Pulling Outward but Reacting Inward: Mechanically Induced Symmetry-Allowed Reactions of cis- and trans-Diester-Substituted Dichlorocyclopropanes

Abstract

The mechanically induced symmetry-allowed disrotatory ring openings of cis- and trans-gem-dichlorocyclopropane (gDCC) diesters are demonstrated through sonication and single-molecule force spectroscopy (SMFS) studies. In contrast to the previously reported symmetry-forbidden conrotatory ring opening of alkyl-tethered trans-gDCC, we show that the diester-tethered trans-gDCC primarily undergoes a symmetry-allowed disrotatory pathway even at the high forces (>2 nN) and short-time scales (ms or less) of sonication and SMFS experiments. The quantitative force-rate data obtained from SMFS data is consistent with computational models of transition-state geometry for the symmetry-allowed process, and activation lengths of 1.41 ± 0.02 Å and 1.08 ± 0.03 Å are inferred for the cis-gDCC diester and trans-gDCC diester, respectively. The strong mechanochemical coupling in the trans-gDCC is notable, given that the directionality of the applied force may appear initially to oppose the disrotatory motion associated with the reaction. The stereochemical perturbations of mechanical coupling created by the ester attachments reinforce the complexity that is possible in covalent polymer mechanochemistry and illustrate the breadth of reactivity outcomes that are available through judicious mechanophore design.

Key words

Woodward–Hoffmann - polymer mechanochemistry - structure–activity - gem-dichlorocyclopropane diester - sonication and single-molecule force spectroscopy

• References and Notes

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• 23 Typical Experimental Procedure for the Synthesis of Multimechanophore Polymers P1 and P2 50 mg cis-macrocycle (0.15 mmol) and 105 mg monoepoxidized cyclooctadiene (0.85 mmol), or 84 mg trans-macrocycle (0.25 mmol) and 93 mg monoepoxidized cyclooctadiene (0.75 mmol), were dissolved in 0.15 mL dry DCM and deoxygenated with N₂ for 10 min. 1.0 mg (0.0012 mmol) Grubbs second-generation catalyst was dissolved in 1 mL DCM and deoxygenated for 20 min. 0.1 mL of the Grubbs catalyst solution was transferred to the monomer solution via a syringe. The viscosity of the solution increased after 30 min and stirring ceased quickly. 0.2 mL of DCM was added to the solution to allow the stirring to continue, and the reaction was allowed to proceed for another 2 h. The reaction was quenched with 1 mL of ethyl vinyl ether and stirred for 1 h. The reaction was then precipitated in methanol, redissolved in DCM, and reprecipitated in methanol and dried on a vacuum line. P1: ¹H NMR (500 MHz, CDCl₃): δ = 5.52–5.41 (m, 14 H), 4.22–4.11 (m, 4 H), 2.94–2.91 (m, 12 H), 2.81 (s, 2 H), 2.24–2.13 (m, 25 H), 1.70–1.64 (m, 4 H), 1.68–1.42 (m, 36 H). P2: ¹H NMR (500 MHz, CDCl₃): δ = 5.54–5.41 (m, 9 H), 4.21–4.18 (m, 4 H), 3.05 (s, 2 H), 2.93–2.91 (m, 6.7 H), 2.23–2.11 (m, 18 H), 1.70–1.45 (m, 18 H).