Syntheses of the optically active terpene hydroxyphenylselenides

Article abstract of DOI:10.1080/10426500902947682

The optically active hydroxyphenylselenides derived from the p-menthane, carane, and pinane systems have been obtained. Two methods of hydroxyphenylselenides synthesis have been compared. The first method is based on the reaction of alkenes with N-(phenylseleno)succinimide in the presence of water, and the second from epoxides as a result of the reaction with sodium benzeneselenolate. The influence of the substrate structures on the composition of the obtained products has been demonstrated.

Full text of DOI:10.1080/10426500902947682

This article was downloaded by: [Moskow State Univ Bibliote]
On: 31 October 2013, At: 00:27
Publisher: Taylor & Francis
Informa Ltd Registered in England and Wales Registered Number: 1072954
Registered office: Mortimer House, 37-41 Mortimer Street, London W1T 3JH,
UK
Phosphorus, Sulfur, and Silicon
and the Related Elements
Publication details, including instructions for
authors and subscription information:
http://www.tandfonline.com/loi/gpss20
Syntheses of the
Optically Active Terpene
Hydroxyphenylselenides
Jacek Ścianowski a & Mirosław Wełniak a
a Faculty of Chemistry , Nicolaus Copernicus
University , Torun, Poland
Published online: 06 Jun 2009.
To cite this article: Jacek Ścianowski & Mirosław Wełniak (2009) Syntheses of the
Optically Active Terpene Hydroxyphenylselenides, Phosphorus, Sulfur, and Silicon and
the Related Elements, 184:6, 1440-1447, DOI: 10.1080/10426500902947682
To link to this article: http://dx.doi.org/10.1080/10426500902947682
PLEASE SCROLL DOWN FOR ARTICLE
Taylor & Francis makes every effort to ensure the accuracy of all the
information (the “Content”) contained in the publications on our platform.
However, Taylor & Francis, our agents, and our licensors make no
representations or warranties whatsoever as to the accuracy, completeness,
or suitability for any purpose of the Content. Any opinions and views
expressed in this publication are the opinions and views of the authors, and
are not the views of or endorsed by Taylor & Francis. The accuracy of the
Content should not be relied upon and should be independently verified with
primary sources of information. Taylor and Francis shall not be liable for any
losses, actions, claims, proceedings, demands, costs, expenses, damages,
and other liabilities whatsoever or howsoever caused arising directly or
indirectly in connection with, in relation to or arising out of the use of the
Content.

This article may be used for research, teaching, and private study purposes.
Any substantial or systematic reproduction, redistribution, reselling, loan,
sub-licensing, systematic supply, or distribution in any form to anyone is
expressly forbidden. Terms & Conditions of access and use can be found at
http://www.tandfonline.com/page/terms-and-conditions

Phosphorus, Sulfur, and Silicon, 184:1440–1447, 2009
Copyright © Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426500902947682
Syntheses of the Optically Active Terpene
Hydroxyphenylselenides
´
Jacek Scianowski and Miroslꢀaw Welꢀniak
Faculty of Chemistry, Nicolaus Copernicus University, Torun, Poland
The optically active hydroxyphenylselenides derived from the p-menthane, carane,
and pinane systems have been obtained. Two methods of hydroxyphenylselenides
synthesis have been compared. The first method is based on the reaction of alkenes
with N-(phenylseleno)succinimide in the presence of water, and the second from
epoxides as a result of the reaction with sodium benzeneselenolate. The influence
of the substrate structures on the composition of the obtained products has been
demonstrated.
Keywords Epoxides; hydroxyphenylselenides; selenides; terpenes
INTRODUCTION
Recently the synthetic role of the selenoorganic compounds has grown
up. Numerous methods using selenoorganic compounds are employed
for the synthesis of olefins, alcohols, amines, ethers, heterocyclic sys-
tems, and others.1–4
In previous articles, we presented syntheses of terpene allyl
phenylselenides, convenient precursors for the synthesis of allyl
alcohols,5 allyl toluenesulfonamides,6–8 and allyl methylcarbamates.5
Using the optically active allyl phenylselenides, we obtained the re-
spective optically active oxygen and nitrogen derivatives.5–8
Herein, we present the syntheses of the optically active terpene
hydroxyphenylselenides from the p-menthane, carane, and pinane
systems. The hydroxyphenylselenides have great synthetic impor-
tance and have been used for the synthesis of allyl alkohols,9
epoxides,10 amides,11 dihydroxydiselenides,12 and diols.13 The terpene
Received 3 January 2008; accepted 24 January 2008.
Dedicated to Professor Marian Mikolꢀajczyk, CBMiM PAN in Lꢀ o´dz´, Poland, on the
occasion of his 70th birthday.
´
Address correspondence to Jacek Scianowski, Faculty of Chemistry, Nicolaus Coperni-
cus University, 7 Gagarin Street, 87-100 Torun, Poland. E-mail: jsch@chem.uni.torun.pl
1440

Optically Active Terpene Hydroxyphenylselenides
1441
SCHEME 1 Synthesis of N-(phenylseleno)succinimide (1).
hydroxyphenylselenides from the p-menthane series14,15 have been
used as precursors to the isomers of the aggregation pheromone of
the ambrosia beetle, Platypus guercivorus.15
A few methods for the synthesis of hydroxyphenylselenides are
known, for example as a result of the reaction of alkenes with phenylse-
lenenyl chloride,14,16 N-(phenylseleno)succinimide (N-PSS, 1),17 and N-
(phenylseleno)phthalimide (N-PSP)17 in the presence of water or as the
result of the reaction of epoxides with sodium benzeneselenolate.11
RESULTS AND DISCUSSION
For the synthesis of hydroxyphenylselenides, we used two methods:
the addition of N-PSS (1) to alkenes in the presence of water (method
A) and the opening of the epoxide ring with sodium bezeneselenolate
(Ph2Se2 NaBH4, MeOH) (method B). N-PSS (1) was obtained as a result
of the reaction of allyl phenylselenide (2) with NCS (Scheme 1).18
The reaction of cyclohexene (3) with N-PSS (1) in the presence of
water or cyclohexene oxide (4) with sodium benzeneselenolate, hydrox-
yphenylselenide 5 was obtained in the comparable yields (ca. 80%)
(Scheme 2).
SCHEME 2 Syntheses of hydroxyphenylselenide 5.

´
J. Scianowski and M. Welꢀniak
1442
SCHEME 3 Syntheses of hydroxyphenylselenides from p-menthane group.
The chosen methods have been used for a synthesis of the optically
active hydroxyphenylselenides derived from (+) − p-menthene (6),
(−)-p-menthene (7), (+)-3-carene (8), (+)-2-carene (9), (+)-α -pinene
(10), and (−)-β -pinene (11).
(+)-p-Menthene (6) was obtained by the reduction of (+)-limonene
(12) with hydrogen in the presence of PtO2 catalyst. (+)-p-Menthene
(6) with N-PSS (1) and water gave hydroxyphenylselenide 13 in 87%
yield. The epoxidation of (+)-p-menthene (6) with 40% peracetic acid19
led to the cis and trans mixture of p-menthene oxides 14 and 15 in a 1:1
ratio. The reaction of the epoxide ring opening was carried out on the
mixture of epoxides. Three hydroxyselenides 13, 16, and 17 have been
SCHEME 4 Syntheses of hydroxyphenylselenides from (+)-3-carane series.

Optically Active Terpene Hydroxyphenylselenides
1443
SCHEME 5 Synthesis of hydroxyphenylselenide 24 from (+)-2-carene.
obtained in 75% yield (5.4:2.8:1.8 ratio) (Scheme 3). The same three
hydroxydiselenides were obtained by Mori.15 The analogous results we
obtained for (-)-p-menthene (7).
For the reaction of (+)-3-carene (8) with N-PSS (1) and 3-carene
trans-oxide (18) with sodium benzeneselenolate, hydroxyphenylse-
lenides 19 and 20 have been obtained respectively, in 55% and 56%
yield. The application of the (+)-carene cis-oxide (22) gave the hydrox-
yphenylselenide 19, in 84% yield. The (+)-3-carene cis-oxide (22) have
been obtained by the method of Kuczyñski and Chabudziñski20 as the
result of the three-step synthesis, by the epoxide ring opening of the
(+)-3-carene trans-oxide with the 1% solution of sulfuric acid, a syn-
thesis of the hydroxytosylate 21, and the repeated closing of the ring to
the cis-oxide 22 (Scheme 4).
The reaction of (+)-2-carene (9) with N-PSS (1) failed. Instead, the
initial alkene 9 was isolated. The opening of the epoxide ring of the
SCHEME 6 Synthesis of hydroxyphenylselenide from (−)-β -pinene.

´
J. Scianowski and M. Welꢀniak
1444
(+)-2-carene oxide (23) by means of the sodium benzeneselenolate gave
the hydroxyphenylselenide 24 in 93% yield (Scheme 5).
The reactions of α-pinene (10) with N-PSS (1) and α -pinene oxide
with sodium benzeneselenolate failed.
Under the action of N-PSS (1) on (-)-β -pinene (11), a mixture of two
1
phenylselenides was obtained. On the basis of the H and 13C NMR
spectra and a comparison with the data in the literature,6,8 it was
determined that they correspond to two compounds: 10-phenylseleno-
2-pinene (26) and 10-phenylseleno-p-menthadien (27) (3:2 ratio, 40%
yield). The analogous results have been obtained by Sharpless.18 The
reaction of the β -pinene oxide (28) with sodium benzeneselenolate gave
the hydroxyphenylselenide 29 in 72% yield (Scheme 6).
CONCLUSION
Hydroxyphenylselenides from the p-menthane, pinane, and carane sys-
tems were obtained. All bicyclic terpene hydroxyphenylselenides have
been obtained for the first time. The reaction with N-PSS and water
was the most selective method for the p-menthane system. It was estab-
lished that for bicyclic terpenes under investigation the reaction with
sodium benzeneselenolate is the most convenient method.
EXPERIMENTAL
1H NMR and 13C NMR spectra were recorded on a Bruker Avance 300,
Varian Gemini 200 spectrometers at 300 and 200 MHz, respectively (J
values are given in Hz). Optical rotations were measured in a 50 mm
cells with a polAAr 3000 polarimeter. Column chromatography was
performed with Merck silica gel 60 (70–230 mesh). All reactions were
carried out under an argon atmosphere.
General Procedure for Method A
To the mixture of N-(phenylseno)succinimide (2.28 g, 9 mmol), methy-
lene chloride (16 mL) and cyclohexene (0.82 g, 10 mmol), the solution of
camphorsulphonic acid (0.23 g, 1 mmol) in methylene chloride (25 mL),
and water (1 mL) were added. The mixture was stirred 3.5 h under
argon. To the reaction mixture water (100 mL) was added, the organic
layer was separated and aqueous layer was extracted with methylene
chloride and dried over anhydrous MgSO4. The solvent was removed to
give the oil product, which was purified by means of chromatographic
column (silica gel, hexane, then CHCl3) to give the product (1.83 g, 80%
yield).

Optically Active Terpene Hydroxyphenylselenides
1445
General Procedure for Method B
To diphenyldiselenide (2.50 g, 8 mmol) dissolved in methanol (50 mL),
NaBH4 (1.0 g, 26 mmol) was added to decolorization of the reaction
mixture. The cyclohexene oxide (1.7 g, 17 mmol) was added and heated
under reflux for 3 h. After cooling, water (25 mL) was added, and the
reaction mixture was extracted with petroleum ether (120 mL). The or-
ganic layer was separated and dried on anhydrous MgSO4. The solvent
was removed and the product was purified by means chromatographic
column (silica gel, hexane, then CHCl3) to give product (3.18 g, 78%
yield).
2-(Phenylselanyl)cyclohexanol (5)
Yield 80%; oil;1H NMR (200 MHz, CDCl3): δ = 1.11–1.50 (m, 4H),
1.52–1.80 (m, 2H), 2.04–2.26 (m, 2H), 2.80–3.07 (m, 2H), 3.24–3.42 (m,
1H), 7.20–7.40 (m, 3H), 7.52–7.64 (m, 2H); 13C NMR (50 MHz, CDCl3):
δ = 24.4 (CH2), 26.7 (CH2), 33.3 (CH2), 33.9 (CH2), 53.4 (CH), 72.2
(CH), 126.7 (C), 127.9 (CH), 128.9 (2xCH), 135.9 (2xCH); 77Se (38 MHz,
CDCl3): δ = 337.2.
(1 S,2 S,4 R)-4-Isopropyl-1-methyl-2-(phenylselanyl)
cyclohexanol (13)
Yield 87%; oil; [α]2D0 +107.1 (c 5.3, CHCl3); 1H NMR (200 MHz,
CDCl3): δ = 0.81 (d J = 6.4 Hz, 3H, CH3), 0.87 (d, J = 6.6 Hz, 3H,
CH3), 1.38 (s, 3H, CH3), 1.40–2.20 (m, 9H), 3.40 (t-like, 1H, CH), 7.20–
7.35 (m, 3H), 7.52–7.68 (m, 2H); 13C NMR (50 MHz, CDCl3): δ = 19.9
(CH3), 20.0 (CH3), 24.7 (CH2), 29.2 (CH3), 30.9 (CH), 32.3 (CH2), 35.1
(CH2), 38.9 (CH), 54.8 (CH), 72.7 (C), 127.3 (CH), 128.9 (CH), 130.6 (C),
134.2 (CH); 77Se (38 MHz, CDCl3): δ = 359.2.
(1 S,3 R,4 R,6 R)-3,7,7-Trimethyl-4-(phenylselanyl)
bicyclo[4.1.0]heptan-3-ol (19)
Yield 84%; oil; [α]2D0 = –87.7 (c 11.8, CHCl3); H NMR (200 MHz,
1
CDCl3): δ = 0.58–0.98 (m, 2H, CH), 0.98 (s, 6H, CH3), 1.29 (s, 3H,
CH3), 1.28–1.36 (m, 1H, CH), 2.09–2.50 (m, 3H), 2.58 (bs, 1H, OH),
3.05 (dd, J = 7.2 Hz, J = 12.4 Hz, 1H), 7.22-7.30 (m, 3H), 7.57–7.65 (m,
2H); 13C NMR (50 MHz, CDCl3): δ = 15.2 (CH3), 17.5 (C), 20.2 (CH),
20.4 (CH), 23.2 (CH3), 28.6 (CH3), 29.7 (CH2), 33.4 (CH2), 57.6 (CH),
71.4 (C), 127.1 (CH), 128.9 (CH), 130.1 (C), 133.4 (CH);77Se (38 MHz,
CDCl3): δ = 332.1.

´
J. Scianowski and M. Welꢀniak
1446
(1 S,3 S,4 S,6 R)-3,7,7-Trimethyl-4-(phenylselanyl)
bicyclo [4.1.0]heptan-3-ol (20)
Yield 55%; oil;[α]2D0 = +77.8 (c 7,0 CHCl3); 1H NMR (300 MHz,
CDCl3): δ = 0.69–0.80 (m, 2H), 0.99 (s, 6H, CH3), 1.30 (s, 3H, CH3),
1.30–1.40 (m, 2H), 1.96–2.09 (m, 1H); 2.22–2.45 (m, 2H), 3.38–3.43 (dd,
J = 5.4Hz, J = 10.2 Hz 1H), 7.22–7.30 (m, 3H), 7.54–7.63 (m, 2H); 13
C
NMR (75 MHz, CDCl3): δ = 15.3 (CH3), 18.1 (CH), 18.5 (C), 22.7 (CH),
26.6 (CH2), 28.2 (CH3), 28.5 (CH3), 33.0 (CH2), 53.9 (CH), 72.5 (C),
127.2 (CH), 128.9 (CH), 130.3 (C), 133.8 (CH); 77Se (38 MHz, CDCl3): δ
= 355.2.
(1 S,2 R,3 R,6 R)-3,7,7-Trimethyl-2-(phenylselanyl)bicyclo
[4.1.0]heptan-3-ol (24)
Yield 93%; oil; [α]2D0 = –201.8 (c 3.1 CHCl3), 1H NMR (300 MHz,
CDCl3): δ = 0.75–0.88 (m, 1H), 0.98 (s, 3H, CH3), 1.21 (s, 3H, CH3),
1.22 (s, 3H, CH3), 1.25–1.75 (m, 4H), 1.93–2.10 (m, 1H), 2.11–217 (bs,
1H, OH), 4.05 (dd, J = 1.8 Hz, J = 10.2 Hz, 1H), 7.22–7.30 (m, 3H),
7.58–7.64 (m, 2H); 13C NMR (50 MHz, CDCl3): δ = 16.0 (CH2), 17.1
(CH3), 21.1 (CH), 22.0 (C), 25.3 (CH), 28.5 (CH3), 30.1 (CH3), 32.3 (CH2),
52.2 (CH), 72.6 (C), 126.8 (CH), 128.9 (CH), 132.6 (C ), 133.5 (CH);77Se
(38 MHz, CDCl3): δ = 370.9.
(1 R,2 S,5 S)-6,6-Dimethyl-2-(phenylselanylmethyl)bicyclo
[3.1.1.]heptan-2-ol (29)
Yield 72%; oil; [α]20= –55.4 (c 7.6 CHCl3)1H NMR (200 MHz, CDCl3):
δ = 0.86 (s, 3H, CHD3), 1.08 (s, 3H, CH3), 1.52 (d, J = 9.8 Hz, 1H) 1.70–
2.25 (m, 7H), 2.40 (bs, 1H, OH), 3.29 (d, J = 3.6 Hz, 2H), 7.20–7.32 (m,
3H), 7.50–7.63 (m, 2H); 13C NMR (50 MHz, CDCl3): δ = 23.3 (CH3),
24.9 (CH2), 27.2 (CH3), 27.3 (CH2), 30.7 (CH2), 37.9 (C), 40.7 (CH), 45.1
(CH2), 51.7 (CH), 75.7 (C), 127.1 (CH), 129.1 (CH), 130.9 (C), 133.2
(CH); 77Se (38 MHz, CDCl3): δ = 234.6.
REFERENCES
[1] C. Paulmier, Selenium Reagents and Intermediates in Organic Synthesis (Pergamon,
Oxford, 1985).
[2] S. Patai and Z. Rappoport, Eds., Chemistry of Organoselenium and Tellurium Com-
pounds (Wiley, New York, 1987).
[3] T. G. Back, Ed., Organoselenium Chemistry: A Practical Approach (Oxford Univer-
sity Press, Oxford, 1999).
[4] T. Wirth Ed., Topics in Current Chemistry (Springer, Heidelberg, 2000), Vol. 208.
´
[5] J. Scianowski and A. Tafelska-Kaczmarek, Polish J. Chem., 81, 529 (2007).

Optically Active Terpene Hydroxyphenylselenides
1447
´
[6] A. Uzarewicz, J. Scianowski, and J. Bakowska-Janiszewska, Polish J. Chem., 73,
ꢀ
1791 (1999).
´
[7] A. Uzarewicz, J. Scianowski, and J. B„kowska-Janiszewska, Polish J. Chem., 74,
1079 (2000).
´
[8] J. Bakowska-Janiszewska, J. Scianowski, and A. Uzarewicz, Polish J. Chem., 75,
ꢀ
649 (2001).
[9] K. Domon and K. Mori, Eur. J. Org. Chem., 3783 (2000).
[10] P. Ceccherelli, M. Curini, M. C. Marcotullio, and O. Rosati, Tetrahedron Lett., 36,
5079 (1995).
[11] A. Toshimitsu, G. Hayashi, K. Terao, and S. Uemura, J. Chem. Soc., Perkin Trans
1, 343 (1986).
[12] R. Ferritto and P. Vogel, Tetrahedron Lett., 35, 1193 (1994).
[13] C. Santi, M. Tiecco, L. Testaferri, C. Tomassini, S. Santoro, F. Marini, L. Bagnoli,
and A. Temperini, Tenth International Conference on Chemistry of Selenium and
Tellurium, Lꢀ o´dz´, Poland, June 22–27, 2007, SL-1.
[14] P. Ceccherelli, M. Curini, M. C. Marcotullio, and O. Rosati, Tetrahedron Lett., 30,
3175 (1989).
[15] K. Mori, Tetrahedron Asymmetry, 17, 2133 (2006).
[16] A. Toshimitsu, T. Aoai, H. Owada, S. Uemura, and M. Okano, Tetrahedron, 41, 5301
(1985).
[17] K. C. Nicolaou, D. A. Claremon, W. E. Barnette, and S. P. Seitz, J. Am. Chem. Soc.,
101, 3704 (1979).
[18] T. Hori and K. B. Sharpless, J. Org. Chem., 44, 4208 (1979).
[19] F. P. Greenspan, J. Am. Chem. Soc., 69, 907 (1946).
[20] H. Kuczyn´ski and Z. Chabudzin´ski, Rocz. Chem., 34, 177 (1960).