Synlett 2019; 30(15): 1835-1839
DOI: 10.1055/s-0039-1690133
letter
© Georg Thieme Verlag Stuttgart · New York

Enantioselective 1,3-Dipolar Cycloaddition Reaction of Nitrones with α-(Acyloxy)acroleins Catalyzed by Dipeptide-Derived Chiral Tri- or Diammonium Salts

Chihiro Kidou
a   Graduate School of Natural Science and Technology, Okayama University, 3-1-1 Tsushima-naka, Kita-ku, Okayama 700-8530, Japan   Email: sakakura@okayama-u.ac.jp
,
a   Graduate School of Natural Science and Technology, Okayama University, 3-1-1 Tsushima-naka, Kita-ku, Okayama 700-8530, Japan   Email: sakakura@okayama-u.ac.jp
,
Tatsuo Nehira
b   Graduate School of Integrated Sciences for Life, Hiroshima University, 1-7-1 Kagamiyama, Higashi-Hiroshima 739-8521, Japan
,
a   Graduate School of Natural Science and Technology, Okayama University, 3-1-1 Tsushima-naka, Kita-ku, Okayama 700-8530, Japan   Email: sakakura@okayama-u.ac.jp
› Author Affiliations
Further Information

Publication History

Received: 26 June 2019

Accepted after revision: 18 July 2019

Publication Date:
30 July 2019 (online)


Abstract

Organoammonium salts of dipeptide-derived chiral triamines or diamines with TfOH catalyzed the enantioselective 1,3-dipolar cycloaddition reactions of α-acyloxyacroleins with nitrones to give the corresponding adducts in good yields (up to 96%) and with high diastereo- and enantioselectivities (up to 89% ee). Although α-(p-methoxybenzoyloxy)acrolein is rather unstable under the reaction conditions, α-(3-pyrroline-1-carbonyloxy)acrolein is stable enough to be smoothly converted into the corresponding adducts with the aid of the chiral organoammonium salt catalysts.

Supporting Information

 
  • References and Notes

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      For the enantioselective Diels–Alder reaction with α-(N,N-diacylamino)acroleins and α-(acylthio)acroleins, see:
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    • pK a (CD3CO2D) of TfOH: –0.74; pK a (CD3CO2D) of C6F5SO3H: 9.2. See:
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  • 14 When 1a·2.8TfOH or 1b·2TfOH was used as a catalyst in the reaction of 2, a more-labile acrolein than 3, a significant amount of 2 was decomposed.
  • 15 (3S,4R)-2-Benzyl-4-formyl-3-phenylisoxazolidin-4-yl 2,5-Dihydro-1H-pyrrole-1-carboxylate; Typical Procedure To a solution of triamine 1a (3.2 mg, 0.0105 mmol) and TfOH (2.6 μL, 0.0295 mmol) in CHCl3 (0.15 mL) was added a solution of nitrone 4a (21.5 mg, 0.10 mmol) and acrolein 3 (34.5 mg, 0.206 mmol) in CHCl3 (0.30 mL) at 0 °C. The resulting solution was stirred at 0 °C for 48 h and then the reaction was quenched with sat. aq NaHCO3. The mixture was extracted with EtOAc, and the combined organic layers were washed with brine. The organic layer was dried (Na2SO4) and filtered. The solvent was removed in vacuo and the crude product was purified by column chromatography (silica gel, hexane–EtOAc) to give a white solid; yield: 21.9 mg (0.0579 mmol, 58% yield). This product was converted into the corresponding alcohol by reduction with NaBH4 in MeOH at r.t.
  • 16 Although the triammonium salt catalyst was prepared in situ by mixing 1a and 2.8 equivalents of TfOH, the active catalytic species should be 1a·3TfOH (see ref. 7b). To suppress undesired catalysis by TfOH, slightly less than three equivalents of TfOH were used for the preparation of the triammonium salt catalyst.
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