Bisallylation of Zirconacyclopentenes and Ring-Closing Metathesis: A Route to Eight-Membered-Ring Compounds

Dedicated to Professor Ei-ichi Negishi on the occasion of his 80^th birthday

Abstract

The cyclization of various enynes with the Negishi reagent provides the corresponding bicyclic zirconacyclopentenes, which after exposure to allyl chloride in the presence of a catalytic amount of copper(I) chloride, undergo bisallylation to furnish 1,9-decadienes in good yields (42–89%). The dienes are subjected to ring-closing metathesis to afford bicyclic compounds with [6.3.0]bicycloundecane (8,5-fused ring system) or [6.4.0]bicyclododecane (8,6-fused ring system) frameworks in good to excellent yields (52–92%). Selective monoallylation of a selected zirconacyclopentene followed by carboxyethylation with ethyl chloroformate gives rise to the corresponding ester, which after metalation and reaction with allyl bromide, furnishes a 1,9-decadiene. Ring-closing metathesis then yields the expected eight-membered cyclic product in 92% yield. This procedure constitutes a new pathway to bicyclic carbocyclic systems starting from 1,ω-enynes.

Key words

zirconium - allylation - metathesis - enynes - cyclization

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• 32 (E)-{1-[2-(But-3-en-1-yl)cyclopentylidene]but-3-en-1-yl}benzene (4a); Typical Example To a solution of bis(cyclopentadienyl)zirconium dichloride (0.350 g, 1.20 mmol) in dry THF (7 mL) at –78 °C was added dropwise n-BuLi (1.50 mL, 1.6 M in hexanes, 2.40 mmol) over 5 min, and the mixture was stirred for 1 h at the same temperature. Enyne 1a (170 mg, 1.00 mmol) was added and the mixture was allowed to warm gradually to 25 °C. After 3 h, CuCl (0.20 mmol, 0.018 g) and allyl chloride (0.325 mL, 4.00 mmol) were added and the mixture was left to stir at 25 °C for 12 h. The reaction mixture was quenched with 1 M HCl (10 mL) and extracted with EtOAc (3 × 20 mL). The combined organic phase was washed with sat. aq NaHCO₃ (20 mL), H₂O (2 × 20 mL), and brine (20 mL), and then dried over MgSO₄, filtered, and concentrated under reduced pressure. Purification of the residue by column chromatography on silica gel (hexanes) gave the title compound. Yield: 224 mg (89%); colorless liquid; R_f  = 0.36 (hexanes). IR (KBr): 3072, 3052, 3019, 2977, 2950, 2929, 2863, 1643, 1595, 1494, 1440, 994, 908, 776, 701 cm^–1. ¹H NMR (600 MHz, CDCl₃): δ = 7.30–7.28 (m, 2 H), 7.20–7.15 (m, 3 H), 5.92–5.85 (m, 1 H), 5.76–5.70 (m, 1 H), 5.08–4.90 (m, 4 H), 3.21–3.13 (m, 2 H), 2.81–2.77 (m, 1 H), 2.25–2.17 (m, 2 H), 2.12–2.05 (m, 2 H), 1.83–1.77 (m, 1 H), 1.70–1.63 (m, 2 H), 1.59–1.54 (m, 1 H), 1.51–1.41 (m, 2 H). ¹³C NMR (151 MHz, CDCl₃): δ = 145.5, 143.5, 138.9, 136.6, 129.7, 128.5, 127.8, 125.9, 115.1, 114.5, 41.2, 39.0, 34.2, 32.0, 31.6, 31.2, 24.3. HRMS (TOF-MS-CI): m/z [M + H]⁺ calcd for C₁₉H₂₄: 252.1878; found: 252.1877.
• 33 (6Z,9E)-9-Phenyl-2,3,3a,4,5,8-hexahydro-1H-cyclopenta[8]annulene (6a); Typical Example Compound 4a (0.39 mmol, 100 mg) was dissolved in CH₂Cl₂ (30 mL) and Ar gas was bubbled through the solution for 15 min. G II (0.019 mmol, 17 mg) was dissolved in CH₂Cl₂ (10 mL) and Ar gas was bubbled through the solution for 15 min. The solution of G II catalyst was transferred to the solution of 4a and the resulting mixture was stirred at reflux temperature for 2 h. The solvent was evaporated under reduced pressure under an Ar atm. Without purification, ¹H NMR spectroscopic analysis of the residue [mesitylene (0.39 mmol) was used as an internal standard] indicated that compound 6a had formed in 99% yield. Purification of the residue by column chromatography on silica gel (hexanes) yielded the title compound. Yield: 57 mg (64%); yellow liquid; R_f  = 0.42 (hexanes). IR (KBr): 3075, 3055, 3022, 2947, 2929, 1595, 1497, 1449, 1437, 1072, 794, 737, 698 cm^–1. ¹H NMR (600 MHz, CDCl₃): δ = 7.36–7.31 (m, 2 H), 7.25–7.20 (m, 3 H), 5.90–5.85 (m, 1 H), 5.67–5.63 (m, 1 H), 3.53–3.49 (m, 1 H), 3.15–3.12 (m, 1 H), 2.74 (q, J = 6.0 Hz, 1 H), 2.51–2.45 (m, 1 H), 2.43–2.37 (m, 1 H), 2.20–2.11 (m, 2 H), 2.06–2.01 (m, 1 H), 1.80–1.75 (m, 1 H), 1.68–1.63 (m, 1 H), 1.47–1.39 (m, 3 H). ¹³C NMR (151 MHz, CD₂Cl₂): δ = 145.0, 143.2, 134.3, 132.1, 130.1, 128.1, 128.0, 125.9, 43.9, 35.8, 35.3, 33.5, 33.3, 27.2, 25.1. HRMS (TOF-MS-CI): m/z [M + H]⁺ calcd for C₁₇H₂₀: 224.1565; found: 224.1564.