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
Type
ArticleAuthors
Ortiz, EliezerShezaf, Jonathan Z.
Chang, Yu-Hsiang
Goncalves, Theo
Huang, Kuo-Wei

Krische, Michael J.

KAUST Department
Chemical Science ProgramHomogeneous Catalysis Laboratory (HCL)
KAUST Catalysis Center (KCC)
Physical Science and Engineering (PSE) Division
Date
2021-10-04Online Publication Date
2021-10-04Print Publication Date
2021-10-13Embargo End Date
2022-10-04Submitted Date
2021-07-27Permanent link to this record
http://hdl.handle.net/10754/672172
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Show full item recordAbstract
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.Citation
Ortiz, E., Shezaf, J. Z., Chang, Y.-H., Gonçalves, T. P., Huang, K.-W., & Krische, M. J. (2021). 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. Journal of the American Chemical Society. doi:10.1021/jacs.1c07857Sponsors
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).Publisher
American Chemical Society (ACS)PubMed ID
34606271Additional Links
https://pubs.acs.org/doi/10.1021/jacs.1c07857ae974a485f413a2113503eed53cd6c53
10.1021/jacs.1c07857
Scopus Count
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