Electronic effects steer the mechanism of asymmetric hydrogenations of unfunctionalized aryl-substituted alkenes. Academic Article

abstract

• Density functional theory (PBE and B3LYP) was used to study asymmetric hydrogenations of alkenes catalyzed by an iridium imidazolylidine oxazoline complex. The calculation predicts that the alkene preferentially coordinates to the site trans to the carbene. The coordinated alkene then reacts first with the H2 ligand, then with the hydride to form alkane. Finally, the alkane is released by equilibrating with extrinsic H2 and alkene. Enantioface selectivities for hydrogenations of trisubstituted alkenes seem to be driven primarily by steric interactions with the adamantyl part of the ligand; only the smallest substituents can adopt a site close to it. Application of this theoretical model leads to correct predictions regarding the experimentally observed sense and magnitude of the enantioselectivities.

authors

• Burgess, Kevin
• Hall, Michael

published proceedings

• J Am Chem Soc

altmetric score

• 3

author list (cited authors)

• Fan, Y., Cui, X., Burgess, K., & Hall, M. B.

citation count

• 137

complete list of authors

• Fan, Yubo||Cui, Xiuhua||Burgess, Kevin||Hall, Michael B

publication date

• December 2004

publisher

• American Chemical Society (ACS)  Publisher

published in

• Journal of the American Chemical Society  Journal

keywords

• 0601 Biochemistry And Cell Biology

PubMed Central ID

• 15612683

Digital Object Identifier (DOI)

• 10.1021/ja044240g

start page

• 16688

end page

• 16689

volume

• 126

issue

• 51

URL

• http://dx.doi.org/10.1021/ja044240g