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Synlett 2018; 29(04): 497-502
DOI: 10.1055/s-0036-1590940
DOI: 10.1055/s-0036-1590940
letter
Pd-Catalyzed One-Pot Borylation/Intramolecular Asymmetric Arylation on α-Ketiminoamides: Innovative Approach to Chiral 3-Amino-2-oxindoles
We are grateful for the award of a post-doctoral grant to C.S.M. (FRH/BPD/92394/2013) from the Fundação para a Ciência e a Tecnologia (FCT). The authors gratefully acknowledge Fundo Europeu de Desenvolvimento Regional (FEDER)-INALENTEJO for funding the program INMOLFARM – Molecular Innovation and Drug Discovery (ALENT-07-0224-FEDER-001743) and for financing the acquisition of the NMR equipment, project LADECA (ALENT-07-0262-FEDER-001878). S.E.L. thanks University College Cork 2013 Research Fund and Science Foundation Ireland under grant no. 05/PICA/B802/EC07.Further Information
Publication History
Received: 30 August 2017
Accepted after revision: 04 October 2017
Publication Date:
03 November 2017 (online)
Abstract
3-Amino-2-oxindole derivatives are a common framework found in many natural products and medicinal compounds and thus their synthesis is of significant importance. We report for the first time a one-pot approach for the synthesis of these compounds, using a borylation/intramolecular asymmetric arylation sequence starting from ortho-bromo-α-ketimino amide derivatives. Pd(OAc)2 was used as the pre-catalyst along with (R)-BINAP as the chiral source. We successfully obtained a family of 3-phenyl-3-(aryl-amino)-indolin-2-one derivatives (11 in total) with excellent yields (up to 98%) and enantioselectivities of up to 76% ee. The reaction is versatile and tolerant of a wide range of functional groups.
Supporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/s-0036-1590940.
- Supporting Information
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References and Notes
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- 18 General Procedure for the Asymmetric Synthesis of Chiral 3-Amino-2-oxindolesIn a Radley’s® 12 position carousel reactor under a nitrogen atmosphere was added Pd(OAc)2 (0.0125 mmol, 5 mol%), chiral ligand (0.025 mmol, 10 mol%), and 1,4-dioxane (1 mL). The mixture was stirred for 30 min at room temperature, then the corresponding ortho-bromo-α-ketimino amide substrate 1 (0.25 mmol), B2Pin2 (0.28 mmol, 1.1 equiv), KOAc (0.76 mmol), and 1,4-dioxane (1 mL) were added sequentially to the reaction vessel. The reaction was left stirring at 100 °C during 18 h. After cooling to room temperature, the crude mixture was purified by silica gel chromatography using hexane/AcOEt (5:1) as eluent to afford the desired 3-phenyl-3-(aryl-amino)-indolin-2-one derivatives 2.Compound 2a: Pale yellow solid; mp 86.2–87.8 °C. 1H NMR (400 MHz, CDCl3) δ = 3.26 (s, CH3, 3 H), 6.34–6.36 (d, Ar, 2 H, J = 8 Hz), 6.67–6.71 (t, Ar, 1 H, J = 8 Hz), 6.92–6.94 (d, Ar, 1 H, J = 8 Hz), 6.98–7.02 (t, Ar, 2 H, J = 8 Hz), 7.08–7.12 (t, Ar, 1 H, J = 8 Hz), 7.33–7.42 (m, Ar, 5 H), 7.55–7.57 (d, Ar, 2 H, J = 8 Hz). 13C NMR (100 MHz, CDCl3) δ = 26.80, 68.08, 108.90, 115.54, 119.40, 123.32, 125.42, 126.73, 128.73, 129.07, 129.12, 129.51, 130.37, 140.19, 143.28, 145.09, 177.05. FTIR: 1499, 1722, 3055, 3373 cm–1. ESI-HRMS: m/z calcd for C21H18N2O: 314.14191; found for C21H18N2ONa: 337.13113 [M+ + Na]. HPLC: Daicel Chiralpak IA column, n-hexane/i-PrOH = 90:10, 1.0 mL/min, 220 nm; t R = 32.447 min (R, minor), 38.080 min (S, major).
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For several examples, see:
For some examples, see:
For examples of arylation reactions in ketimines with boronic acids, see:
For selected examples, see: