Chemo- and Enantioselective Catalytic Hydrogenation of α,β-Unsaturated Ketones and Aldehydes as a Tool to Introduce Chiral Centers at α- or β-Positions of Ketones

For example, Cano R. , Zakarian A. , McGlacken G.P. (2017) Direct asymmetric alkylation of ketones: still unconquered. Angewandte Chemie, International Edition, 56, 9278–9290, and earlier references cited therein.

For example, (a) Wang C. , Goh C.M.T. , Xiao S. , Ye W. , Tan C-H . (2013) Enantioselective protonation catalyzed by chiral Brönsted bases. Journal of Synthetic Organic Chemistry, Japan, 71, 1145–1151; (b) Phelan JP, Ellman JA. (2016) Conjugate addition–enantioselective protonation reactions. Beilstein Journal of Organic Chemistry, 12, 1203–1228, and earlier references cited therein.

For example, (a) Schmid T.E. , Drissi-Amraoui S. , Crévisy C. , Baslé O. , Mauduit M. (2015) Copper-catalyzed asymmetric conjugate addition of organometallic reagents to extended Michael acceptors. Beilstein Journal of Organic Chemistry, 11, 2418–2434; (b) Shockley SE, Holder JC, Stoltz, BM. (2015) Palladium-catalyzed asymmetric conjugate addition of arylboronic acids to α,β-unsaturated cyclic electrophiles. Organic Process Research & Development, 19, 974–981, and earlier references cited therein.

Some recent representative reviews in this area. (a) Ager D.J. , de Vries A.H.M. , de Vries J.G. (2012) Asymmetric homogeneous hydrogenations at scale. Chemical Society Review, 41, 3340–3380; (b) Chen Q-A, Ye Z-S, Duan Y, Zhou Y-G. (2013) Rhodium-catalysed asymmetric hydrogenation as a valuable synthetic tool for the preparation of chiral drugs. Chemical Society Review, 42, 497–511; (c) Etayoa P, Vidal-Ferran A. (2013) Homogeneous palladium-catalyzed asymmetric hydrogenation. Chemical Society Review, 42, 728–754; (d) Zhan E, Chen C, Li Y, Shen W. (2015) Heterogeneous asymmetric hydrogenation over chiral molecule-modified metal particles. Catalysis Science & Technology, 5(2), 650–659; (e) Verendel JJ, Pàmies O, Diéguez M, Andersson PG. (2014) Asymmetric hydrogenation of olefins using chiral Crabtree-type catalysts: Scope and Limitations. Chemical Review, 114, 2130–2169; (f) Chena X-S, Houa C-J, Hub X-P. (2016) Chiral phosphine-phosphoramidite ligands in asymmetric catalysis. Synthetic Communications. 46, 917–941.

Fogassy G. , Tungler A. , Lévai A. , Tóth G. (2002) Enantioselective hydrogenation of exocyclic α,β-unsaturated ketones Part II. Hydrogenation in the presence of (S)-proline. Journal of Molecular Catalysis A: Chemical, 179, 101–106.

Szabados E. , Györffy N. , Tungler A. , Balla J. , Könczö L. (2014) Asymmetric hydrogenation of prochiral and kinetic resolution of chiral cyclohexanone derivatives with Pd catalysts. Reaction Kinetics and Catalysis Letters, 111, 107–114.

(a) Thorey C. , Henin F. , Muzart J. (1996) Enantioselective hydrogenation of α,β-unsaturated ketones over palladium on charcoal in the presence of (-)-ephedrine. Tetrahedron: Asymmetry, 7, 975–976; (b) Thorey C, Bouquillon S, Helimi A, Hénin F, Muzart J. (2002) Palladium on charcoal plus enantiopure amino alcohols as catalytic systems for the enantioselective 1,4-reduction of α-substituted α,β-unsaturated ketones. European Journal of Organic Chemistry, 2151–2159.

Fogassy G. , Tungler A. , Lévai A. (2003) Enantioselective hydrogenation of exocyclic α,β-unsaturated ketones Part III. Hydrogenation with Pd in the presence of cinchonidine. Journal of Molecular Catalysis A: Chemical, 192, 189–194.

Some recent reviews on chiral ligands in asymmetric synthesis. (a) Carroll M.P. , Guiry P.J. (2014) P,N ligands in asymmetric catalysis. Chemical Society Review, 43, 819–833; (b) Chen X, Lu L. (2017) Recent advances in chiral imino-containing ligands for metal-catalyzed asymmetric transformations. Organic & Biomolecular Chemistry, 15, 2280–2306.

For example (a) Lightfoot A. , Schnider P. , Pfaltz A. (1998) Enantioselective hydrogenation of olefins with iridium-phosphanodihydrooxazole catalysts Angewandte Chemie International Edition, 37, 2897–2899; (b) Helmchen G, Pfaltz A. (2000) Phosphinooxazoliness-a new class of versatile, modular P,N-ligands for asymmetric catalysis. Accounts of Chemical Research, 33, 336–345; (c) Roseblade SJ, Pfaltz, A. (2007) Iridium-catalyzed asymmetric hydrogenation of olefins. Accounts of Chemical Research, 40, 1402–1411.

Lu S-M , Bolm C. (2008) Highly enantioselective synthesis of optically active ketones by iridium-catalyzed asymmetric hydrogenation. Angewandte Chemie International Edition, 47, 8920–8923.

Lu W.-J. , Hen Y.-W. , Hon X.-L . (2010) Highly enantioselective iridium-catalyzed hydrogenation of trisubstituted olefins, α,β-unsaturated ketones and imines with chiral benzylic substituted P,N ligands. Advanced Synthesis & Catalysis, 352, 103–107.

Maurer F. , Huch V. , Ullrich A. , Kazmaier U. (2012) Development of catalysts for the stereoselective hydrogenation of α,β-unsaturated ketones. Journal of Organic Chemistry, 77, 5139–5143.

Tian F. , Yao D. , Liu Y. , Xie F. , Zhanga W. (2010) Iridium-catalyzed highly enantioselective hydrogenation of exocyclic α,β-unsaturated carbonyl compounds. Advanced Synthesis & Catalysis, 352, 1841–1845.

Li Q. , Wan P. , He Y. , Zhou Y. , Li L. , Chen B. , Duan K. , Cao R. , Zhou Z. , Qiu L. (2014) Enantioselective hydrogenation of the double bond of exocyclic α,β-unsaturated carbonyl compounds catalyzed by iridium/H₈-BINOL derived phosphine-oxazoline complexes. Asian Journal of Organic Chemistry, 3, 774–783.

Liu X. , Han Z. , Wang Z. , Ding K. (2014) SpinPhox/Iridium(I)-catalyzed asymmetric hydrogenation of cyclic α-alkylidene carbonyl compounds. Angewandte Chemie International Edition, 53, 1978–1982.

Wang X. , Han Z. , Wang Z. , Ding K. (2012) Catalytic asymmetric synthesis of aromatic spiroketals by SpinPhox/Iridium(I)-catalyzed hydrogenation and spiroketalization of α,α'-bis(2-hydroxyarylidene) ketones. Angewandte Chemie International Edition, 51, 936–940.

Ohta T. , Miyake T. , Seido N. , Kumobayashi H. , Takaya H. (1995) Asymmetric hydrogenation of olefins with aprotic oxygen functionalities catalyzed by BINAP-Ru(I1) complexes. Journal of Organic Chemistry, 60, 357–363.

Margalef J. , Caldentey X. , Karlsson E.A. , Coll M. , Mazuela J. , Pàmies O. , Diéguez M. , Pericàs M.A. (2014) A theoretically-guided optimization of a new family of modular P,S-ligands for iridium-catalyzed hydrogenation of minimally functionalized olefins. Chemistry A European Journal, 20, 12201–12214.

(a) Sun T. , Hou G. , Ma M. , Zhang X. (2011) New synthetic strategy for high-enantiopurity N-protected α-amino ketones and their derivatives by asymmetric hydrogenation. Advanced Synthesis & Catalysis, 353, 253–256; (b) Gao W, Wang O, Xie Y, Lv H, Zhang X. (2016) Rhodium-catalyzed asymmetric hydrogenation of α-dehydroamino ketones: A general approach to chiral α-amino ketones. Chemistry An Asian Journal, 11, 231–233.

Sun T. , Zhang X. (2012) A simple synthetic route to enantiopure α-hydroxy ketone derivatives by asymmetric hydrogenation. Advanced Synthesis & Catalysis, 354, 3211–3215.

(a) Tungler A. , Kajtar M. , Mathe T. , Toth G. , Fogassy E. , Petro J. (1989) Enantioselective hydrogenation of α,β-unsaturated ketones. Catalysis Today, 5, 159–171;(b) Fodor M, Tungler A, Vida L. (2009) Asymmetric hydrogenation of isophorone in the presence of (S)-proline: Revival of a 20 years old reaction. Catalysis Today, 140, 58–63.

McIntosh A.I. , Watson D.J. , Burton J.W. , Lambert R.M. (2006) Heterogeneously catalyzed asymmetric C=C hydrogenation: origin of enantioselectivity in the proline-directed Pd/Isophorone system. Journal of the American Chemical Society, 128, 7329–7334.

Györffy N. , Tungler A. , Fodor M. (2010) Stereodifferentiation in heterogeneous catalytic hydrogenation. Kinetic resolution and asymmetric hydrogenation in the presence of (S)-proline: Catalyst-dependent processes. Journal of Catalysis, 270, 2–8.

Tungler A. , Nitta Y. , Fodor K. , Farkas G. , Mathe T. (1999) Comparison of chiral modifiers in the Pd catalysed hydrogenation of phenylcinnamic acid and isophorone. Journal of Molecular Catalysis A: Chemistry, 149, 135–140.

(a) Le Maux P. , Massonneau V. , Simommeaux G. (1985) Asymmetric catalysis by chiral phosphine cobalt carbonyl complexes. Hydrogenation of α,β-unsaturated ketones. Journal of Organometallic Chemistry, 284, 101–108; (b) Le Maux P, Simommeaux G. (1983) Asymmetric hydrogenation of α,β-unsaturated ketones with chiral phosphinecobalt carbonyl catalysts. Journal of Organometallic Chemistry, 252, C60-C62.

Watson D.J. , Jesudason Rjbrj , Beaumont S.K. , Kyriakou G. , Burton J.W. , Lambert R.M. (2009) Heterogeneously catalyzed asymmetric hydrogenation of C=C bonds directed by surface-tethered chiral modifiers. Journal of the American Chemical Society, 131, 14584–14589.

For a recent overview on the use of sulfoximines in asymmetric metal catalysis, see: Bolm C. , in Asymmetric Synthesis with Chemical and Biological Methods (Eds.: Enders D. , Jaeger K.-E. ), Wiley-VCH, Weinheim (Germany), 2007, pp. 149–176.

(a) Lu S-M , Bolm C. (2008) Highly chemo- and enantioselective hydrogenation of linear α,β-unsaturated ketones. Chemistry A European Journal, 14, 7513–7516; (b) Moessner C, Bolm C. (2005) Diphenylphosphanylsulfoximines as ligands in iridium-catalyzed asymmetric imine hydrogenations. Angewandte Chemie International Edition, 44, 7564–7567.

(a) Rageot D. , Woodmansee D.H. , Pugin B. , Pfaltz A. (2011) Proline-based P,O ligand/iridium complexes as highly selective catalysts: asymmetric hydrogenation of trisubstituted alkenes. Angewandte Chemie International Edition, 50, 9598–9601; (b) Rageot D, Pfaltz A. (2012) Chiral proline-based P,O and P,N ligands for iridium-catalyzed asymmetric hydrogenation. Helvetica Chimica Acta, 95, 2176–2193.

Verendel J.J. , Li J-Q , Quan X. , Peters B. , Zhou T. , Gautun O.R. , Go vender T. , Andersson P.G. (2012) Chiral hetero- and carbocyclic compounds from the asymmetric hydrogenation of cyclic alkenes. Chemistry a European Journal, 18, 6507–6513.

Yamamoto T. , Ogura M. , Kanisawa T. (2002) A novel synthetic method for (R)- and (S)-muscones by enantioselective hydrogenation of (E)- and (Z)-3-methyl-2-cyclopentadecen-1-ones catalyzed by p-tolyl-BINAP-Ru(II) complexes. Tetrahedron, 58, 9209–9212.

Wang D-S , Wang D-W , Zhou Y-G . (2011) Pd-catalyzed asymmetric hydrogenation of C=C bond of α,β-unsaturated ketones. Synlett, 947–950.

Geng H. , Huang K. , Sun T. , Li W. , Zhang X. , Zhou L. , Wu W. , Zhang X. (2011) Enantioselective synthesis of optically pure β-amino ketones and γ-aryl amines by Rh-catalyzed asymmetric hydrogenation. Journal of Organic Chemistry, 76, 332–334.

Huang K. , Zhang X. , Geng H. , Li S-K , Zhang X. (2012) Highly enantioselective hydrogenation of β-ketoenamides with the Rh-ZhangPhos catalyst. ACS Catalysis, 2, 1343–1345.

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Calvin J.R. , Frederick M.O. , Laird D.L.T. , Remacle J.R. , May S.A. (2012) Rhodium-catalyzed and Zinc(II)-triflate-promoted asymmetric hydrogenation of tetrasubstituted α,β-unsaturated ketones. Organic Letters, 14, 1038–1041.

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Recent review: Chao Zheng C. , You S-L . (2012) Transfer hydrogenation with Hantzsch esters and related organic hydride donors. Chemical Society Review, 41, 2498–2518.

Ouellet G.S. , Tuttle B.M. , MacMillan C.W.D. (2005) Enantioselective organocatalytic hydride reduction. Journal of the American Chemical Society, 127, 32–33.

Tang W.J. , Fonseca H.T.M. , Vignola N. , List B. (2005) Metal-free, organocatalytic asymmetric transfer hydrogenation of α,β-unsaturated aldehydes, Angewandte Chemie International Edition, 44, 108–110.

Tuttle J.B. , Ouellet S.G. , MacMillan D.W.C. (2006) Organocatalytic transfer hydrogenation of cyclic enones. Journal of the American Chemical Society, 128, 12662–12663.

Martin N.J.A. , List B. (2006) Highly enantioselective transfer hydrogenation of a,|3-unsaturated ketones. Journal of the American Chemical Society, 128, 13368–13369.