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

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

Research output: Contribution to journalArticle

23 Citations (Scopus)

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).

LanguageEnglish
Pages7717-7720
Number of pages4
JournalJournal of the American Chemical Society
Volume139
Issue number23
Early online date30 May 2017
DOIs
StatusPublished - 14 Jun 2017

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Chronology
Phosphoric acid
Molecular Dynamics Simulation
Hydrogen Bonding
Molecular dynamics
Hydrogen
Hydrogen bonds
Toluene
phosphoric acid
benzaldehyde
Gases
Oxygen
Computer simulation

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Chronology of CH···O Hydrogen Bonding from Molecular Dynamics Studies of the Phosphoric Acid-Catalyzed Allylboration of Benzaldehyde. / Grayson, Matthew N.; Yang, Zhongyue; Houk, K. N.

In: Journal of the American Chemical Society, Vol. 139, No. 23, 14.06.2017, p. 7717-7720.

Research output: Contribution to journalArticle

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