Diselenophosphinates of lupinine or anabasine via a new three-component reaction of secondary phosphines, elemental selenium, and amines

Article abstract of DOI:10.1016/j.tetlet.2010.01.116

Secondary phosphines, elemental selenium, and the natural alkaloids, lupinine and anabasine, interact in a three-component-type reaction under mild conditions (70 °C, 1-1.5 h, EtOH) without the formation of any by-products to give diselenophosphinates of the above-mentioned alkaloids (in almost quantitative yields) with the retention of their intrinsic optical activity. Thus, the developed synthesis represents an atom-economic route to new selenophosphorus derivatives of alkaloids.

Full text of DOI:10.1016/j.tetlet.2010.01.116

Tetrahedron Letters 51 (2010) 1840–1843
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Tetrahedron Letters
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Diselenophosphinates of lupinine or anabasine via a new three-component
reaction of secondary phosphines, elemental selenium, and amines
Nina K. Gusarova a, Alexander V. Artem’ev a, Svetlana F. Malysheva a, Sergei V. Fedorov a, Olga N. Kazheva b,
Grigorii G. Alexandrov c, Oleg A. Dyachenko b, Boris A. Trofimov a,
*
a A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, 1 Favorsky Str., 664033 Irkutsk, Russian Federation
b Institute of Problems of Chemical Physics, Russian Academy of Sciences, 1 Academician N. N. Semenov Str., 142432 Chernogolovka, Russian Federation
c N. S. Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, 119991 Moscow, Russian Federation
a r t i c l e i n f o
a b s t r a c t
Article history:
Secondary phosphines, elemental selenium, and the natural alkaloids, lupinine and anabasine, interact in
a three-component-type reaction under mild conditions (70 °C, 1–1.5 h, EtOH) without the formation of
any by-products to give diselenophosphinates of the above-mentioned alkaloids (in almost quantitative
yields) with the retention of their intrinsic optical activity. Thus, the developed synthesis represents an
atom-economic route to new selenophosphorus derivatives of alkaloids.
Received 16 December 2009
Revised 20 January 2010
Accepted 29 January 2010
Available online 4 February 2010
Ó 2010 Elsevier Ltd. All rights reserved.
Keywords:
Secondary phosphines
Elemental selenium
Lupinine
Anabasine
Diselenophosphinates
The alkaloids lupinine and anabasine, which can be easily ex-
tracted from natural products,1 possess a wide spectrum of biolog-
ical activity2,3 and are used as precursors for drug design and
pesticide preparation. For example, anabasine hydrochloride is em-
ployed in medicine as an antismoking agent,4 anabasine sulfate is
an efficient insecticide,5 and lupicaine (a lupinine derivative)
exhibits anesthetic action.6 Among the phosphorylated derivatives
of lupinine and anabasine are compounds showing antitumor,
antituberculosis, hepatoprotective, antiviral, antibacterial, anti-
fungal, anticholinesterase, anthelmintic, and other activities.7,8
Examples of lupinine and anabasine derivatives containing a dise-
lenophosphinate group (Se2PR2) are lacking in the literature.
It should be emphasized that selenium itself is a biologically
important element and occurs as a key active factor in several
drugs.9 Therefore, combination of these pharmacophore functions
with molecules of lupinine and anabasine should allow promising
new drug candidates and/or precursors to be developed. Thus, the
synthesis and investigations of lupinine and anabasine derivatives
functionalized with diselenophosphinate moieties represent an
interesting research area.
inate group via a recently discovered10 three-component reaction
between secondary phosphines, elemental selenium, and amines.
We found that lupinine 1a reacts with secondary phosphines
2a,b and elemental selenium under mild conditions (70 °C, 1 h,
EtOH) quantitatively (31P NMR) to give the diselenophosphinates
of lupinine, 3a,b in 91% and 89% isolated yields, respectively11
(Scheme 1).
The reaction of natural anabasine 1b, secondary phosphines
2a,c, and elemental selenium proceeds under similar conditions
(70 °C, 1.5 h, EtOH) to afford salts 3c,d (according to literature
data,12 including X-ray analysis, anabasine is regiospecifically pro-
tonated at the piperidine nitrogen) in high yields11 (Scheme 2).
The site of protonation in salts 3c,d is supported by their 13C
NMR spectra: the chemical shifts of the pyridine carbon atoms of
salts 3c,d are close to those of free anabasine 1b.12
Owing to the mild reaction conditions the intrinsic optical
activity of the starting natural alkaloids is retained. The value of
the specific rotation for lupinine released from salt 3a under the
action of NaOH (rt, EtOH) was the same as for authentic lupinine
(½a 2D4
ꢁ1.77, c 4.0% in EtOH).
ꢀ
In this Letter, we report on the direct one-pot synthesis of deriv-
atives of lupinine 1a and anabasine 1b containing a diselenophosph-
The secondary phosphines 2 employed in this work are readily
available from the reaction of elemental phosphorus with the cor-
responding electrophiles (styrene,13 4-t-butylstyrene14 or 2-vinyl-
furan13) in superbase systems.
The reactions described herein (Schemes 1 and 2) are not
accompanied by the formation of any by-products and hence are
* Corresponding author. Tel.: +7 395242 14 11; fax: +7 395241 93 46.
E-mail address: boris_trofimov@irioch.irk.ru (B.A. Trofimov).
0040-4039/$ - see front matter Ó 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tetlet.2010.01.116

N. K. Gusarova et al. / Tetrahedron Letters 51 (2010) 1840–1843
1841
OH
OH
H
N
H
R
R
R
Se
Se
70 ºC, 1 h
9
6
1
4
9a
+
Se
P
+
P
H
EtOH
N
R
H
2a R = Ph
3a R = Ph (91%)
1a
2b R = 2-fur
3b R = 2-fur (89%)
Scheme 1.
H
R
H
R
Se
70 ºC, 1.5 h
EtOH
+
+ Se
H P
P
N
N
H
Se
R
H
R
H
N
N
2a
R = Ph
3c
3d
R = Ph (94%)
1b
2c R = 4-t-BuC6H4
R = 4-t-BuC6H4 (91%)
Scheme 2.
atom-economic and ‘green’ (ethanol, a non-toxic recoverable sol-
vent is used).
dihedral angle between the six-membered rings is equal to
86.3(3)°. Maximum deviations out of the plane of the six-mem-
bered rings are 0.01 Å for C(20) of the C(15)C(16)ꢂ ꢂ ꢂC(20) ring
and 0.01 Å for C(26) of the C(21)C(22)ꢂ ꢂ ꢂC(26) ring. The bond dis-
tances are as follows: P–Se(1) = 2.136(3) Å, P–Se(2) = 2.153(3) Å,
P–C(11) = 1.800(4) Å, P–C(13) = 1.799(4) Å. The angles at the P
atom are: C(11)–P–C(13) = 102.0(5)°, C(13)–P–Se(1) = 111.5(4)°,
C(11)–P–Se(1) = ꢂ ꢂ ꢂ110(4)°, C(13)–P–Se(2) = 109.1(4)°, C(11)–P–
Se(2) = 106.5(4)°, Se(1)–P–Se(2) = 116.57(15)°. The values of the
P–Se(1) and P–Se(2) bond distances in the anion are similar which
can indicate to delocalization of the double bond, as has been ob-
served for analogous compounds of four-coordinated phosphorus.
Both six-membered rings of the lupinine cation adopt a chair con-
formation. The cation is significantly distorted unlike neutral lupi-
nine,17 and is similar to the methyl-substituted cation in
iodomethylate salts.18
A probable mechanism for the formation of diselenophosphi-
nates 3 is shown in Scheme 3. In the first stage (1), the secondary
phosphine 2 reacts with one equivalent of elemental selenium to
give secondary phosphine selenide A. The latter is deprotonated
by the nitrogen base (lupinine 1a or anabasine 1b) to afford P,Se-
ambident selenophosphinite anion B (stage 2), which reacts with
a second equivalent of elemental selenium to provide the dise-
lenophosphinate anion C (stage 3).
All the compounds synthesized are stable to air, are poorly sol-
uble in water and highly soluble in organic solvents (EtOH, THF,
DMSO). Lupininium salts 3a,b are crystalline solids, whereas ana-
basinium salts 3c,d are oils. Their structures have been established
by single-crystal X-ray diffraction analysis and/or multinuclear
(1H, 13C, 31P and 77Se) NMR spectroscopy.
The molecular structure of the salt 3a consists of an anion of the
bis(2-phenethyl)diselenophosphinic acid and a protonated lupi-
nine cation (Fig. 1).15 The geometry of the anion is characterized
by high symmetry with respect to the phosphorus atom and differs
substantially from that of the same anion in the salt, 4-aza-1-
azoniabicyclo[2.2.2]octane bis(2-phenethyl)diselenophosphinate,
studied previously.16
A fragment of the crystal structure of compound 3a is shown in
Figure 2. The cations and anions are bound by short intermolecular
bonding O(1)ꢂ ꢂ ꢂSe(2) 3.26(1) Å and N(1)ꢂ ꢂ ꢂSe(2) 3.360(8) (sum of
van der Waals radii: Oꢂ ꢂ ꢂSe = 3.40 Å, Nꢂ ꢂ ꢂSe = 3.50 Å19).
Torsion angles in the anion are PC(11)C(12)C(15) = 171.7(8)°;
PC(13)C(14)C(21) = 177.1(7)°; C(13)PC(11)C(12) = 173.4(8)°. The
Se
H
Se
(1)
P
H
P
2
A
Se
Se
H
H
+
+
P
N
P
P
Se
(2)
N
B
A
1a or 1b
Se
Se
Se
P
(3)
B
C
Scheme 3.
Figure 1. ORTEP diagram of 3a.

1842
N. K. Gusarova et al. / Tetrahedron Letters 51 (2010) 1840–1843
10. Artem’ev, A. V.; Malyisheva, S. F.; Gusarova, N. K.; Trofimov, B. A. Russ. J. Org.
Chem. 2009, in press.
11. Experimental procedure: Amorphous grey selenium (0.158 g, 2 mmol) was
added to a solution of phosphine 2 (1.1 mmol) in EtOH (5 mL) at 70 °C under
argon. Lupinine 1a (0.169 g, 1 mmol) or anabasine 1b (0.162 g, 1 mmol) in
EtOH (2 mL) was added to the stirred suspension which was stirred until
complete dissolution of selenium (ca. 1–1.5 h) at 70 °C; this gave a colorless,
transparent soln. The solvent was removed under reduced pressure and the
residue was washed with cold Et2O (6 mL ꢃ 1) and dried in vacuo (1 Torr, rt) to
give salts 3.
Compound 3a: (1R,9aR)-1-(hydroxymethyl)octahydro-2H-quinolizinium bis(2-
phenylethyl)diselenophosphinate: colorless crystalline powder, yield 0.518 g
(91%), mp 164–167 °C (EtOH), ½a 2D1 /cmꢁ1): 3335,
ꢁ19.1 (c 2.0, EtOH). IR (KBr, m
ꢀ
3083, 3061, 2943, 2865, 2838, 2727, 1601, 1583, 1496, 1451, 1432, 1425, 1408,
1396, 1378, 1362, 1348, 1334, 1314, 1298, 1270, 1260, 1212, 1198, 1188, 1158,
1124, 1106, 1076, 1056, 1047, 1024, 1013, 986, 968, 946, 930, 906, 894, 877,
859, 834, 825, 808, 764, 751, 735, 713, 695, 596, 579, 509, 481, 382. 1H NMR
(400.13 MHz, CDCl3, ppm), d: 1.15–1.25 (m, 1H, H-C8), 1.61–1.93 (m, 10H, H-
C
2,3,4ax,7–9), 2.20–2.53 (m, 1H, H-C6ax), 2.55–2.62 (m, 4H, CH2P), 2.68–2.73 (m,
1H, H-C1), 2.90–2.97 (m, 1H, H-C9a), 3.11–3.17 (m, 4H, CH2Ph), 3.35–3.40 (m,
1H, H-C6eq), 3.50–3.70 (m, 1H, H-C4eq), 3.78–4.16 (m, 2H, CH2OH), 7.16–7.37
(m, 10H, Ph), 9.50 (s, 2H, NH, OH). 13C NMR (100.62 MHz, CDCl3, ppm), d: 17.77
and 18.53 (C-3), 19.92 and 20.49 (C-8), 22.46 and 22.85 (C-7), 23.19 and 23.50
(C-9), 28.03 and 28.75 (C-2), 31.27 (CH2Ph), 37.27 and 40.07 (C-1), 44.53 (d,
1JP,C = 36.4 Hz, CH2P), 45.65 and 53.53 (C-6), 56.61 and 57.20 (C-4), 59.45 (C-
10), 62.05 (C-9a), 62.85 (C-10), 67.27 (C-9a), 126.10 (C-p in Ph), 128.63, 128.69
(C-o,m in Ph), 142.17 (d, 3JP,C = 17.2 Hz, C-i in Ph). 31P NMR (161.98 MHz, CDCl3,
ppm), d: 25.13 (satellites 1JP,Se = 573 Hz). 77Se NMR (76.31 MHz, CDCl3, ppm), d:
1
ꢁ59.40 (d, JP,Se = 573 Hz). Calcd for C26H38NOPSe2 (%): C, 54.84; H, 6.73; N,
2.46; P, 5.44; Se, 27.73. Found (%): C, 54.90; H, 6.76; N, 2.40; P, 5.38; Se, 27.70.
In the 13C NMR spectra of salts 3a,b, the presence of two signals for all the
carbon atoms in the lupinine unit is due to the equilibrium (in solution)
between two protonated forms of this alkaloid (s-cis and s-trans), which differ
in the spatial location of the proton conjugated with nitrogen atom. Similar
duplication of signals in the 13C NMR spectra of known salts of lupinine (for
example, in the 13C NMR spectrum of lupinine hydrochloride) has been
reported.20
Figure 2. Packing diagram of the structure of 3a.
In conclusion, a three-component reaction between secondary
phosphines, elemental selenium, and natural lupinine or anabasine
has been shown to be a convenient one-pot, atom-economic route
to optically active diselenophosphinates of alkaloids, as potential
drug candidates and/or precursors for the synthesis of pharmaceu-
tically important compounds.
Compound 3b: (1R,9aR)-1-(hydroxymethyl)octahydro-2H-quinolizinium bis[2-
(2-furyl)ethyl]diselenophos-phinate: colorless crystalline powder, yield 0.489 g
(89%), mp 90–92 °C (EtOH), ½a 2D1 /cmꢁ1): 3332,
ꢁ9.6 (c 2.0, EtOH). IR (KBr, m
ꢀ
2927, 2889, 2855, 2720, 2700, 2653, 2590, 1727, 1656, 1638, 1628, 1588, 1543,
1506, 1472, 1448, 1410, 1371, 1357, 1338, 1330, 1312, 1282, 1265, 1230, 1218,
1166, 1147, 1128, 1105, 1074, 1059, 1048, 1024, 1008, 969, 947, 932, 910, 883,
858, 844, 825, 807, 793, 756, 743, 732, 696, 678, 598, 584, 548, 499, 478, 455.
1H NMR (400.13 MHz, CDCl3, ppm), d: 1.15–1.25 (m, 1H, H-C8), 1.40–2.08 (m,
10H, H-C2,3,4ax,7–9), 2.16–2.40 (m, 1H, H-C6ax), 2.51–2.60 (m, 4H, CH2P), 2.61–
2.69 (m, 1H, H-C1), 2.98–3.06 (m, 1H, H-C9a), 3.10–3.16 (m, 4H, CH2Fur), 3.25–
3.50 (m, 1H, H-C6eq), 3.60–3.75 (m, 1H, H-C4eq), 3.78–4.10 (m, 2H, CH2OH),
6.01–6.02 (m, 2H, H-C2 in Fur), 6.25–6.26 (m, 2H, H-C3 in Fur), 7.28–7.29 (m,
2H, H-C4 in Fur), 9.30 (s, 2H, NH, OH). 13C NMR (100.62 MHz, CDCl3, ppm), d:
17.35 and 18.13 (C-3), 19.50 and 20.06 (C-8), 22.04 and 22.43 (C-7), 22.73 and
23.12 (C-9), 23.68 (CH2 Fur), 27.65 and 28.23 (C-2), 36.62 and 39.72 (C-1),
Acknowledgments
This work was supported by the President of the Russian Feder-
ation (program for the support of leading scientific schools, Grant
No. NSh-263.2008.3) and the Russian Foundation for Basic Re-
search (project No. 08-03-00251).
1
40.30 (d, JP,C = 38.1 Hz, CH2P), 45.78 and 53.13 (C-6), 56.15 and 56.71 (C-4),
59.08 (C-10), 61.73 (C-9a), 62.35 (C-10), 66.78 (C-9a), 104.76 (C-2 in Fur),
3
109.99 (C-3 in Fur), 140.70 (C-4 in Fur), 155.10 (d, JP,C = 20.3 Hz, C-1 in Fur).
References and notes
1
31P NMR (161.98 MHz, CDCl3, ppm), d: 23.60 (satellites JP,Se = 581 Hz). 77Se
1
NMR (76.31 MHz, CDCl3, ppm), d: ꢁ60.10 (d, JP,Se = 581 Hz). Calcd for
1. (a) Marion, L. The Alkaloids, R. H. F. Manske (Ed.), New York, 1950; (b) Robins, D.
J. In The Alkaloids, Chemistry and Pharmacology; Cordell, G., Ed.; Academic Press:
San Diego, 1995; pp 1–57; (c) Mizrachi, N.; Levy, S.; Goren, Z. J. Forensic Sci.
2000, 45, 736; (d) Steenkamp, P. A.; Heerden, F. R.; Wyk, B. E. J. Forensic Sci.
2002, 127, 208.
C22H34NO3PSe2 (%): C, 48.09; H, 6.24; N, 2.55; P, 5.64; Se, 28.74. Found (%):
C, 48.11; H, 6.26; N, 2.56; P, 5.50; Se, 28.63.
Compound 3c: (S)-2-(pyridin-3-yl)piperidinium bis(2-phenylethyl)diseleno-
phosphinate: colorless oil, yield: 0.529 g (94%), ½a D21
ꢁ4.9 (c 2.0, EtOH). IR (film,
ꢀ
m
/cmꢁ1): 3354, 3083, 3025, 2922, 2851, 2352, 2197, 1951, 1881, 1811, 1751,
2. (a) Daly, J. W.; Carraffo, H. M.; Spande, T. F. In Alkaloids: Chemical and Biological
Perspectives; Pelletier, S. W., Ed.; Wiley: New York, 1999; Vol. 13, p 1; (b)
Michael, J. P. In The Alkaloids, Chemistry and Pharmacology; Cordell, G., Ed.;
Academic Press: New York, 2001; pp 91–258; (c) Michael, J. P. Nat. Prod. Rep.
2008, 25, 139–187.
3. (a) Navashin, S. M.; Fomina, I. P. Rational Therapy with Antibiotics (A Handbook);
Meditsina: Moscow, 1983 (in Russian); (b) Abdulina, G. A.; Gazaliev, A. M.;
Baikenova, G. G. Khim.-Farm. Zh. 2002, 36, 11.
4. (a) Mashkovsky, M. D. In Lekarstvennye sredstva [Pharmaceuticals]; Novaya
volna: Moscow, Russia, 2000; Vol. 1 (in Russian); (b) Jacob, P.; Hatsukami, D.;
Severson, H.; Hall, S.; Yu, L.; Benowitz, N. L. Cancer Epidemiology, Biomarkers
Prevention 2002, 11, 1668.
5. (a) Roark, R. C. Ind. Eng. Chem. 1935, 27, 530; (b) Klyshev, A. K. The Biology of
Anabasis aphylla L. Izd. Akad. Nauk Kaz. SSR: Alma-Ata, 1961 (in Russian).
6. Gafurova, Sh. M.; Abduvakhabov, A. A.; Aslanov, Kh. A. Uzb. Khim. Zhurn. 1979,
56.
7. Aimakov, O. Ph.D. Thesis, Moscow, 2002.
8. Tilyabaev, Z.; Baimirzaev, S. S.; Kushiev, Kh. Kh.; Dalimov, D. N.; Gafurov, M. B.
Chem. Nat. Compd. 1994, 30, 57.
9. (a) Parker, J. N.; Parker, P. M. Selenium: A Medical Dictionary, Bibliography, and
Annotated Research Guide to Internet References; ICON Group International: San
Diego, 2004; (b) Reilly, C. Selenium in Food and Health; Springer: New York,
2006.
1602, 1581, 1496, 1454, 1434, 1326, 1298, 1280, 1263, 1206, 1193, 1153, 1126,
1102, 1077, 1049, 1029, 944, 910, 835, 807, 757, 663, 643, 631, 618, 574, 507, 478,
444. 1H NMR (400.13 MHz, CDCl3, ppm), d: 1.75–2.05 (m, 6H, H-C3–5), 2.03–2.37
(m, 4H, CH2P), 2.83–2.90 (m, 4H, CH2Ph), 3.02 (ddd, 1H, 2J = 12.8 Hz, 3J = 9.6 Hz,
3J = 2.9 Hz, HaxC6), 3.67 (d, 1H, 2J = 12.8 Hz, HeqC6), 4.22 (d, 1H, 3J = 10.5 Hz,
HaxC2), 7.05–7.15 (m, 11H in Ph, H-C5 in Py), 8.13 (d, 1H, 3J = 8.2 Hz, H-C4 in Py),
8.29 (d, 1H, 3J = 4.7 Hz, H-C6 in Py), 8.69 (s, 1H, H-C2 in Py), 9.08 (s, 2H, NH). 13
C
NMR (100.62 MHz, CDCl3, ppm), d: 22.35 (C-4), 23.05 (C-5), 30.85 (CH2Ph, C-3),
44.79 (d, 1JP,C = 36.5 Hz, CH2P), 45.52(C-6), 58.63(C-2), 124.06 (C-5 inPy), 125.94
(C-p in Ph), 128.38 (C-o in Ph), 128.41 (C-m in Ph), 133.12 (C-3 in Py), 136.34 (C-4
in Py), 141.61 (d, 3JP,C = 17.2 Hz, C-i in Ph), 148.92 (C-2 in Py), 149.86 (C-6 in Py).
31P NMR (161.98 MHz, CDCl3, ppm), d: 25.49 (satellites 1JP,Se = 573 Hz). 77Se NMR
(76.31 MHz, CDCl3, ppm), d: ꢁ68.56 (d, 1JP,Se = 573 Hz). Calcd for C26H33N2PSe2
(%): C, 55.52; H, 5.91; N, 4.98; P, 5.51; Se, 28.08. Found (%): C, 55.58; H, 6.00; N,
4.94; P, 5.39; Se, 28.04.
Compound 3d: (S)-2-(pyridin-3-yl)piperidinium bis[2-(4-tertbutylphenyl)ethyl] -
diselenophosphinate: colorless oil, yield: 0.614 g (91%), ½a D21
ꢁ4.1 (c 2.0, EtOH). IR
ꢀ
(film, m
/cmꢁ1): 3443, 2959, 2904, 2864, 2804, 2774, 2705, 1633, 1596, 1577,
1516, 1463, 1444, 1432, 1416, 1363, 1326, 1294, 1268, 1201, 1132, 1108, 1077,
1048, 1017, 1008, 941, 910, 875, 853, 838, 812, 769, 730, 710, 661, 631, 616, 563,
526, 493, 443. 1H NMR (400.13 MHz, CDCl3, ppm), d: 1.28 (s, 18H, Me), 1.90–2.15
(m, 6H, H-C3–5), 2.39–2.45 (m, 4H, CH2P), 2.90–2.96 (m, 4H, CH2Ph), 3.10 (t, 1H,
2J = 11.2 Hz, HaxC6), 3.84 (d, 1H, 2J = 11.2 Hz, HeqC6), 4.27 (d, 1H, 3J = 12.0 Hz,

N. K. Gusarova et al. / Tetrahedron Letters 51 (2010) 1840–1843
1843
HaxC2), 7.11–7.27 (m, 9H in C6H4, H-C5 in Py), 8.26 (d, 1H, 3J = 7.5 Hz, H-C4 in Py),
8.45 (d, 1H, 3J = 3.8 Hz, H-C6 in Py), 8.55 (s, 2H, NH), 8.76 (s, 1H, H-C2 in Py). 13
of refined parameters = 280, R-factor 0.110 for 2277 reflections with
[F0 > 4 (F0)]. The crystal structure was solved by direct methods followed with
Fourier synthesis using SHELX-97.21 The structure was refined using full-matrix
least-square anisotropic approximation for all non-hydrogen atoms with SHELXL
C
r
NMR (100.62 MHz, CDCl3, ppm), d: 22.19 (C-4), 22.97 (C-5), 30.21 (CH2Ph), 30.66
(C-3), 31.29 (Me), 34.21 (CMe), 43.74 (d, 1JP,C = 39.4 Hz, CH2P), 45.41 (C-6), 58.60
(C-2), 123.92 (C-5 in Py), 125.15 (C-o in C6H4), 127.97 (C-m in C6H4), 132.78 (C-3
in Py), 136.29 (C-4 inPy), 138.46 (d, 3JP,C = 18.9 Hz, C-iin C6H4), 148.57 (C-2inPy),
148.87 (C-p in C6H4), 149.87 (C-6 in Py). 31P NMR (161.98 MHz, CDCl3, ppm), d:
25.95 (satellites 1JP,Se = 570 Hz). 77Se NMR (76.31 MHz, CDCl3, ppm), d: ꢁ69.51
(d, 1JP,Se = 570 Hz). Calcd for C34H49N2PSe2 (%): C, 60.53; H, 7.32; N, 4.15; P, 4.59;
Se, 23.41. Found (%): C, 60.58; H, 7.20; N, 4.10; P, 4.40; Se, 23.44.
-
97.21 Coordinates of hydrogen atoms were defined experimentally and refined
isotropically. Atomic coordinates, bond lengths, bond angles, and thermal
parameters 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 deposit@ccdc.cam.ac.uk). Any request to the CCDC for data
should quote the full literature citation and CCDC reference number 754636.
16. Trofimov, B. A.; Artem’ev, A. V.; Gusarova, N. K.; Malysheva, S. F.; Fedorov, S. V.;
Kazheva, O. N.; Alexandrov, G. G.; Dyachenko, O. A. Synthesis 2009, 3332.
17. (a) Koziol, A. E.; Gdaniec, M.; Kosturkiewicz, Z. Acta Crystallogr., Sect. B 1980, 36,
982; (b) Koziol, A. E.; Kosturkiewcz, Z.; Podkowinska, H. Acta Crystallogr., Sect. B
1978, 34, 3491.
12. Wojciechowska-Nowak, M.; Boczon, W.; Rychlewska, U.; Warzajtis, B. J. Mol.
Struct. 2007, 840, 44.
13. Trofimov, B. A.; Brandsma, L.; Arbuzova, S. N.; Malysheva, S. F.; Gusarova, N. K.
Tetrahedron Lett. 1994, 35, 7647.
14. Gusarova, N. K.; Malysheva, S. F.; Kuimov, V. A.; Belogorlova, N. A.;
Mikhailenko, V. L.; Trofimov, B. A. Mendeleev Commun. 2008, 18, 260.
15. X-ray crystallographic data for compound 3a. C26H38NOPSe2, Mr = 569.48,
monoclinic, space group P21, a = 12.278(2), b = 9.879(2) and c = 12.307(2),
18. Koziol, A. E. Acta Crystallogr., Sect. C 1983, 39, 1375.
19. Pauling, L. The Nature of the Chemical Bond and the Structure of Molecules and
Crystals; Cornell University Press: London, 1939.
20. Golebiewski, W. M.; Spenser, I. D. Can. J. Chem. 1985, 63, 2707.
21. Sheldrick, G. M. SHELXS-97, SHELXL-97, Programs for Crystal Structure Determination
and Refinement; Göttingen University: Göttingen, 1997. Germany.
b = 115.465(3)°, V = 1347.8(4) Å3, Z = 2, dcalc = 1.40 g cmꢁ3
,
l(MoK ) =
a
2.820 mmꢁ1. X-ray diffraction studies were carried out using a Bruker SMART
APEX2 CCD diffractometer at 200 K (Mo-K radiation). The number of measured
a
reflections = 10,289, the number of independent reflections = 4524, the number