Total Synthesis of (±)-Spirobenzofuran

Hang Su; Ting Zhou; Bo Liu

doi:10.1055/s-0032-1318310

Synlett, Inhaltsverzeichnis

Synlett 2013; 24(5): 615-618
DOI: 10.1055/s-0032-1318310

letter

Total Synthesis of (±)-Spirobenzofuran

Hang Su

^aKey Laboratory of Green Chemistry & Technology of Ministry of Education, College of Chemistry, Sichuan University, Chengdu 610 064, P. R. of China Fax: +86(28)85413712 eMail: chembliu@scu.edu.cn

,

Ting Zhou

^aKey Laboratory of Green Chemistry & Technology of Ministry of Education, College of Chemistry, Sichuan University, Chengdu 610 064, P. R. of China Fax: +86(28)85413712 eMail: chembliu@scu.edu.cn

,

Bo Liu*

^aKey Laboratory of Green Chemistry & Technology of Ministry of Education, College of Chemistry, Sichuan University, Chengdu 610 064, P. R. of China Fax: +86(28)85413712 eMail: chembliu@scu.edu.cn

^bKey Laboratory of Synthetic Chemistry of Natural Substances, Shanghai Institute of Organic Chemistry, 345 Lingling Road, Shanghai 200 032, P. R. of China

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Abstract

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Abstract

Spirobenzofuran, embracing a cyclopentane-spirofused benzofuran carbon framework, was efficiently assembled via semipinacol rearrangement with Me₃Al from 2,5-dimethoxy-4-methylacetophenone.

Key words

spirobenzofuran - semipinacol rearrangement - trimethylaluminium - total synthesis - sesquiterpenoid

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Referenzen

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18 Synthesis of Aldehyde 5 To a solution of compound 6 (200 mg, 0.59 mmol) in CH₂Cl₂ (10 mL) was added Me₃Al (0.59 mL, 1.18 mol, 2.0 M in toluene) dropwise at –10 °C under argon. The reaction was warmed to r.t. slowly and stirred for 4 h. Then it was quenched with sat. aq NaHCO₃ (2 mL) at 0 °C. Sat. aq sodium potassium tartrate (10 mL) was added, and the biphasic mixture was stirred overnight. The aqueous layer was separated and extracted with CH₂Cl₂ (3 × 5 mL). The residue was purified by flash chromatography (silica gel, PE–EtOAc = 10:1) to give compound 5 as a yellow solid (176 mg, 88%).¹H NMR (400 MHz, CDCl₃): δ = 9.87 (s, 1 H), 6.92 (s, 1 H), 6.69 (s, 1 H), 3.93–3.88 (m, 4 H), 3.79 (s, 3 H), 3.67 (s, 3 H), 2.77 (d, J = 15.2 Hz, A of AB, 1 H), 2.31 (d, J = 15.2 Hz, B of AB, 1 H), 2.27 (d, J = 14.0 Hz, A′ of A′B′, 1 H), 2.20 (s, 3 H), 1.99 (d, J = 13.6 Hz, B′of A′B′, 1 H), 1.27 (s, 3 H), 0.83 (s, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 201.8, 151.8, 150.7, 127.0, 125.8, 114.8, 114.8, 112.3, 64.3, 64.3, 63.3, 56.3, 55.9, 51.9, 44.2, 43.8, 27.0, 23.9, 16.2. IR (thin film): 2959, 1716, 1213, 858 cm^–1.
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23 Analytical Data ¹H NMR (400 MHz, DMSO-d ₆): δ = 8.66 (s, 1 H), 7.14 (d, J = 5.6 Hz, 1 H), 6.52 (s, 2 H), 5.79 (d, J = 5.6 Hz, 1 H), 2.83 (d, J = 18.8 Hz, A of AB, 1 H), 2.44 (d, J = 18.8 Hz, B of AB, 1 H), 2.34 (d, J = 18.4 Hz, A′ of A′B′, 1 H), 2.24 (d, J = 18.0 Hz, B′ of A′B′, 1 H), 2.07 (s, 3 H), 0.98 (s, 3 H), 0.85 (s, 3 H). ¹³C NMR (100 MHz, DMSO-d ₆): δ = 216.2, 150.3, 148.9, 126.5, 123.8, 111.2, 111.0, 102.1, 59.2, 51.9, 42.7, 41.2, 24.6, 23.0, 16.3. IR (thin film): 3395, 1732, 1412, 1085, 923 cm^–1. HRMS (ES⁺): m/z calcd for C₁₅H₁₈O₄Na [M + Na]⁺: 285.1103; found: 285.1101.

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