Work

Chronology of CH···O Hydrogen Bonding from Molecular Dynamics Studies of the Phosphoric Acid-Catalyzed Allylboration of Benzaldehyde

Year: 2017

Type: article

Abstract: CH···O hydrogen bonds involving formyl groups have been invoked as a crucial factor controlling many asymmetric transformations. We conducted quasi-classical direct molecular dynamics simulations on the phosphoric acid-catalyzed allylboration of benzaldehyde to understand the synergy between the phosphoric acid OH···O hydrogen bond and the secondary CH···O formyl hydrogen bond as the reaction occurs. In the gas phase, both the CH···O and OH···O hydrogen bonds are enhanced from reactants to transition states. In toluene, the trend of H-bond enhancement is observed with a smaller magnitude because of solvent caging. The strength of the formyl hydrogen bond in the TS, a second CH···O interaction between the P═O oxygen and ortho -hydrogen of the phenyl ring and the OH···O hydrogen bond were determined using quantum mechanical calculations (4.6, 1.0, and 14.5 kcal mol –1, respectively).

Source: Journal of the American Chemical Society

DOI: 10.1021/jacs.7b03847

Authors: Matthew N. Grayson, Zhongyue Yang, K. N. Houk

Institutions: University of Cambridge, University of California, Los Angeles

Language: English

Topic: Crystallography and molecular interactions

Subfield: Physical and Theoretical Chemistry

Field: Chemistry

Domain: Physical Sciences

Open Access status: green

Funders: English-Speaking Union, Girton College, University of Cambridge, Division of Chemistry

Award: G1455760090