Deciphering the exceptional selectivity of semipinacol rearrangements in cis-fused β-lactam diols using high-level quantum chemical methods
Literature Information
Publication Date
2018-11-20
DOI
10.1039/C8QO01092G
Impact Factor
5.281
Authors
Abdulkader Baroudi, Amir Karton
View Original
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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Source Journal
Organic Chemistry Frontiers
CiteScore:
7.8
Self-citation Rate:
8.7%
Articles per Year:
724
Organic Chemistry Frontiers publishes high-quality research from across organic chemistry. Emphases are placed on studies that make significant contributions to the field of organic chemistry by reporting either new or significantly improved protocols or methodologies. Topics include, but are not limited to the following: Organic synthesis Development of synthetic methodologies Catalysis Natural products Functional organic materials Supramolecular and macromolecular chemistry Physical and computational organic chemistry
Recommended Compounds
Oxalic acid compound with cyclohexylsulfamothioic O-acid (11)
CAS Number:
31895-22-4
Molecular Formula:
C7H13NO4S3
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