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Intermolecular Michael reactions: a computational investigation.

Eugene E Kwan1, David A Evans

  • 1Department of Chemistry and Chemical Biology, Harvard University, 12 Oxford Street, Cambridge, Massachusetts 02138, United States. ekwan@fas.harVard.edu

Organic Letters
|October 5, 2010
PubMed
Summary
This summary is machine-generated.

Computational studies reveal that lithium enolates are key reactive intermediates. Explicitly solvated acetone enolates are primarily O-bound, influencing the stereochemical course of Michael additions.

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Area of Science:

  • Organic Chemistry
  • Computational Chemistry
  • Physical Chemistry

Background:

  • Lithium enolates are crucial reactive intermediates in organic synthesis.
  • The bonding nature (C-bound vs. O-bound) of lithium enolates influences their reactivity and stereochemical outcomes.
  • Previous computational studies suggested η(3)-lithium enolates, with partial cation binding to both carbon and oxygen, as important intermediates.

Purpose of the Study:

  • To investigate the bonding characteristics of explicitly solvated acetone enolates using computational methods.
  • To examine the stereochemical course of intermolecular Michael additions based on the determined enolate structure.
  • To evaluate the consistency of computational findings with experimental observations and existing models.

Main Methods:

  • Density Functional Theory (DFT) calculations were employed.
  • Explicit solvation models were used to simulate the acetone enolate environment.
  • Analysis of the stereochemical outcomes of intermolecular Michael addition reactions.

Main Results:

  • DFT calculations demonstrate that explicitly solvated acetone enolates are predominantly O-bound.
  • The O-bound nature of the enolates provides a basis for understanding the stereoselectivity observed in Michael additions.
  • The computational results align well with experimental data and the Heathcock model.

Conclusions:

  • Explicitly solvated acetone enolates exhibit a strong preference for O-binding.
  • This O-bound character is a key factor governing the stereochemical pathways in intermolecular Michael additions.
  • The study validates computational approaches for elucidating the mechanisms of organolithium reactions.