Asymmetric, Organocatalytic Bromolactonization of Allenoic Acids

Abstract

Asymmetric, reagent-controlled bromolactonizations of allenoic acids have been achieved by using (DHQD)₂PHAL as catalyst. A range of substrates can be cyclized in good yields and moderate to good enantioselectivities under operationally simple conditions.

Key words

allenes - asymmetric synthesis - cyclization - electrophilic addition - halogenation

• References and Notes

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• 13 CCDC-992322 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
• 14 A more extensive table of reaction conditions can be found in the Supporting Information.
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• 16 Enantioselective Halolactonization using 1,3-Dibromo-5,5-dimethylhydantoin (DBDMH); General Procedure (Conditions A): In a flame-dried Schlenk tube, the corresponding carboxylic acid (0.300 mmol, 1.0 equiv), benzoic acid (36.6 mg, 0.300 mmol, 1.0 equiv) and (DHQD)₂PHAL (23.4 mg. 30.0 μmol, 10 mol%) were dissolved in anhydrous CHCl₃/n-hexane (1:1, 6 mL), cooled to –30 °C and stirred for 15 min. DBDMH (103 mg, 0.360 mmol, 1.2 equiv) was added and stirring was continued at that temperature for 15 h. Sat. aq Na₂S₂O₃ (6 mL) was added to the reaction mixture and the aqueous layer was extracted with CH₂Cl₂ (3 × 10 mL). The combined organic layers were dried over Na₂SO₄, filtered, and the solvents were removed in vacuo. Purification by flash chromatography afforded the desired cyclization product.
• 17 The isolated yield of 5b was surprisingly low because full conversion of the starting material was observed and no detectable side products were formed (6-endo cyclization product was not formed). The reason for the low mass balance is unclear. Similar observations were made for 5d and 5e.
• 18 Enantioselective Halolactonization using N-Bromosuccinimide (NBS; General Procedure (Conditions B): In a flame-dried Schlenk tube, the corresponding carboxylic acid (0.300 mmol, 1.0 equiv) and (DHQD)₂PHAL (23.4 mg. 30.0 μmol, 10 mol%) were dissolved in anhydrous CHCl₃/n hexane (1:1, 6 mL), cooled to –30 °C and stirred for 15 min. NBS (64.1 mg, 0.360 mmol, 1.2 equiv) was added and stirring was continued at that temperature for 15 h. Sat. aq Na₂S₂O₃ (6 mL) was added to the reaction mixture and the aqueous layer was extracted with CH₂Cl₂ (3 × 10 mL). The combined organic layers were dried over Na₂SO₄, filtered, and the solvents were removed in vacuo. Purification by flash chromatography afforded the desired cyclization product.