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(a) Dub, P. A.; Ikariya, T. Quantum Chemical Calculations with the
Inclusion of Nonspecific and Specific Solvation: Asymmetric Transfer
Hydrogenation with Bifunctional Ruthenium Catalysts. J. Am. Chem.
Soc., 2013, 135, 2604. (b) Dub, P. A.; Gordon, J. C. The mechanism of
enantioselective ketone reduction with Noyori and Noyori–Ikariya bi-
functional catalysts. Dalton Trans. 2016, 45, 6756.
(a) Catalysis Without Precious Metals; R.M. Bullock, Eds.;Wiley-VCH,
Weinheim, 2010. (b) Topics in Organometallic Chemistry; H. Nakaza-
wa, M. Itazaki, Eds.; Springer 2011. (c) M. Darwish, M. Wills, Asym-
metric catalysis using iron complexes – ‘Ruthenium lite’? Catal. Sci.
Technol. 2012, 2, 243. (d) B. A. F. Le Bailly, S. P. Thomas, Iron-
catalysed reduction of carbonyls and olefins. RSC Adv. 2011, 1, 1435.
ral Macrocyclic N
ganometallics 2014, 33, 4086. (g) Bigler, R. ETH Thesis No. 23398,
2016.
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P Ligands and Iron(II): A Marriage of Interest. Or-
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10 (a) Zuo, W. W.; Prokopchuk, D. E.; Lough, A. J.; Morris, R. H. Details
of the Mechanism of the Asymmetric Transfer Hydrogenation of Ace-
tophenone Using the Amine(imine)diphosphine Iron Precatalyst: The
Base Effect and The Enantiodetermining Step. ACS Catal. 2016, 6,
301. (b) Prokopchuk, D. E.; Morris, R. H. Inner-Sphere Activation,
Outer-Sphere Catalysis: Theoretical Study on the Mechanism of
Transfer Hydrogenation of Ketones Using Iron(II) PNNP Eneamido
Complexes. Organometallics 2012, 31, 7375. (c) Prokopchuk, D. E.;
Sonnenberg, J. F.; Meyer, N.; Zimmer-De Iuliis M.; Morris, R. H.
Spectroscopic and DFT Study of Ferraaziridine Complexes Formed in
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e) Chakraborty, S.; Guan, H. R. First-row transition metal catalyzed
reduction of carbonyl functionalities: a mechanistic perspective. Dal-
ton Trans. 2010, 39, 7427. (f) Morris, R. H. Asymmetric hydrogena-
tion, transfer hydrogenation and hydrosilylation of ketones catalyzed
by iron complexes. Chem. Soc. Rev. 2009, 38, 2282. (g) Junge, K.;
Schröder, K.; Beller, M. Homogeneous catalysis using iron complexes:
recent developments in selective reductions. Chem. Commun. 2011,
the Transfer Hydrogenation of Acetophenone Catalyzed Using trans-
4
-κ P,N,N,P](BF
[Fe(CO)(NCMe)(PPh
2
C
6
H
4
CH=NCH
2
−)
2
4
)
2
.
Or-
ganometallics 2012, 31, 3056. (d) Morris, R. H. Iron Group Hydrides
in Noyori Bifunctional Catalysis. Chem. Rec. 2016, 16, 2644. (e) Gor-
gas, N.; Stöger, B.; Veiros, L. F.; Pittenauer, E.; Allmaier, G.; Kirchner,
K. Efficient Hydrogenation of Ketones and Aldehydes Catalyzed by
Well-Defined Iron(II) PNP Pincer Complexes: Evidence for an Inser-
tion Mechanism. Organometallics, 2014, 33, 6905. (f) Lu, X.; Zhang, Y.
W.; Yun, P.; Zhang, M. T.; Li, T. L. The mechanism for the hydrogena-
tion of ketones catalyzed by Knölker's iron-catalyst. Org. Biomol. Chem.
2013, 11, 5264.
4
7, 4849. (h) Garbe, M.; Junge, K.; Beller, M. Homogeneous Catalysis
by Manganese‐Based Pincer Complexes. Eur. J. Org. Chem. 2017,
4344.
7
(a) Sui-Seng, C.; Freutel, F.; Lough, A. J.; Morris, R. H. Highly Effi-
cient Catalyst Systems Using Iron Complexes with a Tetradentate
PNNP Ligand for the Asymmetric Hydrogenation of Polar Bonds. An-
gew. Chem. Int. Ed. 2008, 47, 940. (b) Mikhailine, A.; Lough, A. J.;
Morris, R. H. Efficient Asymmetric Transfer Hydrogenation of Ke-
tones Catalyzed by an Iron Complex Containing a P−N−N−P Tetra-
dentate Ligand Formed by Template Synthesis. J. Am. Chem. Soc.
11 Samec, J. S. M.; Bäckvall, J. E.; Andersson, P. G.; Brandt, P. Mechanis-
tic aspects of transition metal-catalyzed hydrogen transfer reactions.
Chem. Soc. Rev. 2006, 35, 237.
12 (a) Smith, S. A. M.; Lagaditis, P. O.; Lüpke, A.; Lough, A. J.; Morris, R.
H. Unsymmetrical Iron P-NH-P’ Catalysts for the Asymmetric Pres-
sure Hydrogenation of Aryl Ketones. Chem. Eur. J. 2017, 23, 7212. (b)
Lagaditis, P. O.; Sues, P.E.; Sonnenberg, J. F.; Wan, K. Y.; Lough, A. J.;
Morris, R. H. Iron(II) Complexes Containing Unsymmetrical P–N–P’
Pincer Ligands for the Catalytic Asymmetric Hydrogenation of Ke-
tones and Imines. J. Am. Chem. Soc. 2014, 136, 1367. (c) Langer, R.;
Leitus, G.; Ben-David, Y.; Milstein, D. Efficient Hydrogenation of Ke-
tones Catalyzed by an Iron Pincer Complex. Angew. Chem. Int. Ed.
2011, 50, 2120. (d) Huber, R.; Passera, A.; Mezzetti, A. Iron(II)-
Catalyzed Hydrogenation of Acetophenone with a Chiral, Pyridine-
Based PNP Pincer Ligand: Support for an Outer-Sphere Mechanism.
Organometallics 2018, 37, 396. (e) Huber, R.; Passera, A.; Gubler, E.;
Mezzetti, A. P-Stereogenic PN(H)P Iron(II) Catalysts for the Asym-
metric Hydrogenation of Ketones: The Importance of Non-Covalent
Interactions in Rational Design by Computation. Adv. Synth. Catal.
2018, 360, 2900.
2
009, 131, 1394. (c) Lagaditis, P. O.; Lough, A. J.; Morris, R. H. Low-
Valent Ene–Amido Iron Complexes for the Asymmetric Transfer Hy-
drogenation of Acetophenone without Base. J. Am. Chem. Soc. 2011,
1
33, 9662. (d) Sonnenberg, J. F.; Coombs, N.; Dube, P. A.; Morris, R.
H. Iron Nanoparticles Catalyzing the Asymmetric Transfer Hydro-
genation of Ketones. J. Am. Chem. Soc. 2012, 134, 5893. (e) Mi-
khailine, A. A.; Maishan, M. I.; Lough, A. J.; Morris, R. H. The Mecha-
nism of Efficient Asymmetric Transfer Hydrogenation of Acetophe-
none Using an Iron(II) Complex Containing an (S,S)-
Ph
2
PCH
2
CH=NCHPhCHPhN=CHCH
2
PPh Ligand: Partial Ligand
2
Reduction Is the Key. J. Am. Chem. Soc. 2012, 134, 12266. (f) Zuo, W.
W.; Lough, A. J.; Li, Y. F.; Morris, R. H. Amine(imine)diphosphine
Iron Catalysts for Asymmetric Transfer Hydrogenation of Ketones and
Imines. Science 2013, 342, 1080. (g) Morris, R. H. Exploiting Metal–
Ligand Bifunctional Reactions in the Design of Iron Asymmetric Hy-
drogenation Catalysts. Acc. Chem. Res. 2015, 48, 1494. (h) Demmans,
K. Z.; Seo, C. S. G.; Lough, A. J.; Morris, R. H. From imine to amine:
an unexpected left turn. Cis-β iron(II) PNNP′ precatalysts for the
asymmetric transfer hydrogenation of acetophenone. Chem. Sci. 2017,
8, 6531. (j) Smith, S. A. M.; Prokopchuk, D. E.; Morris, R. H. Asym-
metric Transfer Hydrogenation of Ketones Using New Iron(II) (P‐
NH‐N‐P′) Catalysts: Changing the Steric and Electronic Properties at
Phosphorus P′. Isr. J. Chem. 2017, 57, 1204.
13 See, for instance: Rautenstrauch, V.; Xuan, H. C.; Churlaud, R.; Ab-
dur-Rashid, K.; Morris, R. H. Hydrogenation versus Transfer Hydro-
genation of Ketones: Two Established Ruthenium Systems Catalyze
Both. Chem. Eur. J. 2003, 9, 4954.
14 (a) Elangovan, S.; Topf, C.; Fischer, S.; Jiao, H.; Spannenberg, A.;
Baumann, W.; Ludwig, R.; Junge, K.; Beller, M. Selective Catalytic
Hydrogenation of Nitriles, Ketones, and Aldehydes by Well-Defined
Manganese Pincer Complexes. J. Am. Chem. Soc. 2016, 138, 8809.
(b) Elangovan, S.; Garbe, M.; Jiao, H.; Spannenberg, A.; Junge, K.; Bel-
ler, M. Hydrogenation of Esters to Alcohols Catalyzed by Defined
Manganese Pincer Complexes. Angew. Chem. Int. Ed. 2016, 55, 15364.
(c) Papa, V.; Cabrero-Antonino, J. R.; Alberico, E.; Spanneberg, A.;
Junge, K.; Junge, H.; Beller, M. Efficient and selective hydrogenation of
amides to alcohols and amines using a well-defined manganese–PNN
pincer complex. Chem. Sci. 2017, 8, 3576. (d) Kallmeier, F.; Irrgang,
T.; Dietel, T.; Kempe, R. Highly Active and Selective Manganese C=O
bond Hydrogenation Catalysts: The Importance of the Multidentate
Ligand, the Ancillary Ligands, and the Oxidation State. Angew. Chem.
Int. Ed. 2016, 55, 11806. (e) Espinosa-Jalapa, N. A.; Nerush, A.;
Shimon, L. J. W.; Leitus, G.; Avram, L.; Ben-David, Y.; Milstein, D.
Manganese-Catalyzed Hydrogenation of Esters to Alcohols. Chem.
Eur. J. 2017, 23, 5934.
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(a) Li, Y. Y.; Yu, S. L.; Shen, W. Y.; Gao, J. X. Iron-, Cobalt-, and Nick-
el-Catalyzed Asymmetric Transfer Hydrogenation and Asymmetric
Hydrogenation of Ketones. Acc. Chem. Res. 2015, 48, 2587.
(a) Bigler, R.; Huber, R.; Mezzetti, A. Highly Enantioselective Transfer
Hydrogenation of Ketones with Chiral (NH)
Complexes. Angew. Chem. Int. Ed. 2015, 54, 5171. (b) Bigler, R.;
Huber, R.; Stöckli, M.; Mezzetti, A. Iron(II)/(NH) Macrocycles:
2
2
P Macrocyclic Iron(II)
P
2 2
Modular, Highly Enantioselective Transfer Hydrogenation Catalysts.
ACS Catal. 2016, 6, 6455. (c) Bigler, R.; Mezzetti, A. Highly Enantio-
selective Transfer Hydrogenation of Polar Double Bonds by Macrocy-
clic Iron(II)/(NH)
d) Bigler, R.; Huber, R.; Mezzetti, A. Iron Chemistry Made Easy: Chi-
ral N Ligands for Asymmetric Catalysis. Synlett 2016, 27, 831. (e)
Bigler, R.; Mezzetti, A. Isonitrile Iron(II) Complexes with Chiral N
2
2
P Catalysts. Org. Process Res. Dev. 2016, 20, 253.
(
P
2 2
P
2 2
Macrocycles in the Enantioselective Transfer Hydrogenation of Keto-
nes. Org. Lett. 2014, 16, 6460. (f) Bigler, R.; Otth, E.; Mezzetti, A. Chi-
15 Ohkuma, T.; Koizumi, M.; Muniz, K.; Hilt, G.; Kabuto, C.; Noyori, R.
1
trans-RuH(η -BH
4
)(binap)(1,2-diamine): A Catalyst for Asymmetric
1
0
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