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The mechanism of enantioselective ketone reduction with Noyori and Noyori–Ikariya bifunctional catalysts

Journal Article · · Dalton Transactions
DOI:https://doi.org/10.1039/C6DT00476H· OSTI ID:1409757
 [1];  [1]
  1. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
+ Show Author Affiliations

The catalytic hydrogenation of prochiral ketones with second and third-row transition metal complexes bearing chelating chiral ligands containing at least one N–H functionality has achieved unparalleled performance, delivering, in the best cases, chiral alcohols with up to 99.9% ee using extremely small catalyst loadings (~10-5 mol%). Hence the efficacy of this reaction has closely approached that of natural enzymatic systems and the reaction itself has become one of the most efficient artificial catalytic reactions developed to date. This paper describes the current level of understanding of the mechanism of enantioselective hydrogenation and transfer hydrogenation of aromatic ketones with pioneering prototypes of bifunctional catalysts, the Noyori and Noyori–Ikariya complexes. Finally, analysis presented herein expands the concept of “metal–ligand cooperation”, redefines the term “cooperative ligand” and introduces “H–/H+ outer-sphere hydrogenation” as a novel paradigm in outer-sphere hydrogenation.

Research Organization:
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Sponsoring Organization:
USDOE
Grant/Contract Number:
AC52-06NA25396
OSTI ID:
1409757
Report Number(s):
LA-UR--16-20907
Journal Information:
Dalton Transactions, Journal Name: Dalton Transactions Journal Issue: 16 Vol. 45; ISSN 1477-9226
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English

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A Highly Active Manganese Catalyst for Enantioselective Ketone and Ester Hydrogenation journal April 2017
A Highly Active Manganese Catalyst for Enantioselective Ketone and Ester Hydrogenation journal April 2017
Comparative Study of Bifunctional Mononuclear and Dinuclear Amidoiridium Complexes with Chiral C−N Chelating Ligands for the Asymmetric Transfer Hydrogenation of Ketones journal September 2016
Selective Hydrogenation of α,β-Unsaturated Aldehydes and Ketones by Air-Stable Ruthenium NNS Complexes journal May 2017
Asymmetric transfer hydrogenation by synthetic catalysts in cancer cells journal January 2018
Triaminoborane-bridged diphosphine complexes with Ni and Pd: coordination chemistry, structures, and ligand-centered reactivity journal January 2017
Sequential asymmetric hydrogenation and photoredox chemistry with a single catalyst journal January 2018
Syntheses, characterisation, and catalytic role of (η 5 -C 5 Me 5 )Rh( iii ) guanidinato complexes in transfer hydrogenation (TH) and TH–etherification journal January 2017
Mononuclear complexes of a tridentate redox-active ligand with sulfonamido groups: structure, properties, and reactivity journal January 2018
A computational study on ligand assisted vs. ligand participation mechanisms for CO 2 hydrogenation: importance of bifunctional ligand based catalysts journal January 2019
Mechanisms of the H 2 - and transfer hydrogenation of polar bonds catalyzed by iron group hydrides journal January 2018
Cooperative Mn( i )-complex catalyzed transfer hydrogenation of ketones and imines journal January 2019
Ruthenium p -cymene complexes with α-diimine ligands as catalytic precursors for the transfer hydrogenation of ethyl levulinate to γ-valerolactone journal January 2018
Highly enantioselective Ir/f-amphox-catalyzed hydrogenation of ketoamides: efficient access to chiral hydroxy amides journal January 2018
Which future for stereogenic phosphorus? Lessons from P* pincer complexes of iron( ii ) journal January 2019
Mechanistic insights into asymmetric transfer hydrogenation of pyruvic acid catalysed by chiral osmium complexes with formic acid assisted proton transfer journal January 2019
Theoretical insights into CO 2 hydrogenation to methanol by a Mn–PNP complex journal January 2019
Controlling the selectivity and efficiency of the hydrogen borrowing reaction by switching between rhodium and iridium catalysts journal January 2019
Comparing the Acidity of (R3P)2BH-Based Donor Groups in Iridium Pincer Complexes journal May 2019
Which future for stereogenic phosphorus? Lessons from P* pincer complexes of iron(ii) text January 2019

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