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DOI: 10.1055/s-0035-1560587
Bisallylation of Zirconacyclopentenes and Ring-Closing Metathesis: A Route to Eight-Membered-Ring Compounds
Publication History
Received: 16 September 2015
Accepted after revision: 04 October 2015
Publication Date:
09 November 2015 (online)
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Dedicated to Professor Ei-ichi Negishi on the occasion of his 80th 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.
Supporting Information
- Supporting information for this article is available online at http://dx.doi.org/10.1055/s-0035-1560587.
- Supporting Information
Primary Data
- Primary data for this article are available online at http://www.thieme-connect.com/products/ejournals/journal/10.1055/s-00000083 and can be cited using the following DOI: 10.4125/pd0073th.
- Primary Data
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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; Rf = 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; Rf = 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.
For reviews, see:
For a review, see:
For other typical examples, see:
For reviews, see: