Subscribe to RSS
DOI: 10.1055/a-1934-1346
Ultralong C(sp3)–C(sp3) Single Bonds Shortened and Stabilized by London Dispersion
We are grateful for grants-in-aid from MEXT and JSPS (Nos. 20H02719 and 20K21184 to T.Su, and 21H01912 and 21H05468 to Y.I.). This work was also supported by the Research Program of the Five-Star Alliance in NJRC Mater. & Dev. MEXT and by the Masason Foundation (S.K.).
![](https://www.thieme-connect.de/media/synlett/202310/lookinside/thumbnails/st-2022-b0342-c_10-1055_a-1934-1346-1.jpg)
Abstract
A carbon–carbon (C–C) single bond longer than 1.7 Å shows unique bond flexibility, even though a C–C single bond is typically rigid and robust. We report here that the bond length of flexible C–C single bonds surrounded by bulky alkyl groups in novel hexaphenylethane-type hydrocarbons might be affected by weak noncovalent interactions, such as London dispersion. Thanks to London dispersion, an ultralong and flexible C–C single bond exhibits an obvious bond contraction. X-ray analyses and Raman spectroscopy provided direct information regarding the bond length and strength, whereas density functional theory calculations explained the bond contraction driven by London dispersion. The change in bond length of an extremely elongated flexible C–C bond would be a good probe for quantifying weak interactions that are usually difficult to detect.
Supporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/a-1934-1346.
- Supporting Information
Publication History
Received: 27 July 2022
Accepted after revision: 30 August 2022
Accepted Manuscript online:
30 August 2022
Article published online:
11 October 2022
© 2022 . Thieme. All rights reserved
Georg Thieme Verlag KG
Rüdigerstraße 14, 70469 Stuttgart, Germany
-
References and Notes
- 1 Fenniri H, Mathivanan P, Vidale KL, Sherman DM, Hallenga K, Wood KV, Stowell JG. J. Am. Chem. Soc. 2001; 123: 3854
- 2 Panigrahi SK, Desiraju GR. Proteins: Struct., Funct., Bioinf. 2007; 67: 128
- 3 Jain P, Antilla JC. J. Am. Chem. Soc. 2010; 132: 11884
- 4 Hunter CA. Angew. Chem. Int. Ed. 2004; 43: 5310
- 5 Kahr B, Van Engen D, Mislow K. J. Am. Chem. Soc. 1986; 108: 8305
- 6 Schreiner PR, Chernish LV, Gunchenko PA, Tikhonchuk EY, Hausmann H, Serafin M, Schlecht S, Dahl JE. P, Carlson RM. K, Fokin AA. Nature 2011; 477: 308
- 7 Rösel S, Becker J, Allen WD, Schreiner PR. J. Am. Chem. Soc. 2018; 140: 14421
- 8 Schümann JM, Wagner JP, Eckhardt AK, Quanz H, Schreiner PR. J. Am. Chem. Soc. 2021; 143: 41
- 9 Aikawa H, Takahira Y, Yamaguchi M. Chem. Commun. 2011; 47: 1479
- 10 Yamaguchi M, Shigeno M, Saito N, Yamamoto K. Chem. Rec. 2014; 14: 15
- 11 Ikawa T, Yamamoto Y, Heguri A, Fukumoto Y, Murakami T, Takagi A, Masuda Y, Yahata K, Aoyama H, Shigeta Y, Tokiwa H, Akai S. J. Am. Chem. Soc. 2021; 143: 10853
- 12 Eschmann C, Song L, Schreiner PR. Angew. Chem. Int. Ed. 2021; 60: 4823
- 13 Gomberg M. Ber. Dtsch. Chem. Ges. 1900; 33: 3150
- 14 Gomberg M. J. Am. Chem. Soc. 1900; 22: 757
- 15 Lankamp H, Nauta WT, MacLean C. Tetrahedron Lett. 1968; 9: 249
- 16 Stein M, Winter W, Rieker A. Angew. Chem., Int. Ed. Engl. 1978; 17: 692
- 17 Grimme S, Schreiner PR. Angew. Chem. Int. Ed. 2011; 50: 12639
- 18 Rösel S, Balestrieri C, Schreiner PR. Chem. Sci. 2016; 8: 405
- 19 Rösel S, Schreiner PR. Isr. J. Chem. 2022; 62: e202200002
- 20 Fokin AA, Chernish LV, Gunchenko PA, Tikhonchuk EY, Hausmann H, Serafin M, Dahl JE. P, Carlson RM. K, Schreiner PR. J. Am. Chem. Soc. 2012; 134: 13641
- 21 Ishigaki Y, Shimajiri T, Takeda T, Katoono R, Suzuki T. Chem 2018; 4: 795
- 22 Shimajiri T, Suzuki T, Ishigaki Y. Angew. Chem. Int. Ed. 2020; 59: 22252
- 23 Grimme S, Antony J, Ehrlich S, Krieg H. J. Chem. Phys. 2010; 132: 154104
-
24
Diol 4
A 1.56 M solution of BuLi in hexane (1.35 mL, 2.11 mmol) was added to a suspension of 5,6-dibromo-1,2-dihydroacenaphthylene (3; 312 mg, 1.00 mmol) in dry Et2O (20 mL) at 24 °C, and the mixture was stirred at 24 °C for 1 h. 2,8-Di-tert-butyldibenzosuberenone (669 mg, 2.10 mmol) was added, and the resulting mixture was refluxed for 4.5 h then cooled to 24 °C and diluted with H2O. The mixture was extracted with EtOAc (×3), and the combined organic layers were washed with H2O and brine then dried (Na2SO4), filtered, and concentrated under reduced pressure. The crude product was purified by washing with MeOH (3 × 20 mL) to give a white solid; yield: 451 mg (57%); mp 193.3–203.1 °C (dec).
IR (ATR): 3566, 2960, 2903, 2867, 1596, 1559, 1507, 1490, 1458, 1387, 1362, 1313, 1271, 1215, 1179, 1164, 1145, 1093, 1077, 1044, 1022, 946, 938, 891, 828, 814, 803, 783, 755, 731, 691, 677, 662, 650, 627, 549, 507, 491, 455, 428 cm–1. 1H NMR (400 MHz, CDCl3): δ = 7.88 (d, J = 8.3 Hz, 2 H), 7.84 (d, J = 8.5 Hz, 2 H), 7.68 (dd, J = 2.0, 8.3 Hz, 2 H), 7.25 (dd, J = 2.1, 8.4 Hz, 2 H), 6.97 (d, J = 2.0 Hz, 2 H), 6.72 (d, J = 2.0 Hz, 2 H), 6.69 (d, J = 7.3 Hz, 2 H), 6.58 (d, J = 7.3 Hz, 2 H), 5.63 (d, J = 11.4 Hz, 2 H), 5.55 (d, J = 11.4 Hz, 2 H), 3.29–3.12 (m, 4 H), 1.41 (s, 18 H), 1.18 (s, 18 H), 0.94 (s, 2 H). 13C NMR (100 MHz, CDCl3): δ = 149.16, 147.61, 147.41, 145.21, 138.27, 137.52, 136.41, 134.68, 133.90, 131.68, 131.54, 130.61, 129.33, 126.19, 125.01, 124.41, 124.30, 123.78, 121.38, 116.65, 78.56, 34.54, 34.08, 31.37, 31.34, 29.83. LR-MS (FD): m/z (%): 793.49 (6), 792.49 (23), 791.48 (67), 790.48 (M+, bp), 772.46 (5), 500.24 (6). HRMS (FD): m/z calcd for C58H62O2: 790.47498; found: 790.47359.
Diol 6
A 1.57 M solution of BuLi in hexane (1.35 mL, 2.11 mmol) was added to a suspension of 5,6-dibromoacenaphthylene (5; 310 mg, 1.00 mmol) in dry Et2O (20 mL) at 22 °C, and the mixture was stirred at 22 °C for 1 h. 2,8-di-tert-butyldibenzosuberenone (668 mg, 2.10 mmol) was added, and the resulting mixture was refluxed for 6 h, allowed to cool to 24 °C, diluted with H2O, and extracted with CHCl3 (×3). The combined organic layers were washed with water and brine, dried (Na2SO4), filtered, and concentrated under reduced pressure. The crude product was purified by column chromatography [silica gel CH2Cl2–hexane (1:3)] to give a pale-orange solid; yield: 283 mg (36%); mp 229.5–261.3 ℃ (dec); Rf = 0.42 (silica gel CH2Cl2–hexane, 1:3). IR (ATR): 3560, 2956, 2866, 2362, 1602, 1559, 1507, 1490, 1384, 1361, 1313, 1264, 1206, 1093, 1045, 888, 825, 805, 741, 715, 691, 668, 651, 624, 555, 506 cm–1. 1H NMR (400 MHz, CDCl3): δ = 7.86 (d, J = 8.4 Hz, 2 H), 7.82 (d, J = 8.4 Hz, 2 H), 7.69 (dd, J = 2.2, 8.4 Hz, 2 H), 7.27 (dd, J = 2.2, 8.6 Hz, 2 H), 7.00 (d, J = 1.6 Hz, 2 H), 6.98 (d, J = 7.2 Hz, 2 H), 6.75 (d, J = 2.0 Hz, 2 H), 6.70 (s, 2 H), 6.62 (d, J = 7.2 Hz, 2 H), 5.68 (d, J = 11.2 Hz, 2 H), 5.64 (d, J = 11.6 Hz, 2 H), 1.42 (s, 18 H), 1.18 (s, 18 H), 0.97 (s, 2 H). 13C NMR (100 MHz, CDCl3): δ = 149.50, 147.73, 147.10, 143.23, 138.93, 137.44, 134.41, 134.05, 131.70, 131.03, 130.54, 129.81, 128.70, 127.98, 125.97, 125.07, 124.52, 124.47, 123.80, 121.54, 121.11, 78.62, 34.58, 34.12, 31.35, 31.32. LR-MS (FD): m/z (%): 791.44 (6), 790.44 (25), 789.44 (M+, 65), 788.43 (bp), 773.88 (5), 772.87 (9), 772.43 (10), 771.43 (30), 770.42 (45), 499.24 (8), 498.24 (21), 356.14 (16), 301.09 (7), 300.08 (25), 152.05 (5). HRMS (FD): m/z [M+] calcd for C58H60O2: 788.45933; found: 788.46151. - 25 Polycyclic Hydrocarbon 1- t Bu TfOH (110 μL, 1.24 mmol) was added to a suspension of 4 (100 mg, 126 μmol) in anhyd CH2Cl2 (1 mL) at 0 °C. HFIP (1 mL) was added and the mixture was stirred at 0 °C for 30 min. Anhyd MeCN (2 mL) and activated Zn powder (1.24 g, 18.8 mmol) were added at 0 °C, and the resulting mixture was stirred at 0 °C for 5 min then warmed to 24 °C and stirred at 24 °C for 10 min. The resulting mixture was diluted with water at 0 °C and extracted with CH2Cl2 (×3). The combined organic layer was washed successively with water, sat. aq NaHCO3, and brine then dried (MgSO4), filtered through a silica pad, and concentrated under reduced pressure to give a white solid; yield: 95.4 mg (quant); mp 266.4–279.8 °C (dec). IR (ATR): 3028, 2951, 2864, 1603, 1559, 1500, 1476, 1458, 1440, 1429, 1382, 1359, 1290, 1264, 1230, 1206, 1147, 1065, 1023, 948, 902, 886, 841, 804, 792, 765, 752, 719, 703, 689, 654, 600, 511, 467, 447, 434, 430, 424, 420 cm–1. 1H NMR (400 MHz, CDCl3): δ = 7.42 (d, J = 6.9 Hz, 2 H), 7.15 (d, J = 7.0 Hz, 2 H), 6.77 (d, J = 2.1 Hz, 4 H), 6.46 (dd, J = 2.2, 8.7 Hz, 4 H), 6.33 (s, 4 H), 6.23 (d, J = 8.7 Hz, 4 H), 3.62 (s, 4 H), 1.12 (s, 36 H). 13C NMR (100 MHz, CDCl3): δ = 148.10, 147.37, 141.98, 138.42, 137.81, 137.58, 135.75, 133.49, 132.46, 127.47, 127.38, 123.05, 121.26, 84.88, 33.73, 31.95, 31.21. LR-MS (FD): m/z (%): 759.40 (8), 758.39 (25), 757.39 (66), 756.38 (M+, bp). HRMS (FD): m/z calcd for C58H60: 756.46950; found: 756.47015. Polycyclic Hydrocarbon 2- t Bu A 0.79 M solution TMSClO4 in dry toluene (1.05 mL, 830 μmol) was added to a suspension of 6 (99.7 mg, 126 μmol) in HFIP (3 mL) at 0 °C, and the solution was stirred at 0 °C for 30 min. Anhyd MeCN (7 mL) and activated Zn powder (1.24 g, 190 mmol) were added and the resulting mixture was stirred at 0 °C for 5 min, then warmed to 22 °C and stirred at 22 °C for 5 min. The mixture was then diluted with water at 0 °C and extracted with EtOAc (×3). The combined organic layers were washed with water, sat. aq NaHCO3, and brine then dried (Na2SO4), filtered through a silica pad, and concentrated under reduced pressure. The crude product was purified by column chromatography to give an orange solid; yield: 89.3 mg (93%); mp 208.2–248.6 ℃ (dec.); Rf = 0.30 (silica gel, CH2Cl2–hexane, 1:5). IR (ATR): 3031, 2952, 2865, 2361, 1734, 1700, 1684, 1653, 1603, 1559, 1506, 1458, 1419, 1382, 1360, 1290, 1264, 1206, 1148, 1078, 949, 908, 887, 841, 832, 802, 793, 736, 684, 668, 652, 502 cm–1. 1H NMR (400 MHz, CDCl3): δ = 7.94 (d, J = 6.8 Hz, 2 H), 7.33 (d, J = 7.2 Hz, 2 H), 7.30 (s, 2 H), 6.79 (d, J = 2.0 Hz, 4 H), 6.44 (dd, J = 2.4, 8.8 Hz, 4 H), 6.36 (s, 4 H), 6.12 (d, J = 8.8 Hz, 4 H), 1.12 (s, 36 H). 13C NMR (100 MHz, CDCl3): δ = 153.62, 148.34, 138.16, 135.99, 135.66, 133.38, 132.45, 129.23, 127.47, 127.26, 126.91, 123.15, 85.85, 33.72, 31.13. LR-MS (FD): m/z (%): 757.44 (8), 756.44 (25), 755.44 (M+, 67), 754.43 (M+, bp). HR-MS (FD): m/z [M+] calcd for C58H58: 754.45385; found: 754.45572.
- 26 Takeda T, Uchimura Y, Kawai H, Katoono R, Fujiwara K, Suzuki T. Chem. Lett. 2013; 42: 954
- 27 Suzuki T, Uchimura Y, Nagasawa F, Takeda T, Kawai H, Katoono R, Fujiwara K, Murakoshi K, Fukushima T, Nagaki A, Yoshida J.-i. Chem. Lett. 2014; 43: 86
- 28 CCDC 2192641–2192644 contain the supplementary crystallographic data for compound 1- t Bu at 100, 200, 300, and 400 K, respectively, and CCDC 2192645–2192648 contain those for compound 2- t Bu at 100, 200, 300, and 400 K, respectively. The data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/structures
- 29 Hwang J, Li P, Smith MD, Shimizu KD. Angew. Chem. Int. Ed. 2016; 55: 8086
- 30 Bader RF. W. Acc. Chem. Res. 1985; 18: 9
- 31 Contreras-García J, Johnson ER, Keinan S, Chaudret R, Piquemal JP, Beratan DN, Yang W. J. Chem. Theory Comput. 2011; 7: 625
- 32 Wong MW. Chem. Phys. Lett. 1996; 256: 391
- 33 Van Helvoort K, Knippers W, Fantoni R, Stolte S. Chem. Phys. 1987; 111: 445