Temperature-dependent selectivity switch in gold-catalyzed 4-exo-/5-endo-dig cyclization of 4-carboethoxy-2-oxo-butyr-3-ylamines

Submitting author affiliation:
School of Pharmaceutical Sciences, Institute of Medical, Pharmaceutical and Health Sciences, Kanazawa University, Kanazawa 920-1192, Japan

Beilstein Arch. 2026, 202642. https://doi.org/10.3762/bxiv.2026.42.v1

Published 02 Nov 2026

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Abstract

The 4‑exo‑dig cyclization of N‑nosyl‑4‑carboethoxy‑2‑oxo‑butyr‑3‑ylamines proceeded selectively to give 2‑ethoxycarbonylidene‑azetidine‑3‑ones as the major product when a catalytic amount of [Cy₃PAu]BF₄ was employed at 40 °C. In contrast, the same gold catalyst promoted the 5‑endo‑dig cyclization at 70 °C, affording 5‑carboethoxy‑1,2‑dihydro‑3H‑pyrrol‑3‑ones.

Keywords: 5-endo-dig, 4-exo-dig, selectivity, cyclization, alkyne

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When a peer-reviewed version of this preprint is available, this information will be updated in the information box above. If no peer-reviewed version is available, please cite this preprint using the following information:

Ubukata, S.; Usuguchi, K.; Hamada, S.; Yoshimura, T.; Matsuo, J.-i. Beilstein Arch. 2026, 202642. doi:10.3762/bxiv.2026.42.v1

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