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

Abdulkader Baroudi, Amir Karton

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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.

Original languageEnglish
Pages (from-to)725-731
Number of pages7
JournalOrganic Chemistry Frontiers
Volume6
Issue number6
DOIs
Publication statusPublished - 21 Mar 2019

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Lactams
Density functional theory
semipinacol

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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.",
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