8-Quinolinyl Oxazoline: Ligand Exploration in Enantioselective Ni-Catalyzed Reductive Carbamoyl-Alkylation of Alkene to Access the Chiral Oxindoles

Abstract

Chiral ligands play an essential role in transition-metal-catalyzed enantioselective transformations, in which chiral oxazoline-based scaffolds are the privileged chiral ligand. Nevertheless, 8-quinolinyl oxazoline (8-Quinox) ligands are underexplored in transition-metal-catalyzed asymmetric transformations since their development in 1998. Herein, we report an 8-Quinox ligand promoted Ni-catalyzed enantioselective reductive carbamoyl-alkylation of carbamoyl chloride tethered styrene with unactivated alkyl iodide, providing an expedient access to valuable enantioenriched oxindoles in good results.

Key words

chiral ligand - nickel catalysis - reductive coupling - dicarbofunctionalization of alkene - oxindole

Publication History

Received: 24 April 2022

Accepted after revision: 30 May 2022

Accepted Manuscript online:
30 May 2022

Article published online:
08 July 2022

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• 18 General Procedure To a dried 8 mL vial were added ligand (22 mol%), Mn (2.0 equiv), Ni(ClO₄)₂ ·6H₂O (15 mol%), and carbamoyl chloride (1.0 equiv) (if solid). Then the vial was transferred into glovebox. LiBr (1.0 equiv), NMP (0.2 M), carbamoyl chloride (1.0 equiv) (if liquid), and alkyl halide (3.0 equiv) were added in sequence inside the glovebox. The vial was then put into the glovebox and stirred for the needed time. After completion, the reaction mixture was quenched with H₂O, filtered through a pad of Celite, and extracted with EtOAc for three times. The resulted filtrate was separated. The combined organic phase was washed with brine and concentrated under reduced pressure to yield the crude product, which was purified by silica gel flash column chromatography to afford products 3. (S)-1,3-Dimethyl-3-octylindolin-2-one (3a) Pale yellow oil (31.6 mg, 58%); R_f = 0.56 (PE/EtOAc = 10:1); [α]_D ²³ + 7.90 (c = 1.67, CHCl₃). ¹H NMR (400 MHz, CDCl₃): δ = 7.26 (td, J = 8.0, 1.2 Hz, 1 H), 7.16 (dd, J = 7.2, 0.8 Hz, 1 H), 7.06 (td, J = 7.6, 0.8 Hz, 1 H), 6.84 (d, J = 7.6 Hz, 1 H), 3.21 (s, 3 H), 1.88 (td, J = 12.4, 4.8 Hz, 1 H), 1.71 (td, J = 12.4, 4.4 Hz, 1 H), 1.34 (s, 3 H), 1.25–1.14 (m, 10 H), 1.00–0.77 (m, 5 H). ¹³C NMR (100 MHz, CDCl₃): δ = 181.0, 143.5, 134.5, 127.7, 122.6, 122.5, 108.0, 48.6, 38.7, 31.9, 29.9, 29.4, 29.3, 26.2, 24.6, 23.9, 22.7, 14.2. HRMS (ESI): m/z calcd for C₁₈H₂₈NO⁺: 274.2165; found: 274.2157. HPLC (Chiralpak IC): n-hexane/i-PrOH = 90:10, flow rate 1.0 mL/min, λ = 254 nm, t _R = 6.551 min (major), t _R = 8.110 min (minor); 96:4 e.r. (S)-1-Benzyl-3-methyl-3-octylindolin-2-one (3b) Pale yellow oil (38.1 mg, 55%); R_f = 0.77 (PE/EtOAc = 10:1); [α]_D ²³ + 10.30 (c = 0.66, CHCl₃). ¹H NMR (400 MHz, CDCl₃): δ = 7.29–7.23 (m, 5 H), 7.12 (dd, J = 16.8, 7.8 Hz, 2 H), 7.00 (t, J = 7.2 Hz, 1 H), 6.69 (d, J = 7.6 Hz, 1 H), 4.97 (d, J = 15.6 Hz, 1 H), 4.82 (d, J = 15.6 Hz, 1 H), 1.93 (td, J = 12.0, 2.8 Hz, 1 H), 1.74 (td, J = 12.8, 3.2 Hz, 1 H), 1.38 (s, 3 H), 1.23–1.13 (m, 12 H), 0.82 (t, J = 7.2 Hz, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 181.1, 142.5, 136.3, 134.4, 128.8, 127.6, 127.4, 122.7, 122.5, 109.1, 48.6, 43.7, 38.7, 31.9, 29.9, 29.4, 29.3, 24.8, 24.3, 22.7, 14.2. HRMS (ESI): m/z calcd for C₂₄H₃₂NO⁺: 350.2478; found: 350.2470. HPLC (Chiralpak IC): n-hexane/i-PrOH = 90:10, flow rate 1.0 mL/min, λ = 254 nm, t _R = 5.739 min (major), t _R = 6.239 min (minor); 95.5:4.5 e.r. (S)-1,3-Dimethyl-3-octyl-6-(trifluoromethyl)indolin-2-one (3c) Pale yellow oil (30.7 mg, 45%); R_f = 0.65 (PE/EtOAc = 10:1); [α]_D ²³ + 13.76 (c = 2.95, CHCl₃). ¹H NMR (400 MHz, CDCl₃): δ = 7.27 (d, J = 7.2 Hz, 1 H), 7.18 (d, J = 7.6 Hz, 1 H), 6.96 (s, 1 H), 3.17 (s, 3 H), 1.83 (td, J = 12.0, 3.2 Hz, 1 H), 1.66 (td, J = 12.0, 3.6 Hz, 1 H), 1.28 (s, 3 H), 1.17–1.07 (m, 12 H), 0.76 (t, J = 6.4 Hz, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 180.6, 144.1, 138.4, 130.2 (q, J _C–F = 32.3 Hz), 124.1 (q, J _C–F = 270.2 Hz), 122.7, 119.6 (q, J _C–F = 3.8 Hz), 104.6 (q, J _C–F = 3.7 Hz), 48.7, 38.5, 31.9, 29.8, 29.3, 29.3, 26.4, 24.6, 23.7, 22.7, 14.2. ¹⁹F NMR (376 MHz, CDCl₃): δ = –62.3; HRMS (ESI): m/z calcd for C₁₉H₂₇F₃NO⁺: 342.2039; found: 342.2030. HPLC (Chiralpak IC): n-hexane/i-PrOH = 90:10, flow rate 1.0 mL/min, λ = 254 nm, t _R = 4.627 min (major), t _R = 5.098 min (minor); 95.5:4.5 e.r. ( S )-1,3-Dimethyl-3-propylindolin-2-one (3d) Pale yellow oil (29.7 mg, 73%); R_f = 0.42 (PE/EtOAc = 10:1); [α]_D ²³ +15.04 (c = 2.78, CHCl₃). ¹H NMR (400 MHz, CDCl₃): δ = 7.26 (t, J = 8.0 Hz, 1 H), 7.17 (d, J = 7.2 Hz, 1 H), 7.06 (t, J = 7.6 Hz, 1 H), 6.83 (d, J = 7.2 Hz, 1 H), 3.21 (s, 3 H), 1.88 (td, J = 12.4, 4.4 Hz, 1 H), 1.70 (td, J = 12.0, 4.0 Hz, 1 H), 1.35 (s, 3 H), 1.05–0.96 (m, 1 H), 0.90–0.83 (m, 1 H), 0.77 (t, J = 7.2 Hz, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 181.0, 143.4, 134.4, 127.7, 122.6, 122.5, 107.9, 48.6, 40.9, 26.2, 23.8, 17.9, 14.3. HRMS (ESI): m/z calcd for C₁₃H₁₈NO⁺: 204.1383; found: 204.1378. HPLC (Chiralpak IC): n-hexane/i-PrOH = 90:10, flow rate 1.0 mL/min, λ = 254 nm, t _R = 7.967 min (major), t _R = 8.377 min (minor); 91.5:8.5 e.r.