Highly Activated Second-Generation Grubbs–Hoveyda Catalyst Driven by Intramolecular Steric Strain

We would like to dedicate this letter to Prof. Takayuki Shioiri on his 80^th birthday.

Abstract

Various Grubbs–Hoveyda second-generation catalysts activated by intramolecular steric strain were prepared. The variant bearing a 9-anthracenyl group in the ligand moiety exhibited the highest catalytic activity. The new anthracenyl-type-activated catalyst was used in a ring-closing metathesis reaction to effectively provide a 4-substituted product effectively.

Key words

catalyst - metathesis - activation - ligand - steric strain

• References and Notes

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• 9 Garber SB, Kingsbury JS, Gray BL, Hoveyda AH. J. Am. Chem. Soc. 2000; 122: 8168
• 10 Characterization Data of Catalyst 1g Green crystal, mp 300 °C (dec.). ¹H NMR (270 MHz, CDCl₃): δ = 1.33 (d, J = 5.7 Hz, 6 H), 2.11–2.42 (br m, 18 H), 4.10 (s, 4 H), 4.92–5.01 (m, 1 H), 6.93–6.97 (m, 6 H), 7.28–7.50 (m, 6 H), 7.68 (d, J = 8.9 Hz, 2 H), 7.98 (d, J = 8.4 Hz, 2 H), 8.43 (s, 1 H), 16.64 (s, 1 H). ¹³C NMR (68 MHz, CDCl₃): δ = 21.1, 21.4, 112.9, 125.1, 125.3, 125.5, 126.7, 127.3, 128.3, 129.5, 130.7, 131.4, 132.4, 132.6, 135.6, 139.0, 145.4, 152.0, 211.0, 296.4. HRMS (FAB⁺): m/z calcd for C₄₅H₄₈Cl₂N₂ORu: 804.2162; found: 804.2187.
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