Organocatalytic Asymmetric Oxa-Michael–Michael Reaction of 3-Aryl-2-Nitroprop-2-Enols with Unsaturated Pyrazolones: Synthesis of Spirotetrahydropyranopyrazolones

Abstract

An organocatalytic asymmetric oxa-Michael–Michael reaction of 3-aryl-2-nitroprop-2-enols with alkylidene pyrazolones has been developed. This report describes the first use of a 3-aryl-2-nitroprop-2-enol as an O-nucleophile in enantioselective catalysis. With 10 mol% of a quinine-derived squaramide catalyst, a variety of spirotetrahydropyranopyrazolones were obtained in moderate yields, excellent diastereomeric ratios, and high to excellent enantioselectivities under mild reaction conditions.

Key Words

spiropyrazolones - oxa-Michael reaction - organocatalysis - asymmetric catalysis - enantioselectivity - cascade reaction

Publication History

Received: 30 May 2021

Accepted after revision: 07 September 2021

Accepted Manuscript online:
07 September 2022

Article published online:
28 September 2022

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• 14 4-Methyl-9-nitro-2,6,10-triphenyl-7-oxa-2,3-diazaspiro[4.5]dec-3-en-1-one (3a); Typical ProcedureAn oven-dried round-bottomed flask was charged with pyrazolone 1 (17.9 mg, 0.1 mmol), enol 2 (28.8mg, 0.11 mmol), and catalyst IV (10 mol%). CH₂Cl₂ (0.4 mL) was added and the mixture was stirred at rt for 1 d until the reaction was complete (TLC). The mixture was then concentrated and purified directly by column chromatography [silica gel, hexane–EtOAc (8%)] to give a yellowish sticky solid; yield 24.3 mg (55%, 98% ee).HPLC [Chiralpak IF, hexane–i-PrOH (85:15), 1.0 mL/min, λ = 220 nm]: t _major = 20.99 min, t _minor = 17.90 min. ¹H NMR (500 MHz, CDCl₃): δ = 7.27 (t, J = 4.6 Hz, 4 H), 7.26–7.22 (m, 5 H), 7.19 (t, J = 8.0 Hz, 3 H), 7.11 (d, J = 8.0 Hz, 2 H), 7.07 (t, J = 7.4 Hz, 1 H), 5.68 (dt, J = 12.3, 7.2 Hz, 1 H), 4.77 (s, 1 H), 4.69–4.60 (m, 3 H), 2.33 (s, 3 H). ¹³C NMR (126 MHz, CDCl₃): δ = 171.7, 156.5, 136.9, 135.0, 133.0, 129.3, 129.0, 128.9, 128.7, 128.4, 127.6, 126.2, 125.8, 120.1, 81.7, 78.7, 68.4, 64.1, 45.9, 16.96. HRMS (ESI): m/z [M + H]⁺ calcd for C₂₆H₂₄N₃O₄: 442.1761; found: 442.1750.