Catalyst-Controlled Regio- and Stereoselective Bromolactonization with Chiral Bifunctional Sulfides

Published as part of the Cluster Organosulfur and Organoselenium Compounds in Catalysis

Abstract

Highly regioselective 5-exo bromolactonizations of stilbene-type carboxylic acids bearing electron-withdrawing substituents are achieved for the first time via the use of chiral bifunctional sulfide catalysts possessing a urea moiety. The chiral phthalide products are obtained in moderate to good enantioselectivities as the result of 5-exo cyclizations.

Key words

asymmetric synthesis - lactonization - organocatalysis - regioselectivity­ - sulfides

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• 9 For the reaction with catalyst (S)-4d at low temperature and the reaction with another different catalyst, see Schemes S1 and S2 in the Supporting Information.
• 10 The reaction with bromine (Br₂) may proceed via a non-catalyzed reaction pathway (background reaction pathway). For a reaction using another reactive brominating reagent, see Scheme S3 in the Supporting Information.
• 11 For other control experiments, see Scheme S4 in the Supporting Information.
• 12 Asymmetric Bromolactonizations; General Procedure A solution of substrate 1 (0.10 mmol) and catalyst (S)-4d (10 mol%, 0.010 mmol) in CH₂Cl₂ (2 mL) was cooled to 0 °C. After stirring for 10 min, N-bromosuccinimide (NBS) (0.12 mmol) was added and the resulting mixture was stirred for 24 h at 0 °C. The mixture was quenched with saturated aqueous Na₂SO₃ (4.0 mL) at 0 °C, stirred for 10 min at 0 °C, diluted with CH₂Cl₂ (2 mL) and H₂O (2 mL) and then warmed to room temperature. The organic materials were extracted with CH₂Cl₂ (3 × 5 mL) and the combined extracts dried over Na₂SO₄ and concentrated. (The ¹H NMR analysis of the crude reaction mixture was performed at this stage to determine the regioselectivity of the bromolactonization products.) The residue was purified by flash column chromatography on silica gel (hexane/EtOAc as eluent) to give product 2. The enantioselectivity of the product 2 was determined by HPLC analysis on a chiral stationary phase. Compound 2a⁵ Yield: 31.9 mg (86%); colorless oil; [α]_D ²¹ +4.4 (c = 0.87, CHCl₃); 82:18 er; HPLC (Daicel Chiralpak IC-3, hexane/2-propanol = 10:1, flow rate = 0.5 mL/min, 230 nm): t _R = 59.3 min (major) and 68.8 min (minor). IR (neat): 1769, 1324, 1286, 1167, 1124, 1114, 1067, 1018 cm^–1. ¹H NMR (400 MHz, CDCl₃): δ = 7.85 (d, J = 7.2 Hz, 1 H), 7.67–7.71 (m, 2 H), 7.53–7.60 (m, 5 H), 5.96 (d, J = 6.4 Hz, 1 H), 5.16 (d, J = 6.4 Hz, 1 H). ¹³C NMR (100 MHz, CDCl₃): δ = 168.9, 146.0, 140.1, 134.1, 131.1 (q, J = 32.1 Hz), 130.2, 129.0, 126.5, 126.0 (q, J = 2.5 Hz), 125.7 (m), 123.7, 123.6 (q, J = 272 Hz), 82.1, 51.8.