Stereoselective ring transformation of n-alkyl aziridines into oxazolidin-2-ones

Sepúlveda-Arques, José; Armero‐Alarte, Trinidad; Acero-Alarcón, Alberto; Zaballos-García, Elena; Solesio, B. Yruretagoyena; Carrera, Jesús Ezquerra

doi:10.1016/0040-4020(95)01025-4

Cited by 24 publications

(8 citation statements)

References 8 publications

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“…3‐Benzylhexahydro‐2 H ‐cyclopenta[ d ]oxazol‐2‐one (2 o) : Analytical TLC on silica gel, 2:3 EtOAc/petroleum ether, R f =0.38; colourless liquid; yield 72 % (78 mg); 1 H NMR (400 MHz, CDCl 3 ): δ =7.36–7.27 (m, 5 H, ArH), 4.87–4.84 (m, 1 H, CHO), 4.76 (d, J =15.2 Hz, 1 H, NCH 2 Ph), 4.06 (d, J =15.2 Hz, 1 H, NCH 2 Ph), 3.96 (t, J =6.8 Hz, 1 H, CHN), 2.08–2.04 (m, 1 H, CH 2 ), 1.87–1.83 (m, 1 H, CH 2 ), 1.70–1.60 (m, 3 H, CH 2 CH 2 ), 1.43–1.33 ppm (m, 1 H, CH 2 ); 13 C NMR (100 MHz, CDCl 3 ): δ =158.5, 136.2, 128.9, 128.3, 128.0, 79.2, 59.6, 46.7, 34.0, 30.5, 22.2 ppm; IR (neat):

\overset{ν}{true}

max =1731 cm −1 ; MS (ESI): calcd for C 13 H 16 NO 2 ( M H) + : 218.1176; found: 218.1175, 240.0993 [ M +Na] + .…”

Section: Methodsmentioning

confidence: 99%

“…5‐(Hydroxymethyl)‐3‐(3‐methylphenyl)oxazolidin‐2‐one (toloxatone) (2 r) : Analytical TLC on silica gel, 3:2 EtOAc/petroleum ether, R f =0.09; white solid; yield 70 % (72 mg); m.p. : 78–79 °C (lit . 75–76 °C); 1 H NMR (400 MHz, CDCl 3 ): δ =7.37 (s, 1 H, ArH), 7.31 (d, J =8.4 Hz, 1 H, ArH), 7.24 (t, J =8.0 Hz, 1 H, ArH), 6.96 (d, J =7.6 Hz, 1 H, ArH), 4.74–4.68 (m, 1 H, CHN), 4.03–3.92 (m, 3 H, CH 2 N, CH 2 OH), 3.76–3.70 (m, 1 H, CH 2 OH), 2.80 (t, J =6.8 Hz, 1 H, OH), 2.35 ppm (s, 3 H, CH 3 ); 13 C NMR (100 MHz, CDCl 3 ): δ =155.1, 139.2, 138.1, 129.0, 125.2, 119.3, 115.6, 73.1, 62.9, 46.6, 21.8 ppm; IR (neat):

\overset{ν}{true}

max =3481, 2912, 1722, 1419, 1233 cm −1 ; MS (ESI): calcd for C 11 H 14 NO 3 ( M H) + : 208.0968; found: 208.0968, 230.0788 [ M +Na] + .…”

Section: Methodsmentioning

confidence: 99%

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Synthesis of Oxazolidinones by using Carbon Dioxide as a C₁ Building Block and an Aluminium‐Based Catalyst

2019

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Oxazolidinone synthesis through the coupling of carbon dioxide and aziridines was catalysed by an aluminium(salphen) complex at 50–100 °C and 1–10 bar pressure under solvent‐free conditions. The process was applicable to a variety of substituted aziridines, giving products with high regioselectivity. It involved the use of a sustainable and reusable aluminium‐based catalyst, used carbon dioxide as a C1 source and provided access to pharmaceutically important oxazolidinones as illustrated by a total synthesis of toloxatone. This protocol was scalable, and the catalyst could be recovered and reused. A catalytic cycle was proposed based on stereochemical, kinetic and Hammett studies.

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\overset{ν}{true}

max =1731 cm −1 ; MS (ESI): calcd for C 13 H 16 NO 2 ( M H) + : 218.1176; found: 218.1175, 240.0993 [ M +Na] + .…”

Section: Methodsmentioning

confidence: 99%

\overset{ν}{true}

max =3481, 2912, 1722, 1419, 1233 cm −1 ; MS (ESI): calcd for C 11 H 14 NO 3 ( M H) + : 208.0968; found: 208.0968, 230.0788 [ M +Na] + .…”

Section: Methodsmentioning

confidence: 99%

Synthesis of Oxazolidinones by using Carbon Dioxide as a C₁ Building Block and an Aluminium‐Based Catalyst

2019

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“…Obviously, issues of regioselectivity can be a problem when other substituents are present on the aziridine ring, due to non-regioselective opening of the intermediate aziridinium ion by the halide. Scheme 3 outlines one such example (15 leading to 16 and 17 [24]). On the other hand, since 11 and 13 have a benzylic carbon, they are selectively attacked by the halide, and these reactions occur with high regioselectivity to give 12 and 14 [23,25].…”

Section: Expansions Into Oxazolidinonesmentioning

confidence: 98%

Ring Expansions of Nonactivated Aziridines and Azetidines

Couty

David

2015

Topics in Heterocyclic Chemistry

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Ring expansions promoted by ring strain in aziridines and azetidines are reviewed in this chapter, putting emphasis on recent applications from the last decade. This vast subject cannot be surveyed here exhaustively, and the reader will be guided to relevant precedent reviews or key reports. Rather, special attention will be put on selected examples and their mechanistic details, aiming to demonstrate that high selectivity can be reached in these reactions. In this issue, this fastgrowing topic has been divided into two distinct chapters, this one dealing with "nonactivated" aziridines and azetidines. Therefore, the reader will only find here examples involving NH-or N-alkylaziridines and N-azetidines as substrates for ring expansions, while N-acyl, N-carbamoyl, or N-tosyl compounds, defined as "activated" substrates, will be presented in the next chapter. This distinction can appear quite arbitrary at first sight but is amply justified by the great difference in reactivity of these distinct substrates. The first part focuses on the ring expansions of nonactivated aziridines into up to seven-membered rings and is further divided into expansions involving the incorporation of one (or more) heteroatoms, followed by ring expansions involving only incorporation of carbon atoms. The same model is then followed for azetidines.

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“…The one-pot ring rearrangement of N-alkyl aziridines 62 into N-alkyl-4,5-disubstituted 1,3-oxazolidin-2-ones 63 (Scheme 39a) by reaction with Boc 2 O/NaI in acetone has been extensively studied by Sepúlveda-Arqués and coworkers [64].…”

Section: Aziridinesmentioning

confidence: 99%

Oxazolidin-2-one Ring, a Popular Framework in Synthetic Organic Chemistry: Part 1. The Construction of the Oxazolidin-2-one Ring

Zappia¹,

Gács‐Baitz²,

Monache³

et al. 2007

COS

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Stereoselective ring transformation of n-alkyl aziridines into oxazolidin-2-ones

Cited by 24 publications

References 8 publications

Synthesis of Oxazolidinones by using Carbon Dioxide as a C₁ Building Block and an Aluminium‐Based Catalyst

Synthesis of Oxazolidinones by using Carbon Dioxide as a C₁ Building Block and an Aluminium‐Based Catalyst

Ring Expansions of Nonactivated Aziridines and Azetidines

Oxazolidin-2-one Ring, a Popular Framework in Synthetic Organic Chemistry: Part 1. The Construction of the Oxazolidin-2-one Ring

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Stereoselective ring transformation of n-alkyl aziridines into oxazolidin-2-ones

Cited by 24 publications

References 8 publications

Synthesis of Oxazolidinones by using Carbon Dioxide as a C1 Building Block and an Aluminium‐Based Catalyst

Synthesis of Oxazolidinones by using Carbon Dioxide as a C1 Building Block and an Aluminium‐Based Catalyst

Ring Expansions of Nonactivated Aziridines and Azetidines

Oxazolidin-2-one Ring, a Popular Framework in Synthetic Organic Chemistry: Part 1. The Construction of the Oxazolidin-2-one Ring

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Product

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Synthesis of Oxazolidinones by using Carbon Dioxide as a C₁ Building Block and an Aluminium‐Based Catalyst

Synthesis of Oxazolidinones by using Carbon Dioxide as a C₁ Building Block and an Aluminium‐Based Catalyst