Enhancing the Regioselectivity of B(C6F5)3-Catalyzed Epoxide Alcoholysis Reactions Using Hydrogen-Bond Acceptors

Mihir N. Bhagat, Charmaine K. Bennett, Gao Fong Chang, Youlong Zhu, Arjun Raghuraman, Matthew E. Belowich, Sonbinh T. Nguyen, Linda J. Broadbelt, Justin M. Notestein

Research output: Contribution to journalArticle

Abstract

Epoxide alcoholysis is extensively employed in the synthesis of polymers and chemical intermediates, and it generally requires an acid catalyst for high rates and selectivity. Tris(pentafluorophenyl)borane [B(C6F5)3] is among few catalysts that are selective to primary alcohol products of terminal aliphatic epoxides that do not possess any directing groups. We have previously observed that under many conditions, the reaction regioselectivity increases with conversion. Here, we confirm a prediction from our earlier computational model, and we experimentally demonstrate that this increase is due to a selectivity-enhancing role of the reaction products. We then show that deliberate addition of catalytic amounts of certain diols increases the reaction regioselectivity. Cis-1,2 or 1,3-diols are required to enhance selectivity, consistent with a mechanism where extended hydrogen-bonding networks preferentially organize the reactants. This work presents a route to tune regioselectivity without altering the catalyst backbone and provides another example of the role of H-bonding networks in reactions taking place in protic media.

Original languageEnglish
Pages (from-to)9663-9670
Number of pages8
JournalACS Catalysis
Volume9
Issue number10
DOIs
Publication statusPublished - Oct 4 2019

Fingerprint

Regioselectivity
Epoxy Compounds
Hydrogen bonds
Catalysts
Catalyst selectivity
Reaction products
Polymers
Alcohols
Acids

Keywords

  • boranes
  • hydrogen bonding
  • molecular catalysis
  • ring opening
  • selectivity

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)

Cite this

Enhancing the Regioselectivity of B(C6F5)3-Catalyzed Epoxide Alcoholysis Reactions Using Hydrogen-Bond Acceptors. / Bhagat, Mihir N.; Bennett, Charmaine K.; Chang, Gao Fong; Zhu, Youlong; Raghuraman, Arjun; Belowich, Matthew E.; Nguyen, Sonbinh T.; Broadbelt, Linda J.; Notestein, Justin M.

In: ACS Catalysis, Vol. 9, No. 10, 04.10.2019, p. 9663-9670.

Research output: Contribution to journalArticle

Bhagat, MN, Bennett, CK, Chang, GF, Zhu, Y, Raghuraman, A, Belowich, ME, Nguyen, ST, Broadbelt, LJ & Notestein, JM 2019, 'Enhancing the Regioselectivity of B(C6F5)3-Catalyzed Epoxide Alcoholysis Reactions Using Hydrogen-Bond Acceptors', ACS Catalysis, vol. 9, no. 10, pp. 9663-9670. https://doi.org/10.1021/acscatal.9b03089
Bhagat, Mihir N. ; Bennett, Charmaine K. ; Chang, Gao Fong ; Zhu, Youlong ; Raghuraman, Arjun ; Belowich, Matthew E. ; Nguyen, Sonbinh T. ; Broadbelt, Linda J. ; Notestein, Justin M. / Enhancing the Regioselectivity of B(C6F5)3-Catalyzed Epoxide Alcoholysis Reactions Using Hydrogen-Bond Acceptors. In: ACS Catalysis. 2019 ; Vol. 9, No. 10. pp. 9663-9670.
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