
Hz, CH2N), 34.2, 34.3 [C(CH3)3], 31.2 [C(CH3)3], 30.7 (d, 1J = 40.7 Hz,
CH2P), 29.1, 28.8 (2 d, 2J = 2.7, 2.5 Hz, CH2Ar), 28.8 (d, 1J = 38.8 Hz,
CH2P).
1H NMR (400.13 MHz, CDCl3): δ = 7.44 (s, 1 H, H-5 in fur), 7.16 (t,
3J = 7.3 Hz, 2 H, m-H in C6H5), 7.07, 6.98 (2 d, 3J = 8.0 Hz, each 2 H, H-
2,6 in Ar), 6.91–6.88 (m, 4 H, H-3,5 in Ar), 6.77 (t, 3J = 7.1 Hz, 1 H, p-H
in C6H5), 6.66 (d, 3J = 7.8 Hz, 2 H, o-H in C6H5), 6.43, 6.38 (2 br s, each 1
H, H-3,4 in fur), 5.09 (t, 3J = 7.8 Hz, 1 H, NH), 4.81 (dd, J = 10.3, 8.3 Hz,
1 H, CH), 3.05–2.78 (m, 3 H, CH2Ar), 2.51–2.22 (m, 3 H, CH2Ar, PCH2),
2.06–1.92 (m, 2 H, PCH2), 1.31 (s, 18 H, 2 × t-C4H9).
31P NMR (161.98 MHz, CDCl3): δ = 48.79 (satellites: d, 1JP,Se = 701 Hz).
Anal. Calcd for C34H46NPSe (578.67): C, 70.57; H, 8.01; N, 2.42. Found:
С, 70.33; H, 7.91; N 2.23.
13C NMR (100.61 MHz, CDCl3): δ = 153.8 (d, 3J = 3.1 Hz, C-2 in fur),
3
149.5 (C-4 in Ar), 146.0 (d, J = 11.2 Hz, i-C in Ph), 142.4 (C-5 in fur),
135.2, 135.1 (2 d, 3J = 14.6, 13.9 Hz, C-1 in Ar), 129.2 (m-C in Ph),
128.6, 128.5, 124.4, 124.3 (C-2,4,5,6 in Ar), 119.1 (p-C in Ph), 114.3 (o-
C in Ph), 111.4 (d, 3J = 5.6 Hz, C-3 in fur), 109.4 (C-4 in fur), 78.3
Bis[2-(4-tert-butylphenyl)ethyl][furan-2-yl(phenylamino)meth-
yl]phosphine Sulfide (4g)
1
1
[C(CH3)3], 51.5 (d, J = 55.4 Hz, CH), 32.0, 30.9 (2 d, J = 46.1, 47.0 Hz,
CH2P), 28.72 [C(CH3)3], 27.9, 27.6 (CH2Ar).
Yield: 412 mg (74%); grey powder; mp 123–124 °С.
FT-IR (KBr): 3329 (NH), 1181 (C–N), 750 (P–C), 691 cm–1 (P=S).
31P NMR (161.98 MHz, CDCl3): δ = 59.03.
1H NMR (400.13 MHz, CDCl3): δ = 7.45 (br s, 1 H, H-5 in fur), 7.32–
7.11 (m, 8 H, Ar), 7.02 (d, J = 8.2 Hz, 2 H, m-H in C6H5), 6.78 (t, J = 7.3
Hz, 1 H, p-H in C6H5), 6.67 (d, J = 7.8 Hz, 2 H, o-H in C6H5), 6.44, 6.39 (2
nr m, each 1 H, H-3,4 in fur), 5.10 (t, 3J = 8.2 Hz, 1 H, NH), 4.81 (dd,
J = 10.9, 7.8 Hz, 1 H, CH), 3.06–2.80 (m, 3 H, CH2Ar), 2.54–2.22 (m, 3 H,
CH2Ar, PCH2), 2.02–1.94 (m, 2 H, PCH2), 1.30 (br s, 18 H, 2 × t-C4H9).
Anal. Calcd for C35H44NO3PS (589.77): C, 71.28; H, 7.52; N, 2.37.
Found: С, 71.50; H, 7.29; N, 2.61.
Bis(2-phenylethyl)[phenylamino(2-pyridinyl)methyl]phosphine
Sulfide (4j)
Yield: 240 mg (52%); white powder; mp 106–107 °С.
FT-IR (KBr): 3329 (NH), 751 (P–C), 659, 613, 557 cm–1 (P=S).
13C NMR (100.61 MHz, CDCl3): δ = 149.7 (C-2 in fur), 149.5, 149.3 (C-4
in Ar), 146.1 (d, 3J = 11.1 Hz, i-C in Ph), 142.4 (d, 5J = 3.1 Hz, C-5 in fur),
137.4, 137.3 (2 d, 3J = 15.1, 14.3 Hz, C-1 in Ar), 129.2 (m-C in Ph),
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2016, 48, A–H

G
A. V. Artemev et al.
Paper
Synthesis
1H NMR (400.13 MHz, CDCl3): δ = 8.61 (d, 3J = 4.4 Hz, 1 H, H-6 in Py),
7.70 (t, 3J = 7.5 Hz, 1 H, H-3 in Py), 7.61 (d, 3J = 7.8 Hz, 1 H, H-4 in Py),
7.29–7.14 (m, 11 H, 2 × C6H5, H-5 in Py), 7.03 (d, 3J = 7.1 Hz, 2 H, m-H
in NC6H5), 6.76 (t, 3J = 7.3 Hz, 1 H, p-H in NC6H5), 6.69 (d, 3J = 8.1 Hz, 2
H, o-H in NC6H5), 5.53 (t, 3J = 8.4 Hz, 1 H, CH), 5.06 (nr m, 1 H, NH),
3.02–2.85 (m, 3 H, CH2Ar), 2.56–2.45 (m, 1 H, CH2Ar), 2.39–2.24 (m, 2
H, PCH2), 2.15–1.94 (m, 2 H, PCH2).
13C NMR (100.61 MHz, CDCl3): δ = 156.3 (C-6 in Py), 148.9 (C-1 in Py),
145.9 (d, 3J = 10.6 Hz, i-C in NPh), 140.5, 140.4 (2 d, 3J = 15.3, 14.4 Hz,
i-C in Ph), 136.9 (C-4 in Py), 129.3 (m-C in NPh), 128.6, 128.5, 128.2,
128.0, 126.4, 126.3 (o,m,p-C in Ph), 123.2 (C-5 in Py), 122.9 (C-3 in
Py), 118.8 (p-C in Ph), 114.2 (o-C in Ph), 58.4 (d, 1J = 50.1 Hz, CH), 32.1
(d, 1J = 46.1 Hz, CH2P), 30.5 (d, 1J = 46.8 Hz, CH2P), 28.7, 28.4 (CH2Ar),
Acknowledgment
The authors would like to acknowledge the Multi-Access Chemical
Service Center SB RAS for XRD measurements. The authors are also
grateful to the Baikal Analytical Center for spectral measurements.
This work was supported by the President of the Russian Federation
(program for the support of leading scientific schools, grant NSh-
7145.2016.3).
Supporting Information
Supporting information for this article is available online at
http://dx.doi.org/10.1055/s-0036-1588127. Included are the proce-
dure for synthesis of 1c, crystallography data for 4d, and copies of 1H,
31P NMR (161.98 MHz, CDCl3): δ = 59.27.
13C and 31P NMR spectra for all synthesized compounds.
S
u
p
p
ortiInfogrmoaitn
S
u
p
p
ortioInfgrmoaitn
Anal. Calcd for C28H29N2PS (456.583): С, 73.66; H, 6.40; N, 6.14.
Found: С, 73.82; H, 6.54; N, 6.09.
References
Bis(2-phenylethyl)[prop-2-in-1-ylamino(4-pyridinyl)meth-
yl]phosphine Selenide (4k)
(1) (a) Multicomponent Reactions in Organic Synthesis; Zhu, J.;
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(b) Multicomponent Reactions: Concepts and Applications for
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Yield: 300 mg (64%); light yellow oil.
FT-IR (KBr): 3297 (NH, ≡СН) 2219 (C≡C), 734 (P–C), 540, 569 cm–1
(P=Se).
1H NMR (400.13 MHz, CDCl3): δ = 8.65 (d, 3J = 5.4 Hz, 2 H, H-2,6 in Py),
7.37–7.18 (m, 10 H, 2 × C6H5), 7.07 (d, 3J = 7.2 Hz, 2 H, H-3,5 in Py),
4.40 (d, 2J = 10.2 Hz, 1 H, CHN), 3.57 (dd, 2J = 17.1, 3J = 2.0 Hz, 1 H,
CH2N), 3.14–2.72 (m, 6 H, CH2N, NH, CH2Ar), 2.36–2.15 (m, 3 H, CH2P,
≡СН), 2.09–1.82 (m, 2 H, CH2P).
13C NMR (100.61 MHz, CDCl3): δ = 149.9 (C-2,6 in Py), 143.7 (C-4 in
Py), 139.8 (d, 2J = 13.6 Hz, i-C in Ph), 128.4, 128.3, 128.0, 127.8, 126.3,
136.2 (o,m,p-C in Ph), 123.2 (C-3,5 in Py), 79.7 (≡СН), 72.8 (d, 4J = 4.6
Hz, ≡С–), 59.3 (d, 1J = 49.4 Hz, CH), 35.6 (d, 3J = 15.9 Hz, CH2), 30.1 (d,
1J = 41.2 Hz, CH2P), 29.2, 29.0 (CH2Ar), 28.5 (d, 1J = 38.9 Hz, CH2P).
31P NMR (161.98 MHz, CDCl3): δ = 48.49 (satellites: d, 1JP,Se = 718 Hz).
Anal. Calcd for C25H27N2PSe (465.429): C, 64.51; H, 5.85; N, 6.02.
Found: С, 64.33; H, 5.91; N, 6.23.
{[1,4-Phenylenebis(azanediyl)]bis(phenylmethylene)}bis{bis[4-
(tert-butoxy)phenethyl]}phosphine Sulfide (4l)
Prepared, following the general procedure, from p-phenylenediamine
(2f; 108 mg, 1.0 mmol), phosphine 1c (770 mg, 2.0 mmol), benzalde-
hyde (3a; 210 mg, 2.0 mmol), and elemental sulfur (64 mg, 2.0
mmol); yield: 392 mg (35%); white powder; mp 194–195 °С.
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FT-IR (KBr): 3361 (NH), 1163 (N–C), 768 (P–C), 722, 697 cm–1 (P=S).
1H NMR (400.13 MHz, CDCl3): δ = 7.42–7.29, 7.04–6.82 (m, 26 H, 2 ×
C6H5, Ar), 6.43 (s, 4 H, N–Ar–N), 5.04 (br s, 2 H, NH), 4.50 (d, 2J = 10.5
Hz, 2 H, CH), 3.02–2.84 (m, 4 H, CH2Ar), 2.71–2.61 (m, 2 H, CH2Ar),
2.38–2.16 (m, 6 H, CH2Ar, CH2P), 1.85–1.74 (m, 4 H, CH2P), 1.31, 129
(2 s, each 18 H, 2 × t-C4H9).
13C NMR (100.61 MHz, DMSO-d6): δ = 154.4, 153.0, 150.0, 137.9,
137.6, 136.8, 132.4, 129.8, 129.6, 129.5, 129.3, 129.2, 129.1, 128.9,
128.7, 124.9, 124.8, 117.6, 116.4, 78.8, 56.5 (d, 1J = 55.1 Hz, CH), 29.7,
29.6 [CH2Ar, [C(CH3)3], 28.3 (d, 1J = 50.2 Hz, CH2P).
31P NMR (161.98 MHz, CDCl3): δ = 58.24, 58.28.
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Anal. Calcd for C68H86N2O4P2S2 (1121.49): C, 72.82; H, 7.73; N, 2.50.
Found: С, 72.70; H, 7.52; N, 2.44.
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2016, 48, A–H

H
A. V. Artemev et al.
Paper
Synthesis
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© Georg Thieme Verlag Stuttgart · New York — Synthesis 2016, 48, A–H