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

doi:10.1021/jacs.1c07857

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 journal › Article › peer-review

23 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 language	English (US)
Journal	Journal of the American Chemical Society
DOIs	https://doi.org/10.1021/jacs.1c07857
State	Published - 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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CCDC 2099745: Experimental Crystal Structure Determination : (1-[1-(di-t-butylphosphanyl)ethyl]-2-(dicyclohexylphosphanyl)ferrocene)-allyl-carbonyl-chloro-ruthenium
Goncalves, T. (Creator), Huang, K.-W. (Creator), Ortiz, E. (Creator), Shezaf, J. Z. (Creator), Chang, Y.-H. (Creator) & Krische, M. J. (Creator), Cambridge Crystallographic Data Centre, Oct 4 2021
DOI: 10.5517/ccdc.csd.cc28gyqf, http://hdl.handle.net/10754/687101
Dataset
CCDC 2099746: Experimental Crystal Structure Determination : 3-(bicyclo[4.2.0]octa-1,3,5-trien-3-yl)pent-4-en-2-yl 3,5-dinitrobenzoate
Goncalves, T. (Creator), Huang, K.-W. (Creator), Ortiz, E. (Creator), Shezaf, J. Z. (Creator), Chang, Y.-H. (Creator) & Krische, M. J. (Creator), Cambridge Crystallographic Data Centre, Oct 4 2021
DOI: 10.5517/ccdc.csd.cc28gyrg, http://hdl.handle.net/10754/687102
Dataset
CCDC 2099743: Experimental Crystal Structure Determination : (1-[1-(di-t-butylphosphanyl)ethyl]-2-(dicyclohexylphosphanyl)ferrocene)-allyl-carbonyl-iodo-ruthenium
Goncalves, T. (Creator), Huang, K.-W. (Creator), Ortiz, E. (Creator), Shezaf, J. Z. (Creator), Chang, Y.-H. (Creator) & Krische, M. J. (Creator), Cambridge Crystallographic Data Centre, Oct 4 2021
DOI: 10.5517/ccdc.csd.cc28gync, http://hdl.handle.net/10754/687099
Dataset

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Ortiz, E., Shezaf, J. Z., Chang, Y.-H., Goncalves, T., 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. https://doi.org/10.1021/jacs.1c07857

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title = "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",

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.",

author = "Eliezer Ortiz and Shezaf, {Jonathan Z.} and Yu-Hsiang Chang and Theo Goncalves and Kuo-Wei Huang and Krische, {Michael J.}",

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).",

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Ortiz, E, Shezaf, JZ, Chang, Y-H, Goncalves, T , Huang, K-W & Krische, MJ 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. https://doi.org/10.1021/jacs.1c07857

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. / Ortiz, Eliezer; Shezaf, Jonathan Z.; Chang, Yu-Hsiang et al.
In: Journal of the American Chemical Society, 04.10.2021.

Research output: Contribution to journal › Article › peer-review

TY - JOUR

T1 - 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

AU - Ortiz, Eliezer

AU - Shezaf, Jonathan Z.

AU - Chang, Yu-Hsiang

AU - Goncalves, Theo

AU - Huang, Kuo-Wei

AU - Krische, Michael J.

N1 - 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).

PY - 2021/10/4

Y1 - 2021/10/4

N2 - 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.

AB - 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.

UR - http://hdl.handle.net/10754/672172

UR - https://pubs.acs.org/doi/10.1021/jacs.1c07857

U2 - 10.1021/jacs.1c07857

DO - 10.1021/jacs.1c07857

M3 - Article

C2 - 34606271

SN - 0002-7863

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

ER -

Ortiz E, Shezaf JZ, Chang YH, Goncalves T , Huang KW, Krische MJ. 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. 2021 Oct 4. doi: 10.1021/jacs.1c07857

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

Abstract

Bibliographical note

ASJC Scopus subject areas

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Datasets

CCDC 2099745: Experimental Crystal Structure Determination : (1-[1-(di-t-butylphosphanyl)ethyl]-2-(dicyclohexylphosphanyl)ferrocene)-allyl-carbonyl-chloro-ruthenium

CCDC 2099746: Experimental Crystal Structure Determination : 3-(bicyclo[4.2.0]octa-1,3,5-trien-3-yl)pent-4-en-2-yl 3,5-dinitrobenzoate

CCDC 2099743: Experimental Crystal Structure Determination : (1-[1-(di-t-butylphosphanyl)ethyl]-2-(dicyclohexylphosphanyl)ferrocene)-allyl-carbonyl-iodo-ruthenium

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