Can I read The Role of Noninnocent Solvent Molecules in Organocatalyzed Asymmetric Michael Addition Reactions on EtoBox?

The Role of Noninnocent Solvent Molecules in Organocatalyzed Asymmetric Michael Addition Reactions by Mahendra P. Patil; Raghavan B. Sunoj is a Chemistry article available to read on EtoBox.

What is The Role of Noninnocent Solvent Molecules in Organocatalyzed Asymmetric Michael Addition Reactions about?

## Abstract A proline‐catalyzed asymmetric Michael addition between ketones and __trans__‐β‐nitrostyrene was studied by using the density‐functional theory with mPW1PW91 and B3LYP functionals. Improved insight into the enantio‐ and diastereoselective formation of γ‐nitroketones/‐aldehydes is obtained through transition‐state analysis. Consideration of the activation parameters obtained from gas‐phase calculations and continuum solvation models failed to reproduce the reported experimental stereoselectivities for the reaction between cyclohexanone and 3‐pentanone with __trans__‐β‐nitrostyrene. The correct diastereo‐ and enantioselectivites were obtained only upon explicit inclusion of solvent molecules in the diastereomeric transition states that pertain to the CC bond formation. Among the several transition‐state models that were examined, the one that exhibits cooperative hydrogen‐bonding interactions with two molecules of methanol could explain the correct stereochemical outcome of the Michael reaction. The change in differential stabilization that arises as a result of electrostatic and hydrogen‐bonding interactions in the key transition states is identified as the contributing

Who reads The Role of Noninnocent Solvent Molecules in Organocatalyzed Asymmetric Michael Addition Reactions?

Author

Mahendra P. Patil; Raghavan B. Sunoj

Publisher

John Wiley and Sons; Wiley (John Wiley & Sons); John Wiley & Sons Ltd.; Wiley (ISSN 0947-6539)

Published

2008

Language

EN

Field

Chemistry (Physical Sciences)