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Theoretical Study of the [2+2] Cycloaddition of Thioketenes with Imines To Form β ‐Thiolactams
Author(s) -
López Ramón,
Suárez Dimas,
Sordo Tomás L.,
RuizLópez Manuel F.
Publication year - 1998
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/(sici)1521-3765(19980210)4:2<328::aid-chem328>3.0.co;2-q
Subject(s) - conrotatory and disrotatory , cycloaddition , steric effects , solvent polarity , chemistry , ring (chemistry) , computational chemistry , polarity (international relations) , solvent , closure (psychology) , photochemistry , medicinal chemistry , stereochemistry , organic chemistry , catalysis , biochemistry , economics , market economy , cell
Abstract Zwitterionic intermediates play a crucial role in the [2 + 2] cycloaddition reaction between thioketene and formaldimine to give 2‐thioazetidinone (depicted on the right), for which HF, MP 2, B 3 LYP, and HF SCRF calculations predict conrotatory ring closure to be the rate‐determining step. The reaction rate is not sensitive to solvent polarity, and electronic effects of substituents are more important than the steric effects.

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