The Journal of Organic Chemistry
ARTICLE
(
S,S)-1,2-Bis[2-methyl-5-[p-(6-(1-(2-(octyloxy)naphthalen-
-yl)naphthalen-2-yloxy)hexyloxy)phenyl]-3-thienyl]cyclo-
pentene [(S,S)-1a]. To a solution of 9 (700 mg, 1.58 mmol), K CO
1.31 g, 9.48 mmol), and KI (35 mg, 0.2 mmol) in dry acetone (40 mL)
’ ACKNOWLEDGMENT
1
This work is supported by the Air Force Office of Scientific
Research (AFOSR FA9550-09-1-0254 and FA9950-09-1-0194),
the Department of Energy (DOE DE-SC0001412), and the
National Science Foundation (NSF IIP 0750379). We thank J.
Ma for spectroscopic assistance.
2
3
(
was added compound (S)-13a (1.86 g, 3.31 mmol). The reaction
mixture was then heated to reflux for 15 h. The reaction mixture was
filtered through a pad of Celite to remove K CO and then concen-
2
3
trated under reduced pressure. The residue was purified by chroma-
tography on silica gel (5% EtOAc in hexane) to give the target product
’
REFERENCES
1
(
(
S,S)-1a as a white solid (1.01 g, 46%). Mp 58ꢀ60 °C. H NMR
(
1) (a) Collings, P. J.; Hird, M. Introduction to Liquid Crystals:
CDCl , 400 MHz) δ = 7.92 (d, J = 8.8 Hz, 2H), 7.89 (d, J = 9.2 Hz,
3
Chemistry and Physics; Gray, G. W., Goodby, J. W., Fukuda, A., Eds.;
Taylor & Francis Ltd.: London, 1997. (b) Chilaya, G. Chirality in liquid
Crystals; Kitzerov, H.-S., Bahr, C., Eds.; Springer: New York, 2001.
2
7
H), 7.83 (t, J = 9.2 Hz, 4H), 7.42ꢀ7.38 (m, 8H), 7.32ꢀ7.27 (m, 4H),
.22ꢀ7.14 (m, 8H), 6.93 (s, 2H), 6.81 (d, J = 8.8 Hz, 4H), 4.00ꢀ3.87
(m, 8H), 3.73 (t, J = 6.4 Hz, 4H), 2.84 (t, J = 7.2 Hz, 4H), 2.08 (quintet,
(c) Ikeda, T. J. Mater. Chem. 2003, 13, 2037–2057. (d) Mallia, V. A.;
J = 7.2 Hz, 2H), 1.99 (s, 6H), 1.44ꢀ1.35 (m, 12H), 1.22ꢀ1.19 (m, 4H),
Tamaoki, N. Chem. Soc. Rev. 2004, 33, 76–84. (e) Matharu, A. S.; Jeeva, S.;
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Masiero, S.; Pandolini, O.; Spada, G. P. Chem.—Eur. J. 2004, 10,
1
3
1
5
1
1
2
.22ꢀ0.88 (m, 24H), 0.85 (t, J = 7.2 Hz, 6H). C NMR (CDCl
3
,
0 MHz) δ = 158.4, 154.6, 154.5, 139.6, 136.6, 134.6, 134.3, 133.4,
29.4, 129.3, 129.0, 127.8, 127.3, 126.5, 126.0, 125.5, 123.4, 122.9,
20.9, 120.8, 116.0, 114.8, 69.8, 69.7, 67.9, 38.5, 31.7, 29.4, 29.3, 29.1,
9.0, 25.6, 25.4, 22.6, 14.3, 14.1. HRMS (ESI) calcd for C95H O S
104 6 2
104 6 2
Na : 1427.7172, found: 1427.7177. Anal. Calcd for C95H O S : C,
+
8
1.16; H, 7.46; S, 4.56. Found: C, 80.92; H, 7.55; S, 4.58.
R,R)-1,2-Bis[2-methyl-5-[p-(6-(1-(2-(octyloxy)naphthalen-
-yl)naphthalen-2 yloxy)hexyloxy)phenyl]-3-thienyl]cyclo-
(
5632–5639. (c) Li, Q.; Green, L.; Venkataraman, N.; Shiyanovskaya,
1
I.; Khan, A.; Urbas, A.; Doane, J. W. J. Am. Chem. Soc. 2007, 129,
pentene [(R,R)-1b]. The target compound (R,R)-1b was synthesized
by the same procedure as that used for (S,S)-1a, and the spectral data are
12908–12909. (d) Mathews, M.; Tamaoki, N. J. Am. Chem. Soc. 2008,
130, 11409–11416. (e) White, T. J.; Bricker, R. L.; Natarajan, L. V.;
also the same as those for (S,S)-1. Mp: 57ꢀ59 °C. HRMS (ESI) calcd for
+
Tabiryan, N. V.; Green, L.; Li, Q.; Bunning, T. J. Adv. Funct. Mater. 2009,
9, 3484–3488. (f) Green, L.; Li, Y.; White, T.; Urbas, A.; Bunning, T.;
C
95
(
H
104
O
6
S
2
Na : 1427.7172, found: 1427.7178.
S,S)-1,2-Bis[2-methyl-5-[p-(11-(1-(2-((4-cyano-4 -biphe-
1
0
Li, Q. Org. Biomol. Chem. 2009, 7, 3930–3933. (g) Mathews, M.; Zola,
R. S.; Hurley, S.; Yang, D.-K.; White, T. J.; Bunning, T. J.; Li, Q. J. Am.
Chem. Soc. 2010, 132, 18361–18366. (h) Ma, J.; Li, Y.; White, T.; Urbas,
A.; Li, Q. Chem. Commun. 2010, 3463–3465.
nylyloxy)undecyloxy)naphthalen-1-yl)naphthalen-2-yloxy)-
undecyloxy)phenyl]-3-thienyl]cyclopentene [(S,S)-2]. To a
solution of 9 (380 mg, 0.85 mmol), K CO (345 mg, 2.5 mmol), and
2
3
KI (17.5 mg, 0.1 mmol) in dry acetone (10 mL) was added compound
S)-13c (1.47 g, 1.7 mmol). The reaction mixture was then heated to
(
5) (a) Hattori, H.; Uryu, T. Liq. Cryst. 2001, 28, 25–34. (b) Hattori,
(
H.; Uryu, T. Liq. Cryst. 2001, 28, 1099–1104. (c) Jin, L. M.; Li, Y.; Ma, J.;
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reflux for 15 h. The reaction mixture was filtered through a pad of Celite
to remove K CO and then concentrated under reduced pressure. The
2
3
(6) (a) Janicki, S. Z.; Schuster, G. B. J. Am. Chem. Soc. 1995, 117,
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Soc. 1995, 117, 9929–9930. (b) van Delden, R. A.; van Gelder, M. B.;
Huck, N. P. M.; Feringa, B. L. Adv. Funct. Mater. 2003, 13, 319–324.
residue was purified by chromatography on silica gel (10% EtOAc in
hexane) to give the product (S,S)-2 as a white solid (891 mg, 52%). Mp
1
6
7
7
7
(
4
2ꢀ64 °C. H NMR (CDCl , 400 MHz) δ = 7.94 (d, J = 8.8 Hz, 4H),
3
.86 (d, J = 8.0 Hz, 4H), 7.68 (d, J = 8.8 Hz, 4H), 7.63 (d, J = 8.4 Hz, 4H),
.52 (d, J = 9.2 Hz, 4H), 7.43 (d, J = 8.0 Hz, 4H), 7.42 (d, J = 8.8 Hz, 4H),
.31 (t, J = 6.8 Hz, 4H), 7.23ꢀ7.17 (m, 8H), 7.00 (d, J = 8.8, 4H), 6.95
(c) van Delden, R. A.; Koumura, N.; Harada, N.; Feringa, B. L. Proc. Natl.
Acad. Sci. U.S.A. 2002, 99, 4945–4949. (d) Eelkema, R.; Pollard, M. M.;
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D. J.; Feringa, B. L. Nature 2006, 440, 163. (e) Bosco, A.; Jongejan,
M. G. M.; Eelkema, R.; Katsonis, N.; Lacaze, E.; Ferrarini, A.; Feringa,
B. L. J. Am. Chem. Soc. 2008, 130, 14615–14624.
s, 2H), 6.88 (d, J = 8.4, 4H), 4.03ꢀ3.90 (m, 16H), 2.85 (t, J = 7.6 Hz,
H), 2.09 (quintet, J = 7.2 Hz, 2H), 1.85 (s, 6H), 1.85ꢀ1.78 (m, 8H),
13
1
.48ꢀ1.25 (m, 32H), 1.15ꢀ0.92 (m, 32 H). CNMR(CDCl
3
, 100 MHz)
δ= 159.8, 158.3, 154.5, 145.2, 139.5, 136.5, 134.5, 134.2, 133.3, 132.5, 131.2,
129.2, 129.0, 128.3, 127.7, 127.2, 127.0, 126.5, 125.9, 125.5, 123.34, 123.31,
(
8) (a) Denekamp, C.; Feringa, B. L. Adv. Mater. 1998, 10, 1080–1082.
b) Uchida, K.; Kawai, Y.; Shimizu, Y.; Vill, V.; Irie, M. Chem. Lett. 2000,
9, 654–655. (c) Yamaguchi, T.; Inagawa, T.; Nakazumi, H.; Irie, S.; Irie,
122.8, 120.7, 119.1, 115.8, 115.0, 114.7, 110.0, 109.9, 69.7, 68.1, 68.0, 38.5,
(
2
2
9.51, 29.48, 29.4, 29.3, 29.2, 29.1, 26.0, 25.6, 23.0, 14.3. MS (MALDI): m/z
+
2016 (M + H ). Anal. Calcd for C137H N O S : C, 81.59, H, 7.50; found:
150
2
8 2
M. Mol. Cryst. Liq. Cryst. 2000, 345, 287–292. (d) Yamaguchi, T.; Inagawa,
T.; Nakazumi, H.; Irie, S; Irie, M. Chem. Mater. 2000, 12, 869–871.
C, 81.45, H,7.46.
(e) Yamaguchi, T.; Inagawa, Nakazumi, H.; Irie, S.; Irie, M. Mol. Cryst. Liq.
’
ASSOCIATED CONTENT
Supporting Information. 1 CD spectra, measurement of
Cryst. 2001, 365, 861–866. (f) Yamaguchi, T.; Inagawa, T.; Nakazumi, H.;
Irie, S.; Irie, M. J. Mater. Chem. 2001, 11, 2453–2458. (g) Rameshbabu, K.;
Urbas, A.; Li, Q. J. Phys. Chem. B 2011, 115, 3409–3415. (h) van Leeuwen,
T.; Pijper, T. C.; Areephong, J.; Feringa, B. L.; Browne, W. R.; Katsonis, N.
J. Mater. Chem. 2011, 21, 3142–3146.
(9) (a) Irie., M. Chem. Rev. 2000, 100, 1685–1716. (b) Tian, H.;
Yang, S. Chem. Soc. Rev. 2004, 33, 85–97. (c) Tian, H.; Wang, S. Chem.
Commun. 2007, 781–792.
S
b
pitch and helical twisting power, H NMR changes of compound
1
(
S,S)-1a before and after UV irradiation, and copies of H NMR
13
and C NMR. This material is available free of charge via the
Internet at http://pubs.acs.org.
(
10) Proni, G.; Spada, G. P. J. Org. Chem. 2000, 65, 5522–5527.
(11) Goh, M.; Akagi, K. Liq. Cryst. 2008, 35, 953–965.
12) de Jong, J. J. D.; Lucas, L. N.; Hania, R.; Pugzlys, A.; Kellogg,
R. M.; Feringa, B. L.; Duppen, K.; van Esch, J. H. Eur. J. Org. Chem.
2003, 1887–1893.
’
AUTHOR INFORMATION
(
Corresponding Author
*E-mail: qli1@kent.edu. Tel: 330-672-1537. Fax: 330-672-2796.
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dx.doi.org/10.1021/jo201139t |J. Org. Chem. 2011, 76, 7148–7156