Organometallics
Communication
enantioselective hydrogenation of enol acetates catalyzed by Ru−
TunaPhos complexes. Org. Lett. 2002, 4, 4495−4497.
cobalt-catalyzed alkene hydrogenation: Catalysis with both redox-
active and strong field ligands. Acc. Chem. Res. 2015, 48, 1687−1695.
(6) (a) Semproni, S. P.; Milsmann, C.; Chirik, P. J. Four-coordinate
cobalt pincer complexes: electronic structure studies and ligand
modification by homolytic and heterolytic pathways. J. Am. Chem. Soc.
2014, 136, 9211−9224. (b) Schmidt, V. A.; Hoyt, J. M.; Margulieux,
G. W.; Chirik, P. J. Cobalt-catalyzed [2π + 2π] cycloadditions of
alkenes: scope, mechanism, and elucidation of electronic structure of
catalytic intermediates. J. Am. Chem. Soc. 2015, 137, 7903−7914.
(c) Hoyt, J. M.; Schmidt, V. A.; Tondreau, A. M.; Chirik, P. J. Iron-
catalyzed intermolecular [2 + 2] cycloadditions of unactivated
alkenes. Science 2015, 349, 960−963. (d) Holland, P. L. Distinctive
reaction pathways at base metals in high-spin organometallic catalysts.
Acc. Chem. Res. 2015, 48, 1696−1702. (e) Zhang, Z.; Butt, N. A.;
Zhou, M.; Liu, D.; Zhang, W. Asymmetric transfer and pressure
hydrogenation with earth-abundant transition metal catalysts. Chin. J.
Chem. 2018, 36, 443−454.
(3) (a) Ojima, I.; Kogure, T.; Yoda, N. J. Asymmetric hydrogenation
of prochiral olefins catalyzed by rhodium complexes with chiral
pyrrolidinodiphosphines. Crucial factors for the effective asymmetric
induction. J. Org. Chem. 1980, 45, 4728−4739. (b) Landis, C. R.;
Halpern, J. Asymmetric hydrogenation of methyl (Z)-alpha-
acetamidocinnamate catalyzed by [1,2-bis(phenyl-o-anisoyl)-
phosphino)ethane]rhodium(I): kinetics, mechanism and origin of
enantioselection. Rhodium-catalysed asymmetric hydrogenation as a
valuable synthetic tool for the preparation of chiral drugs. J. Am.
Chem. Soc. 1987, 109, 1746−1754. (c) Etayo, P.; Vidal-Ferran, A.
Rhodium-catalysed asymmetric hydrogenation as a valuable synthetic
tool for the preparation of chiral drugs. Chem. Soc. Rev. 2013, 42,
728−754. (d) Kita, Y.; Hida, S.; Higashihara, K.; Jena, H. S.;
Higashida, K.; Mashima, K. Chloride-bridged dinuclear rhodium(III)
complexes bearing chiral diphosphine ligands: catalyst precursors for
asymmetric hydrogenation of Simple olefins. Angew. Chem. 2016, 128,
(7) (a) Ohgo, Y.; et al. Asymmetric reactions. X. asymmetric
hydrogenation catalyzed by bis(dimethylglyoximato)cobalt(II)-chiral
cocatalyst (amino alcohol) System. Bull. Chem. Soc. Jpn. 1981, 54,
2124−2135. (b) Leutenegger, U.; Madin, A.; Pfaltz, A. Enantiose-
8
(
439−8443.
4) (a) Blackmond, D. G.; Lightfoot, A.; Pfaltz, A.; Rosner, T.;
Schnider, P.; Zimmermann, N. Enantioselective hydrogenation of
olefins with phosphinooxazoline-iridium catalysts. Chirality 2000, 12,
lective reduction of α, β-unsaturated carboxylates with NaBH and
4
4
42−449. (b) Perry, M. C.; Cui, X.; Powell, M. T.; Hou, D.-R.;
catalytic amounts of chiral cobalt semicorrin complexes. Angew.
Chem., Int. Ed. Engl. 1989, 28, 60−61. (c) Corma, A.; Iglesias, M.; del
Reibenspies, J. H.; Burgess, K. Optically active iridium imidazol-2-
ylidene-oxazoline complexes: preparation and use in asymmetric
hydrogenation of arylalkenes. J. Am. Chem. Soc. 2003, 125, 113−123.
Pino, C.; Sanchez, F. Optically active complexes of transition metals
́
(RhI, RuII, CoII and NiII) with 2-aminocarbonylpyrrolidine ligands.
Selective catalysts for hydrogenation of prochiral olefins. J. Organomet.
Chem. 1992, 431, 233−246. (d) Nindakova, L. O.; Shainyan, B. A.;
Shmidt, F. K. Total synthesis of terpenes. XIX. Synthesis of 8-
methoxy-4a.beta., 10b.beta., 12a.alpha.-trimethyl-3,4,4a,4b.al-
pha.,5,6,10b,11,12,12a-decahydrochrysen-1(2H)-one, a key inter-
mediate in the total synthesis of (+-)-shionone. Russ. J. Org. Chem.
2004, 40, 973−975. (e) Friedfeld, M. R.; Shevlin, M.; Hoyt, J. M.;
Krska, S. W.; Tudge, M. T.; Chirik, P. J. Cobalt precursors for high-
throughput discovery of base metal asymmetric alkene hydrogenation
catalysts. Science 2013, 342, 1076−1080. (f) Monfette, S.; Turner, Z.
(c) Pfaltz, A.; Blankenstein, J.; Hilgraf, R.; Ho
̈
rmann, E.; McIntyre, S.;
stenberg, B.;
Menges, F.; Schonleber, M.; Smidt, S. P.; Wu
Zimmermann, N. Iridium-catalyzed enantioselective hydrogenation
̈
̈
of olefins. Adv. Synth. Catal. 2003, 345, 33−43. (d) Bell, S.;
Wustenberg, B.; Kaiser, S.; Menges, F.; Netscher, T.; Pfaltz, A.
̈
Asymmetric hydrogenation of unfunctionalized, purely alkyl-Sub-
stituted olefins. Science 2006, 311, 642−644. (e) Kallstrom, K.;
̈
̈
Munslow, I. J.; Hedberg, C.; Andersson, P. G. Iridium-catalysed
asymmetric hydrogenation of vinylsilanes as a route to optically active
silanes. Adv. Synth. Catal. 2006, 348, 2575−2578. (f) Roseblade, S. J.;
Pfaltz, A. Iridium-catalyzed asymmetric hydrogenation of olefins. Acc.
Chem. Res. 2007, 40, 1402−1411. (g) Cheruku, P.; Diesen, J.;
Andersson, P. G. Asymmetric hydrogenation of di and trisubstituted
enol phosphinates with N,P-Ligated iridium complexes. J. Am. Chem.
Soc. 2008, 130, 5595−5599. (h) Church, T. L.; Andersson, P. G.
Iridium catalysts for the asymmetric hydrogenation of olefins with
nontraditional functional substituents. Coord. Chem. Rev. 2008, 252,
R.; Semproni, S. P.; Chirik, P. J. Enantiopure C -symmetric
1
bis(imino)pyridine cobalt complexes for asymmetric alkene hydro-
genation. J. Am. Chem. Soc. 2012, 134, 4561−4564. (g) Friedfeld, M.
R.; Shevlin, M.; Margulieux, G. W.; Campeau, L. C.; Chirik, P. J.
Cobalt-catalyzed enantioselective hydrogenation of minimally func-
tionalized alkenes: isotopic labeling provides insight into the origin of
stereoselectivity and alkene insertion preferences. J. Am. Chem. Soc.
2016, 138, 3314−3324. (h) Chen, J.; Chen, C.; Ji, C.; Lu, Z. Cobalt-
catalyzed asymmetric hydrogenation of 1,1-diarylethenes. Org. Lett.
2016, 18, 1594−1597. (i) Guo, J.; Shen, X.; Lu, Z. Regio- and
Enantioselective cobalt-catalyzed sequential hydrosilylation/hydro-
genation of terminal alkynes. Angew. Chem., Int. Ed. 2017, 56, 615−
618. (j) Friedfeld, M. R.; Zhong, H.; Ruck, R. T.; Shevlin, M.; Chirik,
P. J. Cobalt-catalyzed asymmetric hydrogenation of enamides enabled
by single-electron reduction. Science 2018, 360, 888−893.
5
13−531. (i) Cheruku, P.; Paptchikhine, A.; Church, T. L.;
Andersson, P. G. Iridium-N,P-ligand-catalyzed enantioselective hydro-
genation of diphenylvinylphosphine oxides and vinylphosphonates. J.
Am. Chem. Soc. 2009, 131, 8285−8289. (j) Mazuela, J.; Verendel, J. J.;
Coll, M.; Schaf
Dieguez, M. Iridium phosphite-oxazoline catalysts for the highly
enantioselective hydrogenation of terminal alkenes. J. Am. Chem. Soc.
009, 131, 12344−12353. (k) Tolstoy, P. i.; Engman, M.;
fner, B. n.; Borner, A.; Andersson, P. G.; Pamies, O.;
̈ ̈
̀
́
2
Paptchikhine, A.; Bergquist, J.; Church, T. L.; Leung, A. W.-M.;
Andersson, P. G. Iridium-catalyzed asymmetric hydrogenation
yielding chiral diarylmethines with weakly coordinating or non-
coordinating substituents. J. Am. Chem. Soc. 2009, 131, 8855−8860.
(8) (a) Jachak, G. R.; Ramesh, R.; Sant, D. G.; Jorwekar, S. U.;
Jadhav, M. R.; Tupe, S. G.; Deshpande, M. V.; Reddy, D. S. Silicon
incorporated morpholine antifungals: design, synthesis, and biological
evaluation. ACS Med. Chem. Lett. 2015, 6, 1111−1116. (b) Geyer, M.;
Baus, J. A.; Fjellstrom, O.; Wellner, E.; Gustafsson, L.; Tacke, R.
Synthesis and pharmacological properties of silicon-containing
GPR81 and GPR109A agonists. ChemMedChem 2015, 10, 2063−
2070. (c) Geyer, M.; Karlsson, O.; Baus, J. A.; Wellner, E.; Tacke, R.
Si-and C-functional organosilicon building blocks for synthesis based
on 4-silacyclohexan-1-ones containing the silicon protecting groups
MOP (4-methoxyphenyl), DMOP (2,6-dimethoxyphenyl), or TMOP
(2,4,6-trimethoxyphenyl). J. Org. Chem. 2015, 80, 5804−5811.
(d) Ramesh, R.; Reddy, D. S. Quest for novel chemical entities
through incorporation of silicon in drug scaffolds. J. Med. Chem. 2018,
61, 3779−3798. (e) Fujii, S.; Hashimoto, Y. Progress in the medicinal
chemistry of silicon: C/Si exchange and beyond. Future Med. Chem.
2017, 9, 485−505.
(
l) Church, T. L.; Rasmussen, T.; Andersson, P. G. Enantioselectivity
in the iridium-catalyzed hydrogenation of unfunctionalized olefins.
Organometallics 2010, 29, 6769−6781. (m) Mazuela, J.; Pamies, O.;
Dieguez, M. A phosphite-pyridine/iridium complex library as highly
̀
́
selective catalysts for the hydrogenation of minimally functionalized
olefins. Adv. Synth. Catal. 2013, 355, 2569−2583. (n) Bess, E. N.;
Sigman, M. S. Distinctive meta-directing group effect for iridium-
catalyzed 1,1-diarylalkene enantioselective hydrogenation. Org. Lett.
2
013, 15, 646−649. (o) Magre, M.; Pamies, O.; Dieguez, M. PHOX-
̀ ́
based phosphite-oxazoline ligands for the enantioselective Ir-catalyzed
hydrogenation of cyclic β-enamides. ACS Catal. 2016, 6, 5186−5190.
(5) (a) Bullock, R. M. Abundant metals give precious hydrogenation
performance. Science 2013, 342, 1054−1055. (b) Chirik, P. J. Iron and
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