Synlett 2018; 29(16): 2147-2154
© Georg Thieme Verlag Stuttgart · New York
Transmission of Point Chirality to Axial Chirality for Strong Circular Dichroism in Triarylmethylium-o,o -dimers
a
Department of Chemistry, Faculty of Science, Hokkaido University, Sapporo, Hokkaido 060-0810, Japan Email:
tak@sci.hokudai.ac.jp
,
Tomohiro Iwai
a
Department of Chemistry, Faculty of Science, Hokkaido University, Sapporo, Hokkaido 060-0810, Japan Email:
tak@sci.hokudai.ac.jp
,
Yuki Hayashi
a
Department of Chemistry, Faculty of Science, Hokkaido University, Sapporo, Hokkaido 060-0810, Japan Email:
tak@sci.hokudai.ac.jp
,
Aiichiro Nagaki
b
Department of Synthetic Chemistry and Biological Chemistry, Graduate School of Engineering, Kyoto University, Kyoto 615-8510, Japan
,
Ryo Katoono
a
Department of Chemistry, Faculty of Science, Hokkaido University, Sapporo, Hokkaido 060-0810, Japan Email:
tak@sci.hokudai.ac.jp
,
Kenshu Fujiwara
c
Department of Life Science, Graduate School of Engineering Science, Akita University, Akita 010-8052, Japan
,
Jun-ichi Yoshida
b
Department of Synthetic Chemistry and Biological Chemistry, Graduate School of Engineering, Kyoto University, Kyoto 615-8510, Japan
,
a
Department of Chemistry, Faculty of Science, Hokkaido University, Sapporo, Hokkaido 060-0810, Japan Email:
tak@sci.hokudai.ac.jp
› Author Affiliations This work was also supported by the Research Program of the “Five-star Alliance” in “NJRC Mater. & Dev.” MEXT. We thank Grant-in-Aid for Scientific Research on Innovative Areas: “Middle molecular strategy” (No. 2707) and “Reaction Integration” (No. 2105) from MEXT and Grant-in-Aid from JSPS (Nos. 15H03790, 16K13968, 18K05069) Japan.
In memory of Kurt Mislow (1923–2017) and Shô Itô (1924–2018)
Published as part of the Cluster Atropisomerism
Abstract
Triarylmethylium-o,o -dimers adopt a twisted geometry so that two diarylmethyliums are stacked in a slipped manner. Thus, chiral auxiliaries on the aryl groups induce a preference in the axial chirality of the central biphenyl unit. Strong circular dichroism is attained through exciton coupling, which can be used for additional spectral output in their electrochromic behavior. Diastereoselectivity based on π–π stacking exhibits unique solvent effects, thus endowing multifunctional response properties.
Key words
chiral induction -
axial chirality -
exciton coupling -
redox system -
electrochromism -
flow microreactor -
dication -
dye
Supporting Information
The experimental procedures and characterization data for new compounds are given in the Supporting Information. The cyclic voltammogram of (R ,R ,R ,R )-5
2+ in CH2 Cl2 , VT-NMR spectra of (R ,R )-6
2+ (SbCl6
− )2 in CDCl3 , and CD spectra of (R ,R )-6
2+ (SbCl6
− )2 and the related dication salts in various solvents are also given.
Supporting information for this article is available online at https://doi.org/10.1055/s-0037-1610190.
Supporting Information
References and Notes
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11 Experimental procedures and characterization data for new compounds are given in the Supporting Information. Selected analytical data are as follows:
(R ,R ,R ,R )-5 : Mp 83–86 °C (decomp.). IR (KBr): 2928, 2856, 1608, 1574, 1556, 1460, 1434, 1376, 1280, 1197, 1160, 1110, 1030, 917, 849, 598 cm–1 . 1 H NMR (300 MHz, CD3 CN): δ = 6.73–7.84 (24 H, brm), 4.79 (4 H, m), 1.75 (8 H, brm), 1.24–1.57(44 H, brm), 0.83–1.83 (12 H, brm) ppm. 13 C NMR (75 MHz, CDCl3 ): δ = 190.85, 190.59, 173.70, 173.68, 171.03, 170.85, 146.18, 144.28, 144.17, 142.69, 142.56, 140.63, 136.64, 136.55, 134.18, 134.14, 133.83, 133.81, 133.21, 132.92, 131.88, 131.85, 128.2259, 119.14, 118.33, 118.25, 79.29, 79.19, 77.72, 77.48, 36.35, 36.27, 36.26, 36.20, 32.10, 32.08, 32.05, 29.43, 25.51, 25.49, 25.44, 22.91, 19.76, 19.57, 19.47, 13.98 ppm. FAB-LR-MS: m /z = 997 ([M – 2SbCl6 ]+ , 15%). UV/Vis (CH2 Cl2 ): λmax = 538 (log ε 5.00), 417 (4.57), 280 (4.63) nm. CD (CH2 Cl2 ): λ = 564 (Δε +31), 534 (–19), 406 (+2.9), 281 (–4.6), 267 (+1.5) nm. Anal. Calcd for C70 H92 Cl12 O4 Sb2 : C, 50.45; H, 5.56; Cl, 25.53. Found: C, 50.43; H, 5.31; Cl, 25.45.
(R ,R ,R ,R )-5
2+ (SbCl6
− )2 : Mp 83–86 °C (decomp.). IR (KBr) 2928, 2856, 1608, 1574, 1556, 1460, 1434, 1376, 1280, 1197, 1160, 1110, 1030, 917, 849, 598 cm–1 . 1 H NMR (300 MHz, CD3 CN): δ = 6.73–7.84 (24 H, brm), 4.79 (4 H, m), 1.75 (8 H, brm), 1.24–1.57(44 H, brm), 0.83–1.83 (12 H, brm) ppm. 13 C NMR (75 MHz, CDCl3 ):δ = 190.85, 190.59, 173.70, 173.68, 171.03, 170.85, 146.18, 144.28, 144.17, 142.69, 142.56, 140.63, 136.64, 136.55, 134.18, 134.14, 133.83, 133.81, 133.21, 132.92, 131.88, 131.85, 128.2259, 119.14, 118.33, 118.25, 79.29, 79.19, 77.72, 77.48, 36.35, 36.27, 36.26, 36.20, 32.10, 32.08, 32.05, 29.43, 25.51, 25.49, 25.44, 22.91, 19.76, 19.57, 19.47, 13.98 ppm. FAB-LR-MS: m /z = 997 ([M – 2SbCl6 ]+ , 15%). UV/Vis (CH2 Cl2 ): λmax = 538 (log ε 5.00), 417 (4.57), 280 (4.63) nm. CD (CH2 Cl2 ): λ = 564 (Δε +31), 534 (–19), 406 (+2.9), 281 (–4.6), 267 (+1.5) nm. Anal. Calcd for C70 H92 Cl12 O4 Sb2 : C, 50.45; H, 5.56; Cl, 25.53. Found: C, 50.43; H, 5.31; Cl, 25.45.
(R ,R ,R ,R )-7 : IR (neat): 3406, 2930, 2857, 1606, 1505, 1465, 1376, 1291, 1244, 1175, 1114, 829, 756, 665 cm–1 . 1 H NMR (300 MHz, CDCl3 ): δ = 6.99–7.26 (10 H, m), 6.75–6.83 (12 H, m), 6.07 (2 H, d, J = 7.3 Hz), 4.41 (2 H, s), 4.30–4.36 (4 H, m, J = 6.0 Hz), 1.16–1.82 (52 H, brm), 0.88 (12 H, brm) ppm. 13 C NMR (75 MHz, CDCl3 ): δ = 157.27, 157.07, 144.07, 140.87, 140.58, 138.38, 131.56, 130.24, 129.72, 128.56, 125.84, 125.79, 115.05, 114.89, 83.22, 74.00, 73.82, 36.43, 31.81, 29.28, 25.52, 22.59, 19.73, 14.07 ppm. FD-LR-MS: m /z = 1030 (M+ , BP). FD-HR-MS: m /z calcd for C70 H94 O6 : 1030.7050; found: 1030.7045.
(R ,R )-6 : Mp 138–142 °C (decomp.). IR (KBr): 3042, 2929, 2856, 2799, 1608, 1576, 1505, 1480, 1443, 1376, 1353, 1286, 1247, 1213, 1186, 1125, 1062, 1013, 948, 848, 807, 759, 746, 619, 573 cm–1 . 1 H NMR (300 MHz, C6 D6 ): δ = 7.68–7.63 (3 H, m), 7.59 (1 H, dd, J = 7.9, 1.4 Hz), 7.45 (4 H, br), 7.38 (4H, br), 7.13–7.02 (4 H, m), 6.64 (4 H, brd, J = 7.9 Hz), 6.31 (4 H, brd, J = 7.9 Hz), 4.03 (2 H, br), 2.42 (12 H, s), 1.68–1.52 (2 H, m), 1.39–1.01 (24 H, m), 0.86 (6 H, t, J = 6.9 Hz) ppm. 13 C NMR (100 MHz, C6 D6 ): δ = 156.73, 148.57, 145.79, 145.34, 136.84, 136.64, 129.17, 129.05, 127.90, 127.00, 126.83, 124.68, 124.54, 112.65, 110.03, 73.11, 63.91, 63.65, 39.94, 36.94, 36.88, 32.10, 29.64, 25.80, 22.94, 19.88, 19.85, 14.30 ppm. FD-LR-MS: m /z = 829 (34), 828 (80), 827 (M+ , BP). FD-HR-MS: m /z calcd for C58 H70 N2 O2 : 826.5437; found: 826.5437. UV/Vis (CH2 Cl2 ): λmax = (log ε) 270 (4.61) nm.
(R ,R )-6
2+ (SbCl6
− )2 : Mp 128–132 °C. IR (KBr): 3061, 2927, 2856, 1618, 1606, 1582, 1485, 1464, 1435, 1362, 1315, 1278, 1159, 1109, 1029, 963, 937, 910, 850, 831, 755, 722, 600 cm–1 . 1 H NMR (300 MHz, CDCl3 ): δ = 6.60–8.00 (24 H, brm), 4.72–4.88 (2 H, brm), 3.25 (12 H, m), 1.66–1.90 (4 H, brm), 1.18–1.56 (22 H, brm), 0.87–1.02 (6 H, brm) ppm. 13 C NMR (100 MHz, CDCl3 ): δ = 19.38, 19.45, 19.55, 25.35, 25.47, 29.40, 29.48, 29.49, 32.05, 32.1065, 36.13, 36.18, 36.27, 40.81, 41.36, 41.44, 77.45, 77.61, 78.70, 78.71, 113.92, 114.77, 118.66, 127.24, 127.81, 127.88, 130.70, 130.79, 132.47, 132.52, 132.99, 133.47, 133.64, 133.85, 133.94, 134.17, 136.52, 136.63, 138.98, 140.24, 140.30, 140.38, 140.41, 141.21, 141.26, 142.29, 142.41, 143.08, 143.17, 145.37, 145.39, 157.82, 157.98, 170.95, 172.78, 173.00, 191.52, 191.71 ppm. FD-LR-MS: m /z = 8277 ([M – 2SbCl6 ]+ , BP). FD-HR-MS: m /z calcd for C58 H70 N2 O2 : 826.5437; found: 826.5420.
(R ,R )-8 : Mp 71.0–74.0 °C. IR (KBr): 3411, 2929, 2856, 2800, 1609, 1505, 1466, 1443, 1376, 1351, 1293, 1243, 1162, 1132, 1062, 1132, 1004, 948, 917, 816, 759, 622, 577, 560 cm–1 . 1 H NMR (300 MHz, CDCl3 ): δ = 7.10–6.98 (8 H, m), 6.95 (2 H, d, J = 9.0 Hz), 6.86–6.80 (3 H, m), 6.79–6.73 (5 H, m), 6.63 (4 H, dd, J = 9.0, 1.5 Hz), 6.19 (1 H, d, J = 7.7 Hz), 6.03 (1 H, d, J = 7.7 Hz), 5.17 (1 H, brd, J = 7.9 Hz), 4.39–4.26 (2 H, m), 3.63 (1 H, brd, J = 4.8 Hz), 2.95 (6 H, s), 2.91 (6 H, s) 1.72 (2 H, br), 1.50–1.22 (24 H, m), 0.92–0.83 (6 H, m) ppm. 13 C NMR (100 MHz, CDCl3 ): δ = 157.07, 156.82, 149.56, 149.40, 144.50, 144.03, 141.39, 141.17, 140.71, 138.52, 136.86, 134.69, 131.58, 131.41, 130.28, 130.20, 129.67, 129.37, 128.62, 128.11, 125.92, 125.72, 125.44, 125.39, 114.93, 114.83, 111.73, 111.69, 83.86, 82.64, 82.59, 73.97, 73.92, 73.76, 40.62, 40.55, 36.51, 36.47, 36.37, 31.80, 29.28, 29.25, 25.53, 25.48, 22.57, 19.77, 19.67, 14.06 ppm. FD-LR-MS: m /z = 863 (22), 862 (63), 861 (M+ , BP), 844 (24), 843 (35). FD-HR-MS: m /z calcd for C58 H72 N2 O4 : 860.5492; found: 860.5485.
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