硝酸銀担持シリカゲルの吸着特性を活用した中員環アルケンのE選択的光異性化反応の開発と応用

For reviews, see: (a) J. A. Marshall, Acc. Chem. Res.

1980, 13, 213. (b) M. Nakazaki, K. Yamamoto, K.

Naemura, Top. Curr. Chem. 1984, 125, 1−25. (c) E. L.

Eliel, S. H. Wilen, L. N. Mander in Stereochemistry of

Organic Compounds, Wiley, New York, 1994, pp.

1172−1175.

2) For representative reports, see: (a) A. T. Blomquist, L.

H. Liu, J. C. Bohrer, J. Am. Chem. Soc. 1952, 74, 3643.

(b) A. C. Cope, R. A. Pike, C. F. Spencer, J. Am. Chem.

Soc. 1953, 75, 3212. (c) J. A. Marshall, V. H. Audia, T.

M. Jenson, W. C. Guida, Tetrahedron 1986, 42, 1703.

(d) J. A. Marshall, J. Lebreton, J. Org. Chem. 1988, 53,

4108. (e) A. Sudau, U. Nubbemeyer, Angew. Chem. Int.

Ed. 1998, 37, 1140. (f) K. Tomooka, N. Komine, D.

Fujiki, T. Nakai, S. Yanagitsuru, J. Am. Chem. Soc.

2005, 127, 12182. (g) K. Tomooka, M. Suzuki, M.

Shimada, S. Yanagitsuru, K. Uehara, Org. Lett. 2006,

8, 963. (h) K. Tomooka, M. Suzuki, K. Uehara, M.

Shimada, T. Akiyama, Synlett 2008, 2518. (i) K.

Uehara, K. Tomooka, Chem. Lett. 2009, 38, 1028. (j) K.

Tomooka, K. Uehara, R. Nishikawa, M. Suzuki, K.

Igawa, J. Am. Chem. Soc. 2010, 132, 9232. (k) K.

Igawa, N. Ichikawa, Y. Ano, K. Katanoda, M. Ito, T.

Akiyama, K. Tomooka, J. Am. Chem. Soc. 2015, 137,

7294. (l) J. Hayashi, K. Uehara, Y. Ano, Y. Kawasaki,

K. Igawa, K. Tomooka, Heterocycles 2019, 99, 856. (m)

K. Igawa, Y. Kawasaki, Y. Ano, T. Kashiwagi, K.

Ogawa, J. Hayashi, R. Morita, Y. Yoshioka, K. Uehara,

K. Tomooka, Chem. Lett. 2019, 48, 726.

3) For representative reports on tetrazine click reaction

of medium-sized (E)-cycloalkenes, see: (a) J. L.

Seitchik, J. C. Peeler, M. T. Taylor, M. L. Blackman, T.

W. Rhoads, R. B. Cooly, C. Refakis, J. M. Fox, R. A.

Mehl, J. Am. Chem. Soc. 2012, 134, 2898. (b) R.

Selvaraj, J. M. Fox, Current Opinion in Chemical

Biology 2013, 17, 753. For representative reviews on

tetrazine click reaction of medium-sized cycloalkenes,

see: (c) S. Liu, K. T. Dicker, X. Jia, Chem. Commun.

2015, 51, 5218. (d) J. Escorihuela, A. T. M. Marcelis, H.

Zuilhof, Adv. Mater. Interfaces 2015, 2, 1500135. (e) R.

Bucci, N. L. Sloan, L. Topping, M. Zanda, Eur. J. Org.

Chem. 2020, 5278.

4) For representative reports on RCM for synthesis of

medium-sized

cycloalkenes,

see:(a),

For

representative reviews, see: (a) A. Fürstner, Top.

1)

25

Catal. 1997, 4, 285. (b) L. Yet, Chem. Rev. 2000, 100,

2963. (c) A. Michaut, J. Rodriguez, Angew. Chem. Int.

Ed. 2006, 45, 5740.

5) Pioneering works on photochemical isomerization of

(Z)-cycloalkenes: (a) J. S. Swenton, J. Org. Chem.

1969, 34, 3217. (b) Y. Inoue, S. Takamuku, H. Sakurai,

J. Phys. Chem. 1977, 81, 7. (c) Y. Inoue, S. Takamuku,

Y. Kunitomi, H. Sakurai, J. Chem. Soc., Perkin Trans.

II 1980, 1672.

6) For a representative review on chromatographic

separation of (E)- (Z)-alkenes using Ag silica-gel, see:

C. M. Williams, L. N. Mander, Tetrahedron 2001, 57,

425.

7) M. A. Muhs, F. T. Weiss, J. Am. Chem. Soc. 1962, 84,

4697.

8) 関連研究として，Fox らは(Z)-シクロアルケンの光異性化

の際に反応溶液を銀シリカゲルを充填したカラムを通し

て循環させることで(E)-シクロアルケンを選択的に吸着

する手法を報告している: (a) M. Royzen, G. P. A. Yap, J.

M. Fox, J. Am. Chem. Soc. 2008, 130, 3760. (b) M.

Royzen, M. T. Taylor, A. DeAngelis, J. M. Fox, Chem.

Sci. 2011, 2, 2162.

9) (a) K. Tomooka, C. Iso, K. Uehara, M. Suzuki, R.

Nishikawa-Shimono, K. Igawa, Angew. Chem. Int. Ed.

2012, 51, 10355. (b) K. Igawa, K. Machida, K. Noguchi,

K. Uehara, K. Tomooka, J. Org. Chem. 2016, 81,

11587.

10) K. Tomooka, S. Miyasaka, S. Motomura, K. Igawa,

Chem. Eur. J. 2014, 20, 7598.

11) 10 wt%銀シリカゲルの調製方法:アルミホイルで覆った

300 mL の丸底フラスコに蒸留水 (100 mL)と硝酸銀(1.0

g)を入れて均一になるまで攪拌し，そこにシリカゲル

(9.0 g)を加える. その懸濁液を 20 分間撹拌した後に，ロ

ータリーエバポレーターを用いて 55 °C で水を減圧留去

した．さらに，オイルバスで 90−110 °C に加熱しつつ，

油回転式真空ポンプで 2 時間乾燥させて銀シリカゲルを

調製した．

12) Pioneering works on (E)-2a: A. C. Cope, M. W. Fordice,

J. Am. Chem. Soc. 1967, 89, 6187.

13) (E)-2aの各種スペクトルデータ：1H NMR (CDCl3, 300

MHz) δ: 7.20−7.04 (m, 4H), 5.52 (ddd, J = 15.4, 10.7,

5.0 Hz, 1H), 4.65 (ddd, J = 15.4, 11.0, 3.9 Hz, 1H),

2.81−2.75 (m, 1H), 2.59−2.47 (m, 3H), 2.45−2.24 (m,

3H), 2.05−1.86 (m, 2H), 1.77−1.65 (m, 1H) ; 13C NMR

(CDCl3, 300 MHz) δ: 145.3, 138.2, 131.37, 131.31, 130.7,

130.5, 126.2, 125.6, 36.01, 35.99, 34.1, 33.6, 29.7; IR

(neat) cm–1: 3012, 2929, 2856, 1488, 1443, 976, 801,

754; Analytical HPLC [column: CHIRALCEL OD-H

(4.6 mm × 25 cm), eluent: hexane, flow rate: 0.5

mL/min, detection: UV 254 nm, temperature: rt,

retention time: 14.7 min for (−)-(S)-isomer and 16.3

min for (+)-(R)-isomer]; HRMS (EI, positive): calcd for

C13H16 [M]+ 172.1252, found 172.1252.

14) (E)-2bの各種スペクトルデータ：1H NMR (CDCl3, 300

MHz) δ: 7.78–7.75 (m, 1H), 7.74 (d, J = 8.0 Hz, 2H),

7.36 (d, J = 8.0 Hz, 2H), 7.32–7.19 (m, 2H), 7.06 (dd, J

= 7.5, 1.8 Hz, 1H), 5.62 (ddd, J = 15.8, 11.1, 5.4 Hz, 1H),

4.70 (ddd, J = 15.8, 10.5, 4.5 Hz, 1H), 4.54 (d, J = 14.1

Hz, 1H), 4.32 (dd, J = 9.9, 4.5 Hz, 1H), 3.40 (d, J = 14.1

26

硝酸銀担持シリカゲルの吸着特性を活用した

中員環アルケンの E 選択的光異性化反応の開発と応用

Hz, 1H), 3.07 (dd, J = 10.5, 9.9 Hz, 1H), 2.86–2.78 (m,

1H), 2.60–2.52 (m, 1H), 2.47 (s, 3H), 2.45–2.35 (m, 1H),

1.82–1.70 (m, 1H); 13C NMR (CDCl3, 300 MHz) δ: 143.3,

138.9, 138.1, 136.7, 134.9, 131.6, 131.1, 129.8, 127.9,

127.4, 127.1, 126.1, 53.1, 46.6, 34.1, 34.0, 21.7; IR

(crystal using a diffuse reflector) cm–1: 2938, 1926,

1721, 1598, 1447, 1271, 1187, 1017, 985; Analytical

HPLC [column: CHIRALCEL OD-H (4.6 mm × 25 cm),

eluent: hexane/EtOH = 1/1, flow rate: 0.5 mL/min,

detection: UV 254 nm, temperature: rt, retention time:

13.9 min for (+)-(S)-isomer, 27.7 min for

(−)-(R)-isomer]; [α]D−4 = +221.2 (c 1.37, CHCl3) for

(S)-isomer (>98% ee); HRMS (EI, positive): calcd for

C19H21NO2S [M]+: 327.1293, found: 327.1295.

15) (E)-2cの各種スペクトルデータ：1H NMR (CDCl3, 300

MHz) δ: 7.38-7.33 (m, 1H), 7.28–7.19 (m, 2H),

7.14–7.09 (m, 1H), 5.91 (ddd, J = 15.6, 11.4, 5.4 Hz, 1H),

4.84 (ddd, J = 15.6, 10.8, 3.9 Hz, 1H), 4.43 (d, J = 12.9

Hz, 1H), 4.36 (dd, J = 10.1, 3.9 Hz, 1H), 4.16 (d, J =

12.9 Hz, 1H), 3.89 (dd, J = 10.8, 10.1 Hz, 1H),

2.94–2.86 (m, 1H), 2.70–2.55 (m, 2H), 1.87–1.74 (m,

1H); 13C NMR (CDCl3, 300 MHz) δ: 142.7, 137.9, 136.7,

131.8, 131.2, 129.5, 127.8, 126.7, 72.6, 64.1, 35.1, 34.0;

IR (neat) cm–1: 3015, 2953, 2859, 1460, 1446, 1345,

1222, 1187, 1026, 985, 812, 766, 750; Analytical HPLC

[column: CHIRALCEL OD-H (4.6 mm × 25 cm), eluent:

hexane/iPrOH = 98/2, flow rate: 0.5 mL/min, detection:

UV 230 nm, temperature: rt, retention time: 11.4 min

for (−)-(S)-isomer, 18.6 min for (+)-(R)-isomer]; [α]D24 =

−96.3 (c 0.92, CHCl3) for (S)-isomer (>98% ee); HRMS

(EI, positive): calcd for C12H14O [M]+ 174.1045, found

174.1050.

16) (E)-4aの各種スペクトルデータ：1H NMR (CDCl3, 300

MHz) δ: 6.17 (ddd, J = 15.3, 9.3, 5.7 Hz, 1H), 5.75 (ddd,

J = 15.3, 8.1, 6.3 Hz, 1H), 4.31–4.21 (m, 2H), 4.18–4.12

(m, 1H), 3.87–3.78 (m, 1H), 2.30–2.23 (m, 2H), 0.99 (s,

9H), 0.97 (s, 9H); 13C NMR (CDCl3, 300 MHz) δ: 139.0,

134.5, 65.6, 65.5, 36.6, 28.6, 28.0, 21.7, 21.3; IR (neat)

cm–1: 2930, 2857, 1652, 1473, 1358, 1240, 1099, 1047,

904, 827; HRMS (EI, positive): calcd for C13H26O2Si

[M]+ 242.1702, found 242.1704.

17) (E)-4bの各種スペクトルデータ：1H NMR (CDCl3, 300

MHz) δ: 7.68–7.63 (m, 4H), 7.43–7.39 (m, 3H),

7.36–7.30 (m, 3H), 6.37 (ddd, J = 15.0, 9.9, 4.5 Hz, 1H),

5.65 (ddd, J = 15.0, 11.7, 4.5 Hz, 1H), 4.67 (dd, J = 9.9,

9.9 Hz, 1H), 4.50 (dd, J = 9.9, 4.5 Hz, 1H), 4.33 (dd, J =

10.5, 5.7 Hz, 1H), 3.88 (ddd, J = 11.7, 10.5, 3.3 Hz, 1H),

2.44 (dddd, J = 11.7, 11.7, 11.7, 5.7 Hz, 1H), 2.25 (ddd,

J = 11.7, 4.5, 3.3 Hz, 1H); 13C NMR (CDCl3, 300 MHz)

δ: 140.5, 135.4, 135.0, 134.9, 134.2, 133.7, 130.0, 129.8,

128.1, 127.7, 66.0, 65.8, 35.9; IR (neat) cm–1: 3069,

2932, 1652, 1590, 1429, 1240, 1125, 1072, 1027, 903,

715, 643; HRMS (EI, positive): calcd for C17H18O2Si

[M]+ 282.1076, found 282.1071.

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