Reduction of 2-phenyl-3a,4,7,7a-tetrahydro-1H-isoindole-1,3(2H)-dione with NaBH4: Investigation of<i> exo</i>-selectivity and reaction mechanism<i> via</i> theoretical computations

GÜNDOĞDU Ö., Atalay A., Turhan P., ANIL B., ŞAHİN E., BOZKAYA U., ...More

JOURNAL OF MOLECULAR STRUCTURE, vol.1319, 2025 (SCI-Expanded) identifier identifier

  • Publication Type: Article / Article
  • Volume: 1319
  • Publication Date: 2025
  • Doi Number: 10.1016/j.molstruc.2024.139520
  • Journal Name: JOURNAL OF MOLECULAR STRUCTURE
  • Journal Indexes: Science Citation Index Expanded (SCI-EXPANDED), Scopus, Academic Search Premier, Chemical Abstracts Core, Chimica, Compendex, INSPEC
  • Hacettepe University Affiliated: Yes

Abstract

The reaction of the bicyclic imide with NaBH4 afforded acylaminocarbinol and carboxamide derivatives. The exact configuration of acylaminocarbinol 7 was determined by X-ray crystal analysis. Theoretical studies were carried out to explain the mechanism of the exo-selectivity observed in the first step of the reduction reaction and the formation of the secondary product in the second step. According to the obtained findings, i) in the first step of the reaction, the exo-path is kinetically more favorable, and ii) an alternative mechanism has been proposed instead of the mechanism proposed in the literature. The canonical forms of the amide group in the lactam ring were found to make an important contribution to the mechanism. iii) The amount of products formed in the reduction reaction depends on the reaction conditions.