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. 2023 Nov 3;88(21):15461-15465.
doi: 10.1021/acs.joc.3c01513. Epub 2023 Oct 12.

Green Oxidation of Heterocyclic Ketones with Oxone in Water

Alessandro Giraudo  1 , Edoardo Armano  1 , Camillo Morano  1 , Marco Pallavicini  1 , Cristiano Bolchi  1
Affiliations

Green Oxidation of Heterocyclic Ketones with Oxone in Water

Alessandro Giraudo et al. J Org Chem. .

Abstract

The recently reported efficient conversion of cyclic ketones to lactones by Oxone in neutral buffered water is extended to heterocyclic ketones, namely, cyclic N-Boc azaketones and oxoethers with the aim of obtaining N-protected azalactones and their analogues with oxygen in place of nitrogen. N-Boc-4-piperidinone and all the cyclic oxoethers were successfully oxidized to lactones, while the azacyclic ketones with nitrogen α-positioned to carbonyl were univocally transformed into N-Boc-ω-amino acids and N-Boc-N-formyl-ω-amino acids operating in alkaline water and DMF, respectively.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Figure 1
Figure 1
Heterocyclic ketones submitted to oxidation with Oxone.
Figure 2
Figure 2
Lactones that may be obtained in principle by the oxidative ring expansion of 1–8. In red, those reported in the literature as BV oxidation products of 4, 7, and 8; in blue, those reported in the literature as resultant from other preparative procedures; and in black, those not described.
Scheme 1
Scheme 1. Oxidations of N-Boc Azacyclic Ketones 1-4 with Oxone
General reaction conditions: (a) ketone (1 mmol), Oxone (8 mmol), 2 M NaH2PO4/Na2HPO4 water solution (pH = 7) (14 mL), room temperature, 24 h; (b) ketone (1 mmol), Oxone (2 mmol), 1 M NaOH (8 mL), room temperature, 30 min; (c) ketone (1 mmol), Oxone (2 mmol), DMF (5–9 mL), room temperature (3 and 2) or 60 °C (1), 1 h (3) or 16 h (2) or 5 h (1); (d) (1) ketone (1 mmol), Oxone (2 mmol), 2 M NaH2PO4/Na2HPO4 water solution (pH = 7) (9 mL), room temperature, 2 h, and (2) 1 M NaOH (9 mL), room temperature, 30 min.
Scheme 2
Scheme 2. Oxidations of Cyclic Oxo-ethers 5–8 with Oxone
General reaction conditions: (a) ketone (1 mmol), Oxone (4 mmol), 1 M NaH2PO4/Na2HPO4 water solution (pH = 7) (4 mL), room temperature, 40 min; (b) ketone (1 mmol), Oxone (2 mmol), 2 M NaH2PO4/Na2HPO4 water solution (pH = 7) (4 mL), 0 °C, 10 min (7 and 6) or 3 min (5).
See this image and copyright information in PMC

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