Understanding Halide Counterion Effects in Enantioselective Ruthenium-Catalyzed Carbonyl (α-Aryl)allylation: Alkynes as Latent Allenes and Trifluoroethanol-Enhanced Turnover in The Conversion of Ethanol to Higher Alcohols via Hydrogen Auto-transfer

Eliezer Ortiz, Jonathan Z. Shezaf, Yu-Hsiang Chang, Theo Goncalves, Kuo-Wei Huang, Michael J. Krische

Research output: Contribution to journalArticlepeer-review

20 Scopus citations

Abstract

Crystallographic characterization of RuX(CO)(η3-C3H5)(JOSIPHOS), where X = Cl, Br, or I, reveals a halide-dependent diastereomeric preference that defines metal-centered stereogenicity and, therefrom, the enantioselectivity of C-C coupling in ruthenium-catalyzed anti-diastereo- and enantioselective C-C couplings of primary alcohols with 1-aryl-1-propynes to form products of carbonyl anti-(α-aryl)allylation. Computational studies reveal that a non-classical hydrogen bond between iodide and the aldehyde formyl CH bond stabilizes the favored transition state for carbonyl addition. An improved catalytic system enabling previously unattainable transformations was developed that employs an iodide-containing precatalyst, RuI(CO)3(η3-C3H5), in combination with trifluoroethanol, as illustrated by the first enantioselective ruthenium-catalyzed C-C couplings of ethanol to form higher alcohols.
Original languageEnglish (US)
JournalJournal of the American Chemical Society
DOIs
StatePublished - Oct 4 2021

Bibliographical note

KAUST Repository Item: Exported on 2021-10-07
Acknowledgements: The Robert A. Welch Foundation (F-0038) and the NIH-NIGMS (RO1-GM069445) are acknowledged for partial support of this research. We are grateful for the assistance of Dr. Vincent Lynch for the acquisition and analysis of X-ray diffraction data. The service of Ibex, Shaheen 2 High Performance Computing Facilities, was provided by King Abdullah University of Science and Technology (KAUST).

ASJC Scopus subject areas

  • Biochemistry
  • Colloid and Surface Chemistry
  • General Chemistry
  • Catalysis

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