Yttrium-Catalyzed Regioselective Aminolysis of 2,3-Epoxy Esters and Amides

Dedicated to 80^th birthday of Professor Hisashi Yamamoto.

Abstract

Herein, an yttrium-catalyzed regioselective ring-opening reaction of 2,3-epoxy esters and amides with amines as nucleophiles is presented. This method features high regiocontrol, an enantiospecific S_N2 reaction pathway, a broad substrate scope, and mild reaction conditions, furnishing a wide range of α-hydroxy β-amino esters and amides in regioisomerically pure forms. Notably, the selective nucleophilic attack to the C-3 position is controlled by the directing effect of the carbonyl group of the substrates.

Key words

yttrium catalysis - epoxides - regioselectivity - aminolysis - ring opening

Publication History

Received: 29 March 2023

Accepted after revision: 19 April 2023

Accepted Manuscript online:
19 April 2023

Article published online:
22 May 2023

• References and Notes


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• 10 Ethyl (±)-erythro-3-[(3-Bromophenyl)amino]-2-hydroxy-5-phenylpentanoate (3ae); Typical Procedure To a suspension of the Y(OTf)₃ (16.1 mg, 0.03 mmol, 15 mol%) in THF (0.5 mL) were added the amine 2e (34.2 mg, 0.2 mmol, 1.0 equiv) and the epoxide 1a (66.0 mg, 0.3 mmol, 1.5 equiv) at rt. The resulting mixture was heated to 60 °C and stirred at this temperature for 24 h. The mixture was then cooled to rt, and the solvent was removed in vacuum. The residue was purified by column chromatography [silica gel, PE–EtOAc (5:1)] to give a yellow oil; yield: 65 mg (83%). ¹H NMR (400 MHz, CDCl₃): δ = 7.30–7.23( m, 2 H), 7.22–7.16 (m, 1 H), 7.13–7.08 (m, 2 H), 7.01 (t, J = 8.0 Hz, 1 H), 6.84 (ddd, J = 7.9, 1.9, 0.9 Hz, 1 H), 6.77 (t, J = 2.1 Hz, 1 H), 6.53 (ddd, J = 8.2, 2.4, 0.9 Hz, 1 H), 4.38–4.27 (m, 1 H), 4.19 (q, J = 7.1 Hz, 2 H), 3.96 (d, J = 10.3 Hz, 1 H), 3.73–3.64 (br s, 1 H), 2.93 (d, J = 5.5 Hz, 1 H), 2.87–2.75 (m, 1 H), 2.73–2.55 (m, 1 H), 1.93–1.79 (m, 1 H), 1.67–1.57 (m, 1 H), 1.22 (t, J = 7.1 Hz, 3 H). ¹³C NMR (101 MHz, CDCl₃): δ = 173.4, 148.5, 141.3, 130.7, 128.5 (4 C), 126.1, 123.4 , 120.8, 116.6, 112.5, 71.3, 62.1, 54.6, 32.1, 31.3, 14.2. HRMS (ESI): m/z [M + H]⁺ calcd for C₁₉H₂₃BrNO₃: 392.0856; found: 392.0866.