Free accessReview articleFirst published online 2018-4
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
Catalytic enantioselective hydrogenations of acyclic and cyclic α,β-unsaturated ketones and aldehydes are useful protocols for introduction of chiral centers at α- and/or β-positions of ketones especially in process scale reactions, which are reviewed in addition to conjugate and organocatalytic transfer reductions from the literatures since 2000.
For example, CanoR., ZakarianA., McGlackenG.P. (2017) Direct asymmetric alkylation of ketones: still unconquered. Angewandte Chemie, International Edition, 56, 9278–9290, and earlier references cited therein.
2.
For example, (a) WangC., GohC.M.T., XiaoS., YeW., TanC-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.
3.
For example, (a) SchmidT.E., Drissi-AmraouiS., CrévisyC., BasléO., MauduitM. (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.
4.
Some recent representative reviews in this area. (a) AgerD.J., de VriesA.H.M., de VriesJ.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.
5.
FogassyG., TunglerA., LévaiA., TóthG. (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.
6.
SzabadosE., GyörffyN., TunglerA., BallaJ., KönczöL. (2014) Asymmetric hydrogenation of prochiral and kinetic resolution of chiral cyclohexanone derivatives with Pd catalysts. Reaction Kinetics and Catalysis Letters, 111, 107–114.
7.
(a) ThoreyC., HeninF., MuzartJ. (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.
8.
FogassyG., TunglerA., LévaiA. (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.
9.
Some recent reviews on chiral ligands in asymmetric synthesis. (a) CarrollM.P., GuiryP.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.
10.
For example (a) LightfootA., SchniderP., PfaltzA. (1998) Enantioselective hydrogenation of olefins with iridium-phosphanodihydrooxazole catalystsAngewandte 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.
11.
LuS-M, BolmC. (2008) Highly enantioselective synthesis of optically active ketones by iridium-catalyzed asymmetric hydrogenation. Angewandte Chemie International Edition, 47, 8920–8923.
12.
LuW.-J., HenY.-W., HonX.-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.
13.
MaurerF., HuchV., UllrichA., KazmaierU. (2012) Development of catalysts for the stereoselective hydrogenation of α,β-unsaturated ketones. Journal of Organic Chemistry, 77, 5139–5143.
LiQ., WanP., HeY., ZhouY., LiL., ChenB., DuanK., CaoR., ZhouZ., QiuL. (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.
16.
LiuX., HanZ., WangZ., DingK. (2014) SpinPhox/Iridium(I)-catalyzed asymmetric hydrogenation of cyclic α-alkylidene carbonyl compounds. Angewandte Chemie International Edition, 53, 1978–1982.
17.
WangX., HanZ., WangZ., DingK. (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.
18.
OhtaT., MiyakeT., SeidoN., KumobayashiH., TakayaH. (1995) Asymmetric hydrogenation of olefins with aprotic oxygen functionalities catalyzed by BINAP-Ru(I1) complexes. Journal of Organic Chemistry, 60, 357–363.
19.
MargalefJ., CaldenteyX., KarlssonE.A., CollM., MazuelaJ., PàmiesO., DiéguezM., PericàsM.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.
20.
(a) SunT., HouG., MaM., ZhangX. (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.
21.
SunT., ZhangX. (2012) A simple synthetic route to enantiopure α-hydroxy ketone derivatives by asymmetric hydrogenation. Advanced Synthesis & Catalysis, 354, 3211–3215.
22.
(a) TunglerA., KajtarM., MatheT., TothG., FogassyE., PetroJ. (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.
23.
McIntoshA.I., WatsonD.J., BurtonJ.W., LambertR.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.
24.
GyörffyN., TunglerA., FodorM. (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.
25.
TunglerA., NittaY., FodorK., FarkasG., MatheT. (1999) Comparison of chiral modifiers in the Pd catalysed hydrogenation of phenylcinnamic acid and isophorone. Journal of Molecular Catalysis A: Chemistry, 149, 135–140.
26.
(a) Le MauxP., MassonneauV., SimommeauxG. (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.
27.
WatsonD.J., JesudasonRjbrj, BeaumontS.K., KyriakouG., BurtonJ.W., LambertR.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.
28.
For a recent overview on the use of sulfoximines in asymmetric metal catalysis, see: BolmC., in Asymmetric Synthesis with Chemical and Biological Methods (Eds.: EndersD., JaegerK.-E.), Wiley-VCH, Weinheim (Germany), 2007, pp. 149–176.
29.
(a) LuS-M, BolmC. (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.
30.
(a) RageotD., WoodmanseeD.H., PuginB., PfaltzA. (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.
31.
VerendelJ.J., LiJ-Q, QuanX., PetersB., ZhouT., GautunO.R., Go venderT., AnderssonP.G. (2012) Chiral hetero- and carbocyclic compounds from the asymmetric hydrogenation of cyclic alkenes. Chemistry a European Journal, 18, 6507–6513.
32.
YamamotoT., OguraM., KanisawaT. (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.
33.
WangD-S, WangD-W, ZhouY-G. (2011) Pd-catalyzed asymmetric hydrogenation of C=C bond of α,β-unsaturated ketones. Synlett, 947–950.
34.
GengH., HuangK., SunT., LiW., ZhangX., ZhouL., WuW., ZhangX. (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.
35.
HuangK., ZhangX., GengH., LiS-K, ZhangX. (2012) Highly enantioselective hydrogenation of β-ketoenamides with the Rh-ZhangPhos catalyst. ACS Catalysis, 2, 1343–1345.
36.
(a) MassonneauV., Le MauxP., SimonneauxG. (1986) Catalytic asymmetric hydrogenation of α,β-unsaturated ketones using chiral ruthenium complexes. Tetrahedron Letters, 27, 5497–5498; (b) Massonneau V, Le Maux P, Simommeaux G. (1987) Catalytic asymmetric syntheses II. Hydrogenation of a,|3-unsaturated ketones using chiral ruthenium complexes. Journal of Organometallic Chemistry, 327, 269–273.
37.
FehrM.J., ConsiglioG., ScaloneM., SchmidR. (1999) Asymmetric hydrogenation of substituted 2-pyrones. Journal of Organic Chemistry, 64, 5768–5776.
38.
ScheuermannCJ, néeTaylor, JaekelC. (2008) Enantioselective hydrogenation of enones with a hydroformylation catalyst. Advanced Synthesis & Catalysis, 350, 2708–2714.
39.
(a) OhshimaT., TadaokaH., HoriK., SayoN., MashimaK. (2008) Highly enantio- and s-trans C=C bond selective catalytic hydrogenation of cyclic enones: alternative synthesis of (-)-menthol. Chemistry A European Journal, 14, 2060–2066; (b) Solodar J. (1978) Asymmetric and regioselective hydrogenation of piperitenone by homogeneous rhodium complexes. Journal of Organic Chemistry, 43, 1787–1789.
40.
ShimizuH., NaganoT., SayoN., SaitoT., OhshimaT., MashimaK. (2009) Asymmetric hydrogenation of heteroaromatic ketones and cyclic and acyclic enones mediated by Cu(I)-chiral diphosphine catalysts. Synlett, 3143–3146.
41.
DobbsD.A., VanhesscheK.P.M., BraziE., RautenstrauchV., LenoirJ-Y, GenetJ-P, WilesJ., BergensS.H. (2000) Industrial synthesis of (+)-cis-methyl dihydrojasmonate by enantioselective catalytic hydrogenation: Identification of the precatalyst [Ru((-)-Me-DuPHOS)(H)-(r|6–1,3,5- cyclooctatriene)](BF4). Angewandte Chemie International Edition, 39, 1992–1995.
42.
CalvinJ.R., FrederickM.O., LairdD.L.T., RemacleJ.R., MayS.A. (2012) Rhodium-catalyzed and Zinc(II)-triflate-promoted asymmetric hydrogenation of tetrasubstituted α,β-unsaturated ketones. Organic Letters, 14, 1038–1041.
43.
MoritaniY., AppellaD.H., ValdasV., BuchwaldS.L. (2000) Synthesis of α-alkyl cyclopentanones in high enantiomeric excess via copper-catalyzed asymmetric conjugate reduction. Journal of the American Chemical Society, 122, 6797–6798.
44.
LipshutzB.H., ServeskoM.J. (2003) CuH-catalyzed asymmetric conjugate reductions of acyclic enones. Angewandte Chemie International Edition, 42, 4789–4792.
45.
LipshutzB.H., ServeskoJ.M., PetersenT.B., PapaP.P., LoverA.A. (2004) Asymmetric 1,4-reductions of hindered α-substituted cycloalkenones using catalytic SEGPHOS-Ligated CuH. Organic Letters, 6, 1273–1275.
(a) KanazawaY., TsuchiyaY., KobayashiK., ShiomiT., ItohJ-I, KikuchiM., YamamotoY., NishiyamaH. (2005) Asymmetric conjugate reduction of α,β-unsaturated ketones and esters with chiral rhodium(2,6-bisoxazolinylphenyl) catalysts. Chemistry a European Journal, 63–71; (b) Nishiyama H, Ito J-i, Shiomi T, Hashimoto T, Miyakawa T, Kitase M. (2008) Chiral phenyl-bis(oxazoline) as an efficient auxiliary for asymmetric catalysis. Pure and Applied Chemistry, 80, 743–749.
48.
(a) TsuchiyaY., HamashimaY., SodeokaM. (2006) A new entry to Pd-H chemistry: catalytic asymmetric conjugate reduction of enones with EtOH and a highly enantioselective synthesis of Warfarin. Organic Letters, 8, 4851–4854; (b) Fujii A, Hagiwara E, Sodeoka M. (1999) Mechanism of palladium complex-catalyzed enantioselective Mannich-type reaction: Characterization of a novel binuclear palladium enolate complex. Journal of the American Chemical Society, 121, 5450–5458.
49.
MonguchiD., BeemelmannsC., HashizumeD., HamashimaY., SodeokaM. (2008) Catalytic asymmetric conjugate reduction with ethanol: A more reactive system Pd(II)-iPr-DUPHOS complex with molecular sieves 4A. Journal of Organometallic Chemistry, 693, 867–873.
50.
BrunnerH., LeitnerW. (1990) Rhodium katalysierte enantioselektive Transferhydrierung von C=C-Doppelbindungen mit dem System HCO2H/NEt3 Wasserstoffquelle. Journal of Organometallic Chemisiry, 387, 209–217.
51.
Recent review: Chao ZhengC., YouS-L. (2012) Transfer hydrogenation with Hantzsch esters and related organic hydride donors. Chemical Society Review, 41, 2498–2518.
52.
OuelletG.S., TuttleB.M., MacMillanC.W.D. (2005) Enantioselective organocatalytic hydride reduction. Journal of the American Chemical Society, 127, 32–33.
53.
TangW.J., FonsecaH.T.M., VignolaN., ListB. (2005) Metal-free, organocatalytic asymmetric transfer hydrogenation of α,β-unsaturated aldehydes, Angewandte Chemie International Edition, 44, 108–110.
54.
TuttleJ.B., OuelletS.G., MacMillanD.W.C. (2006) Organocatalytic transfer hydrogenation of cyclic enones. Journal of the American Chemical Society, 128, 12662–12663.
55.
MartinN.J.A., ListB. (2006) Highly enantioselective transfer hydrogenation of a,|3-unsaturated ketones. Journal of the American Chemical Society, 128, 13368–13369.