Visible-Light Photocatalytic Barbier-Type Reaction of Aziridines and Azetidines with Nonactivated Aldehydes

Dedicated to Prof. Dr. Masahiro Murakami for his great contributions to science.

Abstract

Barbier-type reactions are a classic group of reactions for carbon–carbon bond formation; however, their common use of stoichiometric metals restricts their widespread application. Considering the ready availability and diversity of cyclic amines, we report a visible-light photocatalytic Barbier-type reaction of aziridines and azetidines with nonactivated aldehydes. A series of important γ- and δ-amino alcohols were synthesized in the presence of amines as electron donors. Moreover, this transition-metal-free protocol displays mild reaction conditions, broad functional-group tolerance, and a wide substrate scope. Mechanistic investigations indicated that carbon radicals and carbanions might be generated as key intermediates.

Key words

photocatalysis - Barbier reaction - aziridines - azetidines - C–N bond cleavage

Publication History

Received: 25 January 2023

Accepted after revision: 21 February 2023

Accepted Manuscript online:
21 February 2023

Article published online:
08 March 2023

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• 16 tert-Butyl (3-Biphenyl-4-yl-4-hydroxy-6-phenylhexyl)carbamate ( 3aa): Typical ProcedureAn oven-dried Schlenk tube (10 mL) containing a stirring bar was charged with the 1a (0.2 mmol, 61.9 mg, 1 equiv) and 3DPAFIPN (0.004 mmol, 2.6 mg, 2 mol%). The Schlenk tube was then transferred to a glovebox where it was charged with PivOK (0.2 mmol, 28 mg, 1 equiv). The tube was taken out of the glovebox, connected to a vacuum line, and evacuated and back-filled with N₂ three times. 2a (0.4 mmol, 53.7 mg, 2 equiv), DIPEA (0.4 mmol, 51.7 mg, 2 equiv), and DMA (2 mL) were then added under flowing N₂. Finally, the mixture in the sealed tube was placed 1 cm from a 30 W blue LED lamp and stirred at rt (25 °C) for 36 h. The reaction was quenched with 2 N aq HCl (2 mL), and the mixture was extracted with EtOAc. The extracts were concentrated in vacuo and the residue was purified by flash chromatography [silica gel, PE–EtOAc (10:1 to 3:1)] to give a light yellow viscous liquid; yield: 73 mg (82%). ¹H NMR (400 MHz, CDCl₃, mixture of two diastereomers): δ = 7.61–7.48 (m, 4 H), 7.46–7.38 (m, 2 H), 7.35–7.12 (m, 7 H), 7.11–7.06 (m, 1 H), 4.57–4.44 (m, 1 H), 3.84–3.69 (m, 1 H), 3.15–2.88 (m, 2 H), 2.87–2.76 (m, 1 H), 2.73–2.55 (m, 2 H), 2.21–2.09 (m, 1 H), 1.98–1.80 (m, 2 H), 1.76–1.53 (m, 2 H), 1.41 (s, 9 H). ¹³C NMR (101 MHz, CDCl₃, mixture of two diastereomers): δ = 156.2, 156.1, 142.14, 142.06, 140.93, 140.88, 140.86, 140.0, 139.7, 139.5, 129.4, 128.9, 128.8, 128.6, 128.54, 128.52, 128.47, 127.48, 127.47, 127.34, 127.31, 127.11, 127.09, 126.0, 125.9, 79.3, 75.1, 74.2, 49.9, 49.3, 39.2, 37.1, 36.8, 32.6, 32.4, 32.3, 32.0, 28.5. HRMS (ESI+): m/z [M + Na]⁺ calcd for C₂₉H₃₅NNaO₃: 468.2509; found: 468.2506.