Efficient synthesis of lupininium, anabasinium and quininium thioselenophosphinates via a multi-component reaction between secondary phosphines, sulfur, selenium and alkaloids

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Efficient Synthesis of Lupininium,
Anabasinium and Quininium
Thioselenophosphinates via a Multi-
component Reaction between Secondary
Phosphines, Sulfur, Selenium and
Alkaloids
Alexander V. Artem’ev a , Nina K. Gusarova a , Svetlana F. Malysheva
a , Yuriy V. Gatilov b & Victor I. Mamatyuk b
a A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the
Russian Academy of Sciences, Irkutsk, Russian Federation
b N. N. Vorozhtsov Novosibirsk Institute of Organic Chemistry,
Siberian Branch of the Russian Academy of Sciences, Novosibirsk,
Russian Federation
Available online: 21 May 2012
To cite this article: Alexander V. Artem’ev, Nina K. Gusarova, Svetlana F. Malysheva, Yuriy V.
Gatilov & Victor I. Mamatyuk (2012): Efficient Synthesis of Lupininium, Anabasinium and Quininium
Thioselenophosphinates via a Multi-component Reaction between Secondary Phosphines, Sulfur,
Selenium and Alkaloids, Organic Preparations and Procedures International: The New Journal for
Organic Synthesis, 44:3, 262-270
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Organic Preparations and Procedures International, 44:262–270, 2012
Copyright © Taylor & Francis Group, LLC
ISSN: 0030-4948 print / 1945-5453 online
DOI: 10.1080/00304948.2012.676523
Efficient Synthesis of Lupininium, Anabasinium and
Quininium Thioselenophosphinates via a
Multi-component Reaction between Secondary
Phosphines, Sulfur, Selenium and Alkaloids
Alexander V. Artem’ev,1 Nina K. Gusarova,1 Svetlana F.
Malysheva,1 Yuriy V. Gatilov,2 and Victor I. Mamatyuk2
1A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian
Academy of Sciences, Irkutsk, Russian Federation
2N. N. Vorozhtsov Novosibirsk Institute of Organic Chemistry, Siberian Branch
of the Russian Academy of Sciences, Novosibirsk, Russian Federation
Thioselenophosphinates [R2PSeSM (R = aryl or alkyl, M = alkali metal or ammonium)]
are key starting compounds for the synthesis of S- and Se-esters of thioselenophosphinic
acids1,2 as well as versatile ligands for metal complexes.3–6 The latter are convenient single-
source precursors to produce metal selenides nanocrystals having a wide range of unique
properties.7–9 Moreover, thioselenophosphinates represent rare anionic conjugate triads of
“S-P-Se” type, possessing of S,Se-ambident reactivity, a type of compounds which is nearly
unexplored.1,2
Conventional syntheses of thioselenophosphinates are multi-step and require air-free
manipulations using glove boxes or Schlenk lines due to moisture- and air-sensitive pre-
cursors such as chlorophosphines, Grignard and organolithium reagents, as well as 2-
(trimethylsilyl)ethanethiol.10–14 The data on optically active compounds bearing the thiose-
lenophosphinate groups, [R2PSeS], are lacking in the literature, the only exception being
triethylammonium R-tert-butyl(phenyl)thioselenophosphinate, [t-Bu(Ph)PSeS][HEt3].14
Very recently, we have reported a convenient one-pot synthesis of alkylammonium
thioselenophosphinates via a new multi-component, atom-economic reaction between sec-
ondary phosphines, selenium, sulfur and aliphatic amines.15 It should be noted that only
some simple amines were used in this reaction.15
The aim of this work is to evaluate the scope of this promising reaction. Herein, we
have studied the multi-component, atom-economical reaction between secondary phos-
phines, elemental sulfur, selenium and natural lupinine, anabasine or quinine. The choice
of these alkaloids as N-bases is not arbitrary. It is known, that lupinine,16,17 anabasine18
Received October 24, 2011; in final form February 13, 2012.
Address correspondence to Nina K. Gusarova, A. E. Favorsky Irkutsk Institute of Chemistry,
Siberian Branch of the Russian Academy of Sciences, 1 Favorsky Str., 664033, Irkutsk, Russian
Federation. E-mail: gusarova@irioch.irk.ru
262

Lupininium, Anabasinium and Quininium Thioselenophosphinates
263
and quinine,19 as well as their salts, possess a wide spectrum of biological activity and use
in various pharmaceuticals, soft drinks and agrochemicals. Thus, one might expect that
unknown lupininium, anabasinium and quininium thioselenophosphinates might possess
new promising drugs and agrochemicals.
Secondary phosphines 1a,b, elemental selenium, elemental sulfur and natural lupi-
nine (2) interact in a multi-component type reaction under mild conditions (50–65◦C,
ethanol/toluene, 1 h) to afford optically active lupininium thioselenophosphinates 3a,b in
good isolated yields (Scheme 1).
Scheme 1
It is noteworthy that red selenium (Se8) may be used in the multi-component reaction
instead of amorphous gray selenium.
The atom-economic reaction between secondary phosphines 1b,c, selenium, sulfur and
natural anabasine (4) proceeds under similar conditions (50–65◦C, ethanol/toluene, 1 h) to
give thioselenophosphinates 5a,b (according to literature data,20 including NMR and IR
spectra, anabasine is protonated at the piperidine nitrogen) in high yields (Scheme 2). The
site of protonation in salts 5a,b is supported by their NMR (1H, 13C) spectra.
Scheme 2
The generality and efficacy of the approach elaborated was additionally demonstrated
by the synthesis of optically active quininium thioselenophosphinates 7a,b (78–90%) from
secondary phosphines 1b,c, selenium, sulfur and free quinine (Scheme 3).
Scheme 3

264
Gusarova et al.
Figure 1
Molecular Structure of Lupininium Thioselenophosphinate 3b
1
Multinuclear H, 13C, 31P, 77Se and 2D (COSY, HMBC, HSQC) NMR spectroscopy
data, as well as X-ray diffraction analysis, and IR investigations of thioselenophosphinates
3, 5 and 7 are in agreement with their structures. According to X-ray analysis, the absolute
configuration of the lupinine skeleton in thioselenophosphinate 3b was established as
1R,5S,9aR (Figure 1). Noteworthy, in the crystal structure of lupinine salt 3b, the nitrogen
atom is of the S-configuration. In comparison, the nitrogen atom of lupininium chloride
in solid state has R-configuration.21 Both six-membered cycles of the lupininium cation
have chair conformations. The phosphorus atom of thioselenophosphinate anion adopts a
slightly distorted tetrahedral structure with the bond angles ranging between 101.5◦ and
116.4◦. The sulfur and selenium atoms are disordered and refined with 50% occupancy
for both atoms as observed for the similar structures1,2,9,15 Thus, the molecular structure
of compound 3b is best described as an ion pair of a protonated lupinine and anion of the
bis(2-phenethyl)thioselenophosphinic acid.
Lupininium cation in solution (unlike in the solid state) exists as equilibrium mixture
of the s-cis (1R,5S,9aR) and s-trans (1R,5R,9aR) forms, which differ in the spatial location
of the protons conjugated with nitrogen atom (Scheme 4). This is supported by duplication
Scheme 4

Lupininium, Anabasinium and Quininium Thioselenophosphinates
265
of signals for the carbon atoms of lupinine unit in 13C NMR spectra of salts 3a,b. Similar
duplication of signals in the 13C NMR spectra of lupininium diselenophosphinate22 or
chloride23 has been reported.
The tentative mechanism of the present multi-component, atom-economic reaction can
be rationalized as follows (Scheme 5). In the first stage, the secondary phosphine 1 reacts
with elemental selenium to give secondary phosphine selenide A. The latter is deprotonated
by the alkaloid molecule to afford selenophosphinite B, which further reacts with elemental
sulfur to provide the thioselenophosphinate 3, 5, 7.
Scheme 5
The detection of intermediate secondary phosphine selenide A in the reaction mix-
1
ture by 31P NMR (singlet at 2 ppm with satellites, JPSe = 711 Hz24) supports the above
mechanism (Scheme 5). In addition, the mechanism proposed is in compliance with our
finding that secondary phosphine selenide 8, preparated from phosphine 1b and elemen-
tal selenium,24 reacts with sulfur and lupinine (2) under the same conditions (50–65◦C,
ethanol/toluene, 1 h) to form thioselenophosphinate 3b in 84% yield (Scheme 6).
Scheme 6
Since starting secondary phosphines are readily available from red phosphorus and
styrenes.25–27 The multi-component assembly presented may be considered as the most
concise and expedient approach to the early unknown optically active thioselenophosphi-
nates bearing alkaloid moieties, which are promising pharmaceuticals as well as prospective
agrochemicals.
Experimental Section
1H NMR spectra were recorded on a Bruker DPX 400 and Bruker AV-400 spectrometer
(400.13 MHz) in the solvents indicated at room temperature; chemical shifts are expressed
with respect to the residual protonated solvent (δ 7.27 for CHCl3 and 2.05 for DMSO-d6),
as an internal standard. 13C NMR spectra were recorded on a Bruker DPX 400 (100.61
MHz) instrument; chemical shifts are expressed with respect to the deuterated solvent (δ
77.00 for CDCl3 and 30.05 for DMSO-d6). 1H and 13C NMR signals were assigned using
2D NMR methods (COSY, HSQC, HMBC 1H-13C). The 31P and 77Se NMR spectra were
recorded on a Bruker DPX 400 spectrometer (161.98 and 76.31 MHz, respectively) and

266
Gusarova et al.
referenced to H3PO4 (31P NMR) and Me2Se (77Se NMR). Melting points were determined
on a Kofler micro hot stage apparatus, and the values given in ◦C are uncorrected. Fourier
transform IR spectra were recorded as films or potassium bromide pellets on a Bruker Vertex
70 spectrometer. The optical activity of the compounds was determined on a Polamat A
instrument. All reactions were performed under an argon atmosphere.
Diphenylphosphine (1a) was employed as commercial product (Aldrich). Secondary
phosphines 1b,c were prepared from styrene or 2-vinylfuran and red phosphorus as de-
scribed in the literature.27 bis(2-Phenethyl)phosphine selenide (8) was prepared by selena-
tion of secondary phosphine 1b with powdered gray selenium.24 Commercial ethanol was
used in the reaction as a solvent. Diethyl ether and toluene were dried and freshly distilled
over metal sodium prior to use.
Typical Procedure for the Preparation of Alkaloids Thioselenophosphinates 3, 5 and 7
(Schemes 1–3)
To a solution of secondary phosphine 1a–c (1.05 mmol) in ethanol (5 ml) was added
amorphous grey selenium (79 mg, 1.0 mmol), and the mixture was stirred (ca. 30 min) at
50 ◦C until dissolution of the residue to give a clear solution. Then a solution of powdered
sulfur S8 (32 mg, 0.125 mmol) in toluene (3 ml) and a solution of corresponding alkaloid
(lupinine, anabasine or quinine, 1.0 mmol) in ethanol (2 ml) were added consecutively.
After stirring for 30 minutes at 65◦C, the solvents were removed under reduced pressure,
and the residue was triturated and digested with ether (2 × 10 ml). Decantation of the ether
left the product (white powder or viscous oil) which was dried in vacuo (1 Torr, 40–45◦C)
to afford the corresponding thioselenophosphinates 3, 5 or 7.
Procedure for the Preparation of Thioselenophosphinate 3b from Secondary Phosphine
Selenide 8, Elemental Sulfur and Lupinine (Scheme 6)
To a solution of secondary phosphine selenide 8 (321 mg, 1.0 mmol) in ethanol (5 ml),
a solution of powdered sulfur S8 (32 mg, 0.125 mmol) in toluene (3 ml) and a solution
of lupinine (169 mg, 1.0 mmol) in ethanol (2 ml) were added consecutively. The resultant
solution was stirred (30 min) at 65◦C. The solvents were removed under reduced pressure,
and the residue was digested with ether (2 × 10 ml). Decantation of the ether left a white
powder that was dried in vacuo (1 Torr, 40◦C–45◦C) to afford the thioselenophosphinate
3b, yield: 0.44 g (84%).
(1R,9aR)-1-(Hydroxymethyl)octahydro-2H-quinolizinium Diphenylthioseleno-
phosphinate (3a). Obtained as a white powder. Yield: 0.37 g (79%), mp. > 150◦C (dec.).
[α]D = −30.7 (c 2.1; CHCl3). FTIR (cm−1): 3318 (OH, NH), 558 (P-S), 524 (P-Se). 1H
23
NMR (CDCl3): δ 1.26–1.40 (m, 1H, H-C8ax), 1.62–2.06 (m, 7H, H-C2,3,7,8eq), 2.22–2.50
(m, 2H, H-C9), 2.56–2.70 (m, 1H, H-C9a), 2.73–2.82 and 3.02–3.12 (m, 2H, H-C4ax,6ax),
3.42–3.68 (m, 2H, CH2OH), 3.55–3.89 (m, 1H, H-C1), 4.01–4.09 and 4.15–4.22 (m, 2H,
H-C4eq,6eq), 7.42–7.54 (m, 6H, Cm,p in Ph), 8.27–8.39 (m, 4H, Co in Ph), 9.03 (br s, 1H,
NH), 10.00 (br s, 1H, OH). 13C NMR (DMSO-d6): δ 17.2, 18.2 (C-3), 19.6, 19.9 (C-8),
22.3, 23.0 (C-7), 22.7, 23.7 (C-9), 26.1, 28.0 (C-2), 37.6, 39.5 (C-1), 45.1, 53.0 (C-6),
55.0, 59.2 (C-4), 55.9, 60.1 (C-9a), 61.9, 64.7 (C-9a), 127.3 (d, 2JCP = 12.1 Hz, Co in Ph),

Lupininium, Anabasinium and Quininium Thioselenophosphinates
267
128.8 (d, 4JCP = 2.0 Hz, Cp in Ph), 131.0 (d, 3JCP = 10.6 Hz, Cm in Ph), 145.0 (d, 1JCP
=
1
67.8 Hz, Cipso in Ph). 31P NMR (DMSO-d6): δ 44.76 (s + d satellites, JPSe = 644 Hz).
77Se NMR (DMSO-d6): δ -8 (d, 1JPSe = 644 Hz).
Anal. Calcd. for C22H30NOPSSe: C, 56.64; H, 6.48; N,3.00; P, 6.64; S, 6.87; Se, 16.93.
Found: C, 56.54; H, 6.41; N, 2.91; P, 6.50; S, 6.91; Se, 16.78.
(1R,9aR)-1-(Hydroxymethyl)octahydro-2H-quinolizinium bis(2-phenethyl)thio-
selenophosphinate (3b). Obtained as a white powder. Yield: 0.46 g (88%), mp. 176–178◦C
(EtOH). [α]D = −30.1 (c 2.1; CHCl3). FTIR (cm−1): 3352, 3327 (OH, NH), 594 (P-S), 554
23
(P-Se). 1H NMR (CDCl3): δ 1.14–1.37 (m, 1H, H-C8ax), 1.49–2.04 (m, 7H, H-C2,3,7,8eq),
2.22–2.38 (m, 2H, H-C9), 2.41–2.48 (m, 4H, CH2P), 2.52–2.60 (m, 1H, H-C9a), 2.69–2.79
and 2.83–2.90 (m, 2H, H-C4ax,6ax), 3.07–3.14 (m, 4H, CH2Ph), 3.23-3.78 (m, 3H, H-C1,
CH2OH), 3.90–4.15 (m, 2H, H-C4eq,6eq), 7.11–7.30 (m, 10H, Ph). 13C NMR (CDCl3): δ
17.0, 17.8 (C-3), 19.2, 19.7 (C-8), 21.7, 22.1 (C-7), 22.5, 22.8 (C-9), 27.3, 27.8 (C-2), 30.0
1
(CH2Ph), 36.7, 39.3 (C-1), 44.2 (d, JCP = 42.9 Hz, CH2P), 44.8, 52.6 (C-6), 55.9, 56.5
(C-4), 58.6, 62.1 (C-9a), 61.2, 66.5 (C-9a), 125.3 (Cp in Ph), 127.9 (Co,m in Ph), 142.0 (d,
3JCP = 17.3 Hz, Cipso in Ph). 31P NMR (CDCl3): δ 48.43 (s + d satellites, 1JPSe = 610 Hz).
77Se NMR (CDCl3), ppm: −78 (d, 1JPSe = 610 Hz).
Anal. Calcd. for C26H38NOPSSe: C, 59.76; H, 7.33; N, 2.68; P, 5.93; S, 6.14; Se, 15.11.
Found: C, 59.56; H 7.21; N, 2.51; P, 5.79; S, 6.08; Se, 15.04.
X-ray Crystallographic Data for Compound 3b (C26H38NOPSSe, M = 522.56)
˚
˚
˚
monoclinic, space group P21, a = 12.2867(10) A, b = 9.9339(8) A and c = 12.4158(10) A,
β = 116.041(4), V = 1361.56(19) A , Z = 2, dcalc = 1.275 g/cm−3, µ(MoKα) =
3
˚
1.532 mm−1, (θ)max = 30.00◦, data/restraints/parameters: 7654/1/281, R indices: R1 =
0.0630 [3847 I > 2σ(I)], wR2 (all data) = 0.1736. Colorless crystals of 3b suitable for
X-ray analysis were grown from an ethanolic solution. X-ray diffractions studies were
carried out on Bruker Kappa Apex II diffractometer at 296 K (Mo-Kα radiation). The struc-
ture was solved by direct methods and refined by a full matrix least-squares anisotropic
procedure using SHELXTL97 programs.28 The parameters of the hydrogen atoms were
given geometrically. Atomic coordinates, bond lengths, bond angles and thermal parame-
ters have been deposited at the Cambridge Crystallographic Data Centre (CCDC). These
data can be obtained free of charge via www.ccdc.cam.uk.conts/retrieving.html (or from
the CCDC, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336 033; or de-
posit@ccdc.cam.ac.uk). Any request to the CCDC for data should quote the full literature
citation and CCDC reference number 808439.
(S)-2-(Pyridin-3-yl)piperidinium bis(2-phenethyl)thioselenophosphinate (5a). Ob-
21
tained as a colorless viscous oil. Yield: 0.44 g (85%). [α]D = −4.9 (c 2.0, EtOH). FTIR
(cm−1): 3435 (NH), 585 (P-S), 553 (P-Se). 1H NMR (CDCl3): δ 1.89–2.11 (m, 6H, H-C3-5
in piperidine ring), 2.26–2.37 (m, 4H, CH2P), 2.85–3.00 (m, 4H, CH2Ph), 3.08 (ddd, 1H,
2JHH = 12.8 Hz, 3JHH = 9.9 Hz, 3JHH = 3.1 Hz, H-C6ax in piperidine ring), 3.82 (d, 1H,
2JHH = 12.8 Hz, H-C6eq in piperidine ring), 4.22 (dd, 1H, 3JHH = 9.7 Hz, 3JHH = 12.0 Hz,
H-C2ax in piperidine ring), 7.14-7.28 (m, 11H, Ph, H-C5 in pyridine ring), 8.02 (br. s, 2H,
NH), 8.24 (d, 1H, 3JHH = 8.2 Hz, H-C4 in pyridine ring), 8.42 (d, 1H, 3J = 4.1 Hz, H-C6
in pyridine ring), 8.74 (s, 1H, H-C2 in pyridine ring). 13C NMR (CDCl3): δ 22.0 (C-4 in
piperidine ring), 22.8 (C-5 in piperidine ring), 30.0 (CH2Ph), 30.4 (C-3 in piperidine ring),
43.8 (d, 1JCP = 43.3 Hz, CH2P), 45.4 (C-6 in piperidine ring), 58.5 (C-2 in piperidine ring),

268
Gusarova et al.
123.9 (C-5 in Py), 125.7 (Cp in Ph), 128.2 (Co in Ph), 128.2 (Cm in Ph), 132.5 (C-3 in
pyridine ring), 136.3 (C-4 in pyridine ring), 141.6 (d, 3JCP = 17.3 Hz, Cipso in Ph), 148.7
(C-2 in pyridine ring), 149.8 (C-6 in pyridine ring). 31P NMR (CDCl3): δ 48.56 (s + d
satellites 1JPSe= 572 Hz). 77Se NMR (CDCl3), ppm: −71 (d, 1JPSe = 572 Hz).
Anal. Calcd. for C26H33N2PSSe: C, 60.57; H, 6.45; N, 5.43; P, 6.01; S, 6.22; Se, 15.32.
Found: C, 60.51; C, 6.48; N, 5.54; P, 5.89; S, 6.11; Se, 15.23.
(S)-2-(Pyridin-3-yl)piperidinium bis[2-(2-furyl)ethyl]thioselenophosphinate (5b).
23
Obtained as a colorless viscous oil. Yield: 0.44 g (89%). [α]D = −4.6 (c 2.0, EtOH).
FTIR (cm−1): 3344 (NH), 599 (P-S), 531 (P-Se). 1H NMR (CDCl3): δ 1.85–2.10 (m, 6H,
H-C3-5 in piperidine ring), 2.26–2.32 (m, 4H, CH2P), 2.90–2.97 (m, 4H, CH2Fur), 3.07
(ddd, 1H, 2J = 12.4 Hz, 3JHH = 9.7 Hz, 3JHH = 2.7 Hz, H-C6ax in piperidine ring), 3.71 (d,
1H, 2JHH = 12.4 Hz, HC6eq in piperidine ring), 4.23 (dd, 1H, 3JHH = 9.2 Hz, 3JHH = 13.6
Hz, HC2ax in piperidine ring), 5.94 (d, 2H, 3JHH = 2.4 Hz, H-C4 in furan ring), 6.22 (br.
s, 2H, H-C3 in furane ring), 7.24 (br. s, 2H, H-C5 in furan ring), 7.28-7.31 (m, 1H, H-C5
in pyridine ring), 8.18 (d, 1H, 3JHH = 7.8 Hz, H-C4 in pyridine ring), 8.39 (br. s, 2H, NH),
8.45 (d, 1H, 3JHH = 4.1 Hz, H-C6 in pyridine ring), 8.71 (s, 1H, H-C2 in in pyridine ring).
13C NMR (CDCl3): δ 22.3 (C-4 in piperidine ring), 22.9 (CH2Fur), 23.0 (C-5 in piperidine
ring), 30.7 (C-3 in piperidine ring), 40.0 (d, 1JCP = 44.4 Hz, CH2P), 45.5 (C-6 in piperidine
ring), 58.6 (C-2 in piperidine ring), 104.8 (C-3 in furan ring), 110.0 (C-4 in furan ring),
124.0 (C-5 in furan ring), 133.0 (C-3 in furan ring), 136.2 (C-4 in furan ring), 140.8 (C-5
in furan ring), 148.7 (C-2 in furan ring), 149.8 (C-6 in furan ring), 141.6 (d, 3JCP = 20.6
Hz, C-2 in furan ring). 31P NMR (CDCl3): δ 47.76 (s + d satellites 1JPSe = 576 Hz). 77Se
NMR (CDCl3): δ -78 (d, 1JPSe = 576 Hz).
Anal. Calcd. for C22H29N2O2PSSe: C, 53.33; H, 5.90; N, 5.65; P, 6.25; S, 6.47; Se,
15.94. Found: C, 53.16; H, 5.88; N, 5.49; P, 6.10; S, 6.34; Se, 15.78.
(R)-(6-Methoxyquinolin-4-yl)[(2S,4S,8R)-8-vinylquinuclidin-2-yl]methanol bis(2-
phenethyl)thioselenophosphinate (7a). Obtained as a white powder. Yield: 0.61 g (90%),
mp. 122–125◦C (ether). [α]D = −4.9 (c 2.0, EtOH). FTIR (cm−1): 3427 (OH), 3082,
23
1
3059 and 3024 (NH), 587 (P-S), 528 (P-Se). H NMR (CDCl3): δ 1.22–1.27 (m, 1H, H-
C3ax in quinuclidine ring), 1.76–1.84 (m, 1H, H-C4 in quinuclidine ring), 1.94–2.00 (m,
1H, H-C5ax in quinuclidine ring), 2.07–2.13 (m, 2H, H-C3eq, 5eq in quinuclidine ring),
2.43–2.50 (m, 4H, CH2P), 2.64–2.71 (m, 1H, H-C8 in quinuclidine ring), 3.05–3.11 (m, 4H,
CH2Ph), 3.25–3.31 (m, 1H, H-C7ax in quinuclidine ring), 3.36–3.57 (m, 3H, H-C2,6ax,7eq
in quinuclidine ring), 4.01 (s, 3H, MeO), 4.59–4.66 (m, 1H, H-C6eq in quinuclidine ring),
5.00 (d, 1H, 3JHH = 10.5 Hz, H2C=), 5.05 (d, 1H, 3JHH = 17.0 Hz, H2C=), 5.31 (br s, 2H,
NH, OH), 5.54 (dddd, 1H, 3JHH = 10.5, 17.0 Hz, HC=), 6.81 (s, 1H, CHOH), 7.11–7.24
(m, 10H, Ph), 7.33 (d, 1H, 3JHH = 9.2 Hz, H-C8 in quinoline ring), 7.47 (d, 1H, 3JHH = 2.2
Hz, H-C5 in quinoline ring), 7.67 (d, 1H, 3JHH = 4.5 Hz, H-C3 in quinoline ring), 7.98 (d,
1H, 3JHH = 9.2 Hz, H-C7 in quinoline ring), 8.72 (d, 1H, 3JHH = 4.5 Hz, H-C2 in quinoline
ring). 13C NMR (CDCl3): δ 19.3 (C-3 in quinuclidine ring), 24.6 (C-5 in quinuclidine ring),
26.7 (C-4 in quinuclidine ring), 30.2 (CH2Ph), 37.2 (C-8 in quinuclidine ring), 44.0 (d,
1JCP = 43.3 Hz, CH2P), 45.2 (C-6 in quinuclidine ring), 54.8 (C-7 in quinuclidine ring),
57.2 (MeO), 60.0 (C-2 in quinuclidine ring), 65.9 (CHOH), 100.6 (C-5 in quinoline ring),
117.0 (=CH2), 119.1 (C-7 in quinoline ring), 122.3 (C-3 in quinoline ring), 125.7 (C-9 in
quinoline ring), 125.8 (Cp in Ph), 128.2–128.3 (Co,m in Ph), 131.5 (C-8 in quinoline ring),

Lupininium, Anabasinium and Quininium Thioselenophosphinates
269
137.3 (HC=), 141.6 (d, 3JCP = 17.2 Hz, Cipso in Ph), 143.7 (C-10 in quinoline ring), 143.9
(C-4 in quinoline ring), 147.2 (C-2 in quinoline ring), 158.6 (C-6 in quinoline ring). 31P
NMR (CDCl3): δ 48.63 (s + d satellites 1JPSe = 569 Hz). 77Se NMR (CDCl3): δ −73 (d,
1JPSe = 569 Hz).
Anal. Calcd. for C36H43N2O2PSSe: C, 63.80; H, 6.40; N, 4.13; P, 4.57; S, 4.73; Se,
11.65. Found: C, 63.71; H, 6.45; N, 4.20; P, 4.46; S, 4.57; Se, 11.57.
(R)-(6-Methoxyquinolin-4-yl)[(2S,4S,8R)-8-vinylquinuclidin-2-yl]methanol bis[2-
(2-furyl)ethyl]thioselenophosphinate (7b). Obtained as colorless viscous oil. Yield: 0.51
g (78%). [α]D = −4.7 (c 2.0, EtOH). FTIR (cm−1): 3236 (OH), 3114, 3083 (NH), 599
23
1
(P-S), 529 (P-Se). H NMR (CDCl3): δ 1.15–1.25 (m, 1H, H-C3ax in quinuclidine ring),
1.77–1.84 (m, 1H, H-C4 in quinuclidine ring), 1.94-2.00 (dd, 1H, H-C5ax in quinuclidine
ring), 2.05–2.14 (m, 2H, H-C3eq, 5eq in quinuclidine ring), 2.41–2.47 (m, 4H, CH2P),
2.64–2.72 (m, 1H, H-C8 in quinuclidine ring), 3.05-3.11 (m, 4H, CH2Ph), 3.22–3.35 (m,
1H, H-C7ax in quinuclidine ring), 3.37–3.53 (m, 3H, H-C2,6ax,7eq in quinuclidine ring),
3.94 (s, 3H, MeO), 4.57–4.64 (m, 1H, H-C6eq in quinuclidine ring), 4.98 (d, 1H, 3JHH
=
3
10.5 Hz, H2C=), 5.03 (d, 1H, JHH = 17.1 Hz, H2C=), 5.40 (br s, 2H, NH, OH), 5.51
3
(dddd, 1H, JHH = 10.5, 17.1 Hz, HC=), 5.93 (br s, 2H, H-C4 in furan), 6.19 (br. s,
2H, H-C3 in furan), 6.75 (s, 1H, CHOH), 7.22 (br. s, 2H, H-C5 in furan), 7.28 (dd, 1H,
3JHH = 2.4, 9.1 Hz, H-C8 in quinoline ring), 7.35 (d, 1H, 3JHH = 2.3 Hz, H-C5 in quinoline
3
3
ring), 7.65 (d, 1H, JHH = 4.5 Hz, H-C3 in quinoline ring), 7.94 (d, 1H, JHH = 9.1 Hz,
H-C7 in quinoline ring), 8.70 (d, 1H, JHH = 4.5 Hz, H-C2 in quinoline ring). 13C NMR
3
(CDCl3): δ 19.2 (C-3 in quinuclidine ring), 23.0 (CH2Fur), 24.5 (C-5 in quinuclidine ring),
1
26.6 (C-4 in quinuclidine ring), 37.1 (C-8 in quinuclidine ring), 40.1 (d, JCP = 45.0 Hz,
CH2P), 45.2 (C-6 in quinuclidine ring), 54.8 (C-7 in quinuclidine ring), 57.1 (MeO), 59.9
(C-2 in quinuclidine ring), 65.7 (CHOH), 100.5 (C-5 in quinoline ring), 104.9 (C-3 in Fur),
110.0 (C-4 in furan), 117.1 (=CH2), 119.1 (C-7 in quinoline ring), 122.4 (C-3 in quinoline
ring), 125.6 (C-9 in quinoline ring), 131.5 (C-8 in quinoline ring), 137.1 (=CH), 140.9
(C-5 in furan), 143.4 (C-10 in quinoline ring), 143.9 (C-4 in quinoline ring), 147.1 (C-2 in
quinoline ring), 154.8 (d, 3JCP = 20.1 Hz, C-2 in furan), 158.5 (C-6 in quinoline ring). 31
P
NMR (CDCl3): δ 47.87 (s + d satellites 1JPSe = 573 Hz). 77Se NMR (CDCl3pp): δ −67 (d,
1JPSe = 573 Hz).
Anal. Calcd. for C32H39N2O4PSSe: C, 58.44; H, 5.98; N, 4.26; P, 4.71; S, 4.88; Se,
12.01. Found: C, 58.50; H, 5.90; N, 4.21; P, 4.63; S, 4.79; Se, 11.55.
Acknowledgment
This work has been carried out under financial support the Russian Foundation for Basic
Research (Grant No. 11-03-00334-a) and of leading scientific schools by the President of
the Russian Federation (Grant NSh-3230.2010.3).
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