Synlett 2023; 34(10): 1147-1152
DOI: 10.1055/a-1934-1346
cluster
Dispersion Effects

Ultralong C(sp3)–C(sp3) Single Bonds Shortened and Stabilized by London Dispersion

Takuya Shimajiri  ∗
a   Department of Chemistry, Faculty of Science, Hokkaido University, Sapporo, Hokkaido 060-0810, Japan
b   Creative Research Institution, Hokkaido University, Sapporo, Hokkaido 001-0021, Japan
,
Yuta Kawakami
a   Department of Chemistry, Faculty of Science, Hokkaido University, Sapporo, Hokkaido 060-0810, Japan
,
Soki Kawaguchi
a   Department of Chemistry, Faculty of Science, Hokkaido University, Sapporo, Hokkaido 060-0810, Japan
,
Yuki Hayashi
a   Department of Chemistry, Faculty of Science, Hokkaido University, Sapporo, Hokkaido 060-0810, Japan
,
Kazuto Hada
a   Department of Chemistry, Faculty of Science, Hokkaido University, Sapporo, Hokkaido 060-0810, Japan
,
Takanori Suzuki 
a   Department of Chemistry, Faculty of Science, Hokkaido University, Sapporo, Hokkaido 060-0810, Japan
,
Yusuke Ishigaki  ∗
a   Department of Chemistry, Faculty of Science, Hokkaido University, Sapporo, Hokkaido 060-0810, Japan
› Author AffiliationsWe 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.).
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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.

Key words

strained molecules - hydrocarbons - C–C bond length - X-ray analysis - London dispersion

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

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    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.
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