Molecular metal/NH bifunctional Noyori-type catalysts are remarkable in that they are among the most efficient artificial catalysts developed to date for the hydrogenation of carbonyl functionalities (loadings up to ~10–5 mol %). In addition, these catalysts typically exhibit high C$$=$$O/C$$=$$C chemo- and enantioselectivities. This unique set of properties is traditionally associated with the operation of an unconventional mechanism for homogeneous catalysts in which the chelating ligand plays a key role in facilitating the catalytic reaction and enabling the aforementioned selectivities by delivering/accepting a proton (H+) via its N–H bond cleavage/formation. A recently revised mechanism of the Noyori hydrogenation reaction (Dub, P. A. et al. J. Am. Chem. Soc. 2014, 136, 3505) suggests that the N–H bond is not cleaved but serves to stabilize the turnover-determining transition states (TDTSs) via strong N–H···O hydrogen-bonding interactions (HBIs). Here, the present paper shows that this is consistent with the largely ignored experimental fact that alkylation of the N–H functionality within M/NH bifunctional Noyori-type catalysts leads to detrimental catalytic activity. Finally, the purpose of this work is to demonstrate that decreasing the strength of this HBI, ultimately to the limit of its complete absence, are conditions under which the same alkylation may lead to beneficial catalytic activity.
Dub, Pavel, et al. "Why Does Alkylation of the N–H Functionality within M/NH Bifunctional Noyori-Type Catalysts Lead to Turnover?." Journal of the American Chemical Society, vol. 139, no. 3, Jan. 2017. https://doi.org/10.1021/jacs.6b11666
Dub, Pavel, Gordon, John Cameron, & Scott, Brian Lindley (2017). Why Does Alkylation of the N–H Functionality within M/NH Bifunctional Noyori-Type Catalysts Lead to Turnover?. Journal of the American Chemical Society, 139(3). https://doi.org/10.1021/jacs.6b11666
Dub, Pavel, Gordon, John Cameron, and Scott, Brian Lindley, "Why Does Alkylation of the N–H Functionality within M/NH Bifunctional Noyori-Type Catalysts Lead to Turnover?," Journal of the American Chemical Society 139, no. 3 (2017), https://doi.org/10.1021/jacs.6b11666
@article{osti_1364541,
author = {Dub, Pavel and Gordon, John Cameron and Scott, Brian Lindley},
title = {Why Does Alkylation of the N–H Functionality within M/NH Bifunctional Noyori-Type Catalysts Lead to Turnover?},
annote = {Molecular metal/NH bifunctional Noyori-type catalysts are remarkable in that they are among the most efficient artificial catalysts developed to date for the hydrogenation of carbonyl functionalities (loadings up to ~10–5 mol %). In addition, these catalysts typically exhibit high C$=$O/C$=$C chemo- and enantioselectivities. This unique set of properties is traditionally associated with the operation of an unconventional mechanism for homogeneous catalysts in which the chelating ligand plays a key role in facilitating the catalytic reaction and enabling the aforementioned selectivities by delivering/accepting a proton (H+) via its N–H bond cleavage/formation. A recently revised mechanism of the Noyori hydrogenation reaction (Dub, P. A. et al. J. Am. Chem. Soc. 2014, 136, 3505) suggests that the N–H bond is not cleaved but serves to stabilize the turnover-determining transition states (TDTSs) via strong N–H···O hydrogen-bonding interactions (HBIs). Here, the present paper shows that this is consistent with the largely ignored experimental fact that alkylation of the N–H functionality within M/NH bifunctional Noyori-type catalysts leads to detrimental catalytic activity. Finally, the purpose of this work is to demonstrate that decreasing the strength of this HBI, ultimately to the limit of its complete absence, are conditions under which the same alkylation may lead to beneficial catalytic activity.},
doi = {10.1021/jacs.6b11666},
url = {https://www.osti.gov/biblio/1364541},
journal = {Journal of the American Chemical Society},
issn = {ISSN 0002-7863},
number = {3},
volume = {139},
place = {United States},
publisher = {American Chemical Society (ACS)},
year = {2017},
month = {01}}
Noyori, Ryoji; Sandoval, Christian A.; Muñiz, Kilian
Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences, Vol. 363, Issue 1829https://doi.org/10.1098/rsta.2004.1536