Jump to main content
Jump to site search


Deciphering the exceptional selectivity of semipinacol rearrangements in cis-fused β-lactam diols using high-level quantum chemical methods

Author affiliations

Abstract

The mechanism for the semipinacol rearrangement in cis-fused β-lactam diols has been examined using highly accurate double-hybrid density functional theory methods. This reaction involves a competition between two possible migrating groups (alkyl and acyl), which can undergo a 1,2 C–C bond migration. We find that acyl migration is both kinetically and thermodynamically more favorable. These results are consistent with experimental observations and are rationalized based on conformational, structural, and orbital interaction analysis. We proceed to investigate the semipinacol rearrangement in trans-fused β-lactam diol and propose that this system undergoes a reversed selectivity which favors the alkyl migration.

Graphical abstract: Deciphering the exceptional selectivity of semipinacol rearrangements in cis-fused β-lactam diols using high-level quantum chemical methods

Back to tab navigation

Supplementary files

Publication details

The article was received on 11 Oct 2018, accepted on 19 Nov 2018 and first published on 20 Nov 2018


Article type: Research Article
DOI: 10.1039/C8QO01092G
Citation: Org. Chem. Front., 2019, Advance Article
  •   Request permissions

    Deciphering the exceptional selectivity of semipinacol rearrangements in cis-fused β-lactam diols using high-level quantum chemical methods

    A. Baroudi and A. Karton, Org. Chem. Front., 2019, Advance Article , DOI: 10.1039/C8QO01092G

Search articles by author

Spotlight

Advertisements