Total Synthesis of (+)-Tanikolide by a Traceless Stereoinduction Method Using Rhodium(II)-Catalyzed Oxonium Ylide Formation–[2,3]-Sigmatropic Rearrangement and NHC-Catalyzed Ring-Expansion Lactonization

Abstract

The total synthesis of (+)-tanikolide was accomplished by a traceless stereoinduction method using the key steps of a Rh(II)-catalyzed oxonium ylide formation–[2,3]-sigmatropic rearrangement and an N-heterocyclic carbene-catalyzed ring-expansion lactonization of tetrahydrofurfural. This synthetic route is applicable to the divergent synthesis of tanikolide analogues.

Key words

N-heterocyclic carbine - oxonium ylides - rearrangement - rhodium - total synthesis - traceless stereoinduction

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• 11 Synthesis of (+)-tanikolide (1): Aqueous HCl (4 M, 1.8 mL) was added dropwise to a solution of MOM ether 17 (120 mg, 0.37 mmol) in THF (1.8 mL) at room temperature. After stirring at 50 °C for 6 h, the reaction mixture was saturated with NaCl. The mixture was extracted with CHCl₃ (3 × 20 mL) and the combined organic layers were dried over anhydrous Na₂SO₄. The filtrate was concentrated in vacuo and the residue was purified by column chromatography (silica gel; EtOAc–hexane, 40%) to provide 1 (59 mg, 56%) as colorless crystals. Mp 39–40 °C (Lit.^2g 39−41 °C); [α]_D ²⁴ +2.2 (c 0.65, CHCl₃) {Lit. (Ref. 1) [α]_D ²⁵ +2.3 (c 0.65, CHCl₃)}. IR (neat): 3395, 2923, 2851, 1701, 1468, 1265, 1051 cm^–1. ¹H NMR (400 MHz, CDCl₃): δ = 3.67 (d, J = 12.0 Hz, 1 H), 3.54 (d, J = 12.0 Hz, 1 H), 2.94 (br. s, 1 H), 2.47 (t, J = 6.6 Hz, 1 H), 1.97–1.80 (m, 3 H), 1.75–1.61 (m, 3 H), 1.26 (br. s, 18 H), 0.88 (t, J = 6.8 Hz, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 172.0, 86.6, 67.3, 36.7, 31.8, 29.9, 29.7, 29.53, 29.51, 29.47, 29.3, 29.2. 26.6, 23.3, 22.6, 16.6, 14.0.